Sample records for degassed cation conductivity

  1. Degassed conductivity - comments on an interesting and reasonable plant cycle chemistry monitoring technique. Part 1. Degassing of low-molecular-weight organic acis in technical degassed cation conductivity monitors

    Energy Technology Data Exchange (ETDEWEB)

    Gruszkiewicz, M. [Oak Ridge National Lab., Oak Ridge, TN (United States). Chemical Sciences Div.; Bursik, A. [PowerPlant Chemistry GmbH, Neulussheim (Germany)


    Degassed cation conductivity monitoring is not as common as specific and cation conductivity monitoring even though this technique offers some very interesting features. This technique can help to distinguish between plant cycle contamination with inorganic and/or organic acids and/or their salts and that caused by carbon dioxide. This may be important, e.g., during startup of a unit. Two issues are often discussed in connection with degassed conductivity monitoring: the behavior of formic and acetic acid during degassing and the correct conversion of values measured at nearly 100 C to standard temperature (25 C). This first part of a two-part publication focuses on the first issue. A rigorous thermodynamic approach was chosen for the evaluation of conditions in the degassing part of the monitoring system. The results of calculations clearly show that the actual loss of formic and acetic acid in a technical atmospheric degassing system via system vents is so low that it can be disregarded. In contrast, the concentration of formic and acetic acid in the sample exiting the technical atmospheric degassing system is somewhat higher than that in the original sample. The actual increase in concentration is based on the volatility behavior of both acids and depends additionally on the evaporation rate of the system. (orig.)

  2. Measurement of degassed cation conductivity from the point of view of an independent consultant

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    Heijboer, Rob; Butter, Leo; Deelen, Marga van; Vos, Frank de [Process and Cooling Water Group, KEMA Nederland B.V., Arnhem (Netherlands)


    It is a known and widely accepted fact that Cation Conductivity (CC) is one of the key parameters to monitor the quality of the water/steam cycle. However, the presence of CO{sub 2} in the cycle also contributes to the CC value but on the other hand is not such a threat to the integrity of the cycle and is more a nuisance. Kema, as an independent consultant, investigated reasons for CO{sub 2} ingress. The results demonstrate the reliable CO{sub 2} surveillance will considerably contribute to optimisation of the water-steam cycle. (orig.)

  3. Modified cation conductivity[Monitoring water/steam chemistry]; Modifierad sur konduktivitet

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    Staalenheim, Annika [Vattenfall Utveckling AB, Aelvkarleby (Sweden)


    A commercially available instrument for monitoring of cation conductivity after removal of carbon dioxide (CO{sub 2}) has been investigated. The sample is first treated in an acid cation exchanger. The carbon dioxide is removed in a degasser consisting of a heater and a column and the sample is cooled to ambient temperature. The cation conductivity is measured before as well as after degassing and cooling, so called 'degassed' cation conductivity. The cause of the interest for monitoring degassed cation conductivity is that the high content of CO{sub 2} in certain plants makes it difficult to use conventional cation conductivity to estimate if the level of more aggressive impurities like chloride and sulphate is acceptable. A high content of CO{sub 2} provides a high background level, overshadowing the contribution from the more aggressive compounds. There are alternative methods designed to provide information regarding the content of aggressive anions, usually based on analysis of the composition of the sample, like ion chromatography. These alternative methods are, however, often too expensive and/or too labour intensive to be used in smaller plants. Methods by which the influence of CO{sub 2} on the cation conductivity can be separated from the corresponding influence of more aggressive impurities are therefore of interest. Such alternative methods are usually based on removal of CO{sub 2}. The most common method involves heating as described in ASTM D4519-94. The method investigated follows this ASTM standard, except for the fact that the sample is cooled before the final conductivity measurement. The removal of CO{sub 2} is not the only critical factor. Another is that aggressive impurities like chloride and sulphate must not be removed. The effect on organic acids may also be of interest. Tests have been performed to determine the influence of the flow and temperature as well as of the influence of addition of varying levels and combinations of

  4. Cation Defects and Conductivity in Transparent Oxides

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    Exarhos, Gregory J.; Windisch, Charles F.; Ferris, Kim F.; Owings, Robert R.


    High quality doped zinc oxide and mixed transition metal spinel oxide films have been deposited by means of sputter deposition from metal and metal oxide targets, and by spin casting from aqueous or alcoholic precursor solutions. Deposition conditions and post-deposition processing are found to alter cation oxidation states and their distributions in both oxide materials resulting in marked changes to both optical transmission and electrical response. For ZnO, partial reduction of the neat or doped material by hydrogen treatment of the heated film or by electrochemical processing renders the oxide n-type conducting. Continued reduction was found to diminish conductivity. In contrast, oxidation of the infrared transparent p-type spinel conductors typified by NiCo2O4 was found to increase conductivity. The disparate behavior of these two materials is caused in part by the sign of the charge carrier and by the existence of two different charge transport mechanisms that are identified as free carrier conduction and polaron hopping. While much work has been reported concerning structure/property relationships in the free carrier conducting oxides, there is a significantly smaller body of information on transparent polaron conductors. In this paper, we identify key parameters that promote conductivity in mixed metal spinel oxides and compare their behavior with that of the free carrier TCO’s.

  5. Anion and Cation Ionic Conductivity of Dragon Fruit (United States)

    Hajar, Nadya; Asiah, M. N.; Abdullah, S.; Rusop, M.


    The separation of all ions in a synthetic solution was achieved with an anion eluent containing 0.3392 g Na2CO3 and 0.084 g NaHCO2 and the run around 20 min. Cation eluent containing 0.60 g Tartaric acid and 0.125 g Dipicolinic acid and the run around 16 min. This method was applied to dragon fruit juice with success and has shown sensitivity. Moreover, sample preparation was a simple 1:1, 1:10, 1:100 and 1:1000 ppm with 0.20 mm filtration and direct injection without prior sample clean-up. Due to the use of eluent generator, very low conductance background conductivity can be obtained and sensitivity of dragon fruit has been greatly improved. Under the experimental condition, several inorganic anions, such as F-, NO3-, NO2-, Br- and PO43- obtained from dragon fruit. For cation, inorganic ions that occurred during the experiment were NH3+, Ca+, and Mg+. Conductivity for anion of F-, NO3-, NO2-, Br- and PO43- were approximately 20, 17, 16, 16 and 20 μS/cm, respectively. Concentration for F- is 1.57 mg/l, NO3- is 1.92 mg/l, NO2- is 0.30 mg/l, Br- is 0.45 mg/l and PO43- is 4.45 mg/l. Conductivity for cation of NH3+, Ca+, and Mg+ were approximately 537, 538 and 531 μS/cm, respectively. Concentration for cation of NH3+ is 0.93 mg/l, Ca+ is 1.15 mg/l, and Mg+ 7.285 is mg/l. The method has successfully applied to the determination of inorganic ions in dragon fruit. An ion chromatography method is described for the simultaneous determination of ionic conductivity for dragon fruit juice using a selected anion and cation eluent. The detection of ionic conductivity in dragon fruit juice has been studied.

  6. Increased cation conductance in human erythrocytes artificially aged by glycation. (United States)

    Kucherenko, Yuliya V; Bhavsar, Shefalee K; Grischenko, Valentin I; Fischer, Uwe R; Huber, Stephan M; Lang, Florian


    Excessive glucose concentrations foster glycation and thus premature aging of erythrocytes. The present study explored whether glycation-induced erythrocyte aging is paralleled by features of suicidal erythrocyte death or eryptosis, which is characterized by cell membrane scrambling with subsequent phosphatidylserine exposure at the cell surface and cell shrinkage. Both are triggered by increases of cytosolic Ca(2+) concentration ([Ca(2+)](i)), which may result from activation of Ca(2+) permeable cation channels. Glycation was accomplished by exposure to high glucose concentrations (40 and 100 mM), phosphatidylserine exposure estimated from annexin binding, cell shrinkage from decrease of forward scatter, and [Ca(2+)](i) from Fluo3-fluorescence in analysis via fluorescence-activated cell sorter. Cation channel activity was determined by means of whole-cell patch clamp. Glycation of total membrane proteins, immunoprecipitated TRPC3/6/7, and immunoprecipitated L-type Ca(2+) channel proteins was estimated by Western blot testing with polyclonal antibodies used against advanced glycation end products. A 30-48-h exposure of the cells to 40 or 100 mM glucose in Ringer solution (at 37 degrees C) significantly increased glycation of membrane proteins, hemoglobin (HbA(1c)), TRPC3/6/7, and L-type Ca(2+) channel proteins, enhanced amiloride-sensitive, voltage-independent cation conductance, [Ca(2+)](i), and phosphatidylserine exposure, and led to significant cell shrinkage. Ca(2+) removal and addition of Ca(2+) chelator EGTA prevented the glycation-induced phosphatidylserine exposure and cell shrinkage after glycation. Glycation-induced erythrocyte aging leads to eryptosis, an effect requiring Ca(2+) entry from extracellular space.

  7. Structure-conductivity studies in polymer electrolytes containing multivalent cations

    CERN Document Server

    Aziz, M


    force microscopy (AFM). DSC evidences helped to explain the texture of the iron samples during the drying process, and showed transitions between low melting, PEO and high melting spherulites, and VTPM is able to visualise the spherulites present in the samples. AFM has successfully imaged the as cast PEO sub 8 :FeBr sub 2 sample and the surface effect causing extra resistance in the impedance spectra could be seen. Conductivity studies were carried out using a.c. impedance spectra. Fe(ll) samples exhibit the typical semicircle-spike plot but the Fe(lll) samples displayed an extra semicircle before the spike reflecting a surface effect. This is also manifested in the Arrhenius plots of the same samples where a dip was shown at 100 deg C. From the conductivity studies on the iron systems it was found that for the dry samples the optimum conductivity was observed in PEO sub 8 :FeBr sub x irrespective of the valence state of the cation. For the air-cast samples the optimum conductivity composition depends on the...

  8. Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement (United States)

    Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.


    We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation-glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids.

  9. Chemical mechanical polishing of transparent conductive layers using spherical cationic polymer microbeads

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    Nagaoka, Shoji, E-mail: [Kumamoto Industrial Research Institute, 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Chuouku, Kumamoto 860-8555 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Ryu, Naoya [Kumamoto Industrial Research Institute, 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Yamanouchi, Akio [Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Chuouku, Kumamoto 860-8555 (Japan); Shirosaki, Tomohiro [Kumamoto Industrial Research Institute, 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Horikawa, Maki [Kumamoto Industrial Research Institute, 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Chuouku, Kumamoto 860-8555 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan); Sakurai, Hideo; Takafuji, Makoto; Ihara, Hirotaka [Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Chuouku, Kumamoto 860-8555 (Japan); Kumamoto Institute for Photo-Electro Organics (Phoenics), 3-11-38 Higashimachi, Higashiku, Kumamoto 862-0901 (Japan)


    Spherical cationic polymer microbeads were used to chemically mechanically polish transparent conductive oxide (TCO) layers without the need for inorganic abrasives. Poly(methyl acrylate) (PMA) was used as the polymer matrix. Surface cationization of the spherical PMA microbeads was achieved by aminolysis using 1,2-diaminoethane. The amino group content of the microbeads was controlled using the aminolysis reaction time. The surface roughness of the TCO polished using the cationic polymer microbeads was similar to that of TCO polished with an inorganic abrasive. The microbead-polished TCO layer was slightly thinner than the unpolished TCO layer. The sheet resistance of the TCO layer polished using the microbeads was lower than that polished using the inorganic abrasive. The TCO polishing ability of the microbeads was dependent on their cationic properties and softness. - Highlights: • Indium tin oxide (ITO) layer was planarized using cationic polymer microbeads. • Cationic polymer microbeads planarized, while retaining ITO layer thickness • Cationic polymer microbeads did not degrade the sheet resistance of ITO. • Cationic polymer microbeads could planarize the ITO surface without damaging.

  10. Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement (United States)

    Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.


    We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

  11. Electrochemical ion exchanger in the water circuit to measure cation conductivity

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    Bengtsson, Bernt; Ingemarsson, Rolf; Settervik, Gustav [Ringhals AB, Vaeroebacka (Sweden); Velin, Anna [Vattenfall Research and Development AB, Stockholm (Sweden)


    At Ringhals Nuclear Power Plant (NPP), more than four years of successful operation with a full-scale electrode ionization (EDI) unit for the recycling of steam generator blowdown gave the inspiration to modify and scale down this EDI process. As part of this project, the possibility of replacing the cation exchanger columns used for cation conductivity analysis with some small and integrated electrochemical ion exchange cells was explored. Monitoring the cation conductivity requires the use of a small cation resin column upstream of the conductivity probe and is one of the most important analyses at power plants. However, when operating with high alkaline treatment in the steam circuit, there is the disadvantage of rapid exhaustion of the resins, necessitating frequent replacement or regeneration. This causes interruptions in the monitoring and gives rise to a high workload for the maintenance staff. This paper reports on the optimization and testing of two different two-compartment electrochemical cells for possible replacement of the cation resin columns for analyzing cation conductivity in the secondary steam circuit at Ringhals NPP. Field tests during start-up conditions and more than four months of steady operation together with real and simulated tests for impurity influences indicate that an electrical ion exchange (ELIX) process could be successfully used to replace the resin columns in Ringhals while operating with high-pH all-volatile treatment (AVT) using hydrazine and ammonia. Installation of an ELIX system downstream of a particle filter and upstream of a small cation resin column will introduce additional safety and further reduce the maintenance and possible interruptions. Performance of the ELIX process together with other chemical additives (morpholine, ethanolamine, 3-methoxypropylamine, dimethylamine) and dispersants may be further evaluated to qualify the ELIX process as well as steam generator blowdown electrodeionization for wider use in

  12. Ionic liquids based on dicyanamide anion: influence of structural variations in cationic structures on ionic conductivity. (United States)

    Yoshida, Yukihiro; Baba, Osamu; Saito, Gunzi


    A series of dicyanamide [N(CN)2]-based ionic liquids were prepared using 1-alkyl-3-methylimidazolium cations with different alkyl chain lengths and ethyl-containing heterocyclic cations with different ring structures, and the influence of such structural variations on their thermal property, density, electrochemical window, viscosity, ionic conductivity, and solvatochromic effects was investigated. We found that the 1,3-dimethylimidazolium salt shows the highest ionic conductivity among ionic liquids free from halogenated anions (3.6 x 10(-2) S cm(-1) at 25 degrees C), and the elongation of the alkyl chain causes the pronounced depression of fluidity and ionic conductivity. Also, such an elongation gives rise to the increase in the degree of ion association in the liquids, mainly caused by the van der Waals interactions between alkyl chains. N(CN)2 salts with 1-ethyl-2-methylpyrazolium (EMP) and N-ethyl-N-methylpyrrolidinium (PY(12)) cations as well as 1-ethyl-3-methylimidazolium (EMI) cation are liquids at room temperature (RT), while the N-ethylthiazolium salt shows a melting event at higher temperature (57 degrees C). Among the three RT ionic liquids with ethyl-containing cations, RT ionic conductivity follows the order EMI > PY(12) > EMP, which does not coincide with the order of fluidity at RT (EMI > EMP > PY(12)). Such a discrepancy is originated from a high degree of ion dissociation in the PY(12) salt, which was manifested in the Walden rule deviation and solvatochromic effects. A series of N(CN)2/C(CN)3 binary mixtures of the EMI salts were also prepared. RT ionic conductivity decreases linearly with increasing the molar fraction of C(CN)3 anion.

  13. Influence of the type of exchangeable cation on the electrolytic conductivity of bentonite suspensions

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    Daković Aleksandra S.


    Full Text Available The electrolytic conductivity of bentonite aqueous suspensions was investigated. The starting material (Ca-Mont was exchanged with sodium ions, using an ion exchange column. The sodium form of bentonite (Na-Mont was used to obtain organobentonites. The electrolytic conductivity of the starting material, Na-Mont and organobentonites was studied for different suspension concentration. The highest value of the electrolytic conductivity was obtained for Na-Mont, while the organic cation in the bentonite structure decreased the electrolytic conductivity.

  14. Electromembrane extraction of heavy metal cations followed by capillary electrophoresis with capacitively coupled contactless conductivity detection. (United States)

    Kubáň, Pavel; Strieglerová, Lenka; Gebauer, Petr; Boček, Petr


    Electromembrane extraction (EME) was used as an off-line sample pre-treatment method for the determination of heavy metal cations in aqueous samples using CE with capacitively coupled contactless conductivity detection (CE-C(4) D). A short segment of porous polypropylene hollow fibre was penetrated with 1-octanol and 0.5% v/v bis(2-ethylhexyl)phosphonic acid and constituted a low cost, single use, disposable supported liquid membrane, which selectively transported and pre-concentrated heavy metal cations into the fibre lumen filled with 100 mM acetic acid acceptor solution. Donor solutions were standard solutions and real samples dissolved in deionized water at neutral pH. At optimized EME conditions (penetration time, 5 s; applied voltage, 75 V; and stirring rate, 750 rpm), 15-42% recoveries of heavy metal cations were achieved for a 5 min extraction time. Repeatability of the EME pre-treatment was examined for six independent EME runs and ranged from 6.6 to 11.1%. Limits of detection for the EME-CE-C(4) D method ranged from 25 to 200 nM, resulting into one to two orders of magnitude improvement compared with CE-C(4) D without sample treatment. The developed EME sample pre-treatment procedure was applied to the analysis of heavy metal cations in tap water and powdered milk samples. Zinc in the real samples was identified and quantified in a background electrolyte solution consisting of 20 mM L-histidine and 30 mM acetic acid at pH 4.95 in about 3 min.

  15. Ionic charge transport between blockages: Sodium cation conduction in freshly excised bulk brain tissue

    Energy Technology Data Exchange (ETDEWEB)

    Emin, David, E-mail: [Department of Physics and Astronomy, University of New Mexico, Albuquerque, NM 87131 (United States); Akhtari, Massoud [Semple Institutes for Neuroscience and Human Behavior, David Geffen School of Medicine, University of California at Los Angeles, Los Angeles, CA 90095 (United States); Ellingson, B. M. [Department of Radiology, David Geffen School of Medicine, University of California at Los Angeles, Los Angeles, CA 90095 (United States); Mathern, G. W. [Department of Neurosurgery, David Geffen School of Medicine, University of California at Los Angeles, Los Angeles, CA 90095 (United States)


    We analyze the transient-dc and frequency-dependent electrical conductivities between blocking electrodes. We extend this analysis to measurements of ions’ transport in freshly excised bulk samples of human brain tissue whose complex cellular structure produces blockages. The associated ionic charge-carrier density and diffusivity are consistent with local values for sodium cations determined non-invasively in brain tissue by MRI (NMR) and diffusion-MRI (spin-echo NMR). The characteristic separation between blockages, about 450 microns, is very much shorter than that found for sodium-doped gel proxies for brain tissue, >1 cm.

  16. DFT studies of all fluorothiophenes and their cations as candidate monomers for conductive polymers

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    Shirani, Hossein, E-mail: [Young Researchers Club, Islamic Azad University, Toyserkan Branch, Toyserkan (Iran, Islamic Republic of); Jameh-Bozorghi, Saeed [Department of Chemistry, Islamic Azad University, Arak Branch, Arak (Iran, Islamic Republic of); Yousefi, Ali [Department of Computer Engineering, Islamic Azad University, Hamedan Branch, Hamedan (Iran, Islamic Republic of)


    In this paper, electronic, structural, and properties of mono-, di-, tri-, and tetrafluorothiophenes and their radical cations are studied using the density functional theory and B3LYP method with 6-311++G** basis set. Also, the effects of the number and position of the substituent of fluorine atoms on the properties of the thiophene ring have been studied using optimized structures obtained for these molecules and their radical cations; vibrational frequencies, spin-density distribution, size and direction of the dipole moment vector, ionization potential, electric Polarizabilities, HOMO–LUMO gaps and NICS values of these compounds have been calculated and analyzed.

  17. A Novel Method for the Determination of Membrane Hydration Numbers of Cations in Conducting Polymers

    DEFF Research Database (Denmark)

    Jafeen, M.J.M.; Careem, M.A.; Skaarup, Steen


    . Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance technique was used to determine the amount of charge inserted and the total mass change during the reduction process in a polypyrrole film. From these values, the number of water molecules accompanying each cation was evaluated...

  18. Cation composition effects on oxide conductivity in the Zr_2Y_2O_7-Y_3NbO_7 system

    CERN Document Server

    Marrocchelli, Dario; Norberg, Stefan T; Hull, Stephen


    Realistic, first-principles-based interatomic potentials have been used in molecular dynamics simulations to study the effect of cation composition on the ionic conductivity in the Zr2Y2O7-Y3NbO7 system and to link the dynamical properties to the degree of lattice disorder. Across the composition range, this system retains a disordered fluorite crystal structure and the vacancy concentration is constant. The observed trends of decreasing conductivity and increasing disorder with increasing Nb5+ content were reproduced in simulations with the cations randomly assigned to positions on the cation sublattice. The trends were traced to the influences of the cation charges and relative sizes and their effect on vacancy ordering by carrying out additional calculations in which, for example, the charges of the cations were equalised. The simulations did not, however, reproduce all the observed properties, particularly for Y3NbO7. Its conductivity was significantly overestimated and prominent diffuse scattering featur...

  19. Cation and anion sizes influence in the temperature dependence of the electrical conductivity in nine imidazolium based ionic liquids

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    Vila, J.; Cabeza, O. [Dpto. de Fisica, Fac. de Ciencias, Universidade da Coruna, Campus da Zapateira s/n, 15072 A Coruna (Spain); Varela, L.M. [Dpto. de Fisica, Fac. de Ciencias, Universidade da Coruna, Campus da Zapateira s/n, 15072 A Coruna (Spain); Dpto. de Fisica de la Materia Condensada, Fac. de Fisica, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela (Spain)


    In this paper we present experimental data on the temperature dependence of the electrical conductivity, {sigma}, in nine different imidazolium based ionic liquids. We have measured four 1-(alkyl chain)-3-methyl imidazolium tetrafluoroborate (C{sub n}MIM-BF{sub 4}) ionic liquids, with C{sub n} representing ethyl, butyl, hexyl and octyl chains, to study the dependence of {sigma} with the cation length. Moreover, to study the influence of the anion size in the electrical conductivity, we measured six different EMIM-X, with X being, from smaller to bigger sizes, Cl{sup -}, Br{sup -}, BF{sub 4}{sup -}, PF{sub 6}{sup -}, ethyl sulfate and tosylate. The measurements were performed at atmospheric pressure, and the studied temperature range covers the liquid phase of the analyzed compounds. We have fitted the electrical conductivity data of the nine ionic liquids using a Vogel-Tamman-Fulcher (VTF) equation with high precision. We observe from the measured data that the electrical conductivity decreases its value as the alkyl chain of the cation increases. In contrast, we do not observe that dependence with the anion size, where there seems to be an optimal size (that of BF{sub 4}{sup -}) for which {sigma} reaches its maximum value, being lower for smaller or bigger anion sizes. Finally, if we plot the natural logarithm of {sigma} versus the distance in temperature to the glass transition one for each IL, we observe that the resulting straight lines are ordered with the anion (or cation) sizes for all nine compounds measured, i.e., lower {sigma} values for bigger sizes. (author)

  20. Research for preparation of cation-conducting solids by high-pressure synthesis and other methods (United States)

    Goodenough, J. B.; Hong, H. Y. P.; Kafalas, J. A.; Dwight, K., Jr.


    It was shown that two body-centered-cubic skeleton structures, the Im3 KSbO3 phase and the defect-pyrochlore phase A(+)B2X6, do exhibit fast Na(+)-ion transport. The placement of anions at the tunnel intersection sites does not impede Na(+)-ion transport in (NaSb)3)(1/6 NaF), and may not in (Na(1+2x)Ta2 5F)(Ox). The activation energies are higher than those found in beta-alumina. There are two possible explanations for the higher activation energy: breathing of the bottleneck (site face or edge) through which the A(+) ions must pass on jumping from one site to another may be easier in a layer structure and/or A(+)-O bonding may be stronger in the cubic structures because the O(2-) ion bonds with two (instead of three) cations of the skeleton. If the former explanation is dominant, a lower activation energy may be achieved by optimizing the lattice parameter. If the latter is dominant, a new structural principle may have to be explored.

  1. Integrating high electrical conductivity and photocatalytic activity in cotton fabric by cationizing for enriched coating of negatively charged graphene oxide. (United States)

    Sahito, Iftikhar Ali; Sun, Kyung Chul; Arbab, Alvira Ayoub; Qadir, Muhammad Bilal; Jeong, Sung Hoon


    Electroconductive textiles have attended tremendous focus recently and researchers are making efforts to increase conductivity of e-textiles, in order to increase the use of such flexible and low cost textile materials. In this study, surface conductivity and photo catalytic activity of standard cotton fabric (SCF) was enhanced by modifying its surface charge, from negative to positive, using Bovine Serum Albumin (BSA) as a cationic agent, to convert it into cationised cotton fabric (CCF). Then, both types of fabrics were dip coated with a simple dip and dry technique for the adsorption of negatively charged graphene oxide (GO) sheets onto its surface. This resulted in 67.74% higher loading amount of GO on the CCF making self-assembly. Finally, this coating was chemically converted by vapor reduction using hydrazine hydrate to reduced graphene oxide (rGO) for restoration of a high electrical conductivity at the fabric surface. Our results revealed that with such high loading of GO, the surface resistance of CCF was only 40Ω/sq as compared to 510Ω/sq of the SCF and a 66% higher photo catalytic activity was also achieved through cationization for improved GO coating. Graphene coated SCF and CCF were characterized using FE-SEM, FTIR, Raman, UV-vis, WAXD, EDX and XPS spectroscopy to ascertain successful reduction of GO to rGO. The effect of BSA treatment on adsorption of cotton fabric was studied using drop shape analyzer to measure contact angle and for thermal and mechanical resistance, the fabric was tested for TGA and tensile strength, respectively. rGO coated fabric also showed slightly improved thermal stability yet a minor loss of strength was observed. The high flexibility, photocatalytic activity and excellent conductivity of this fabric suggests that it can be used as an electrode material for various applications.


    Energy Technology Data Exchange (ETDEWEB)

    Xu, Hanbing [University of Tennessee, Knoxville (UTK); Meek, Thomas T. [University of Tennessee, Knoxville (UTK); Han, Qingyou [ORNL


    In order to investigate the effects of ultrasonic vibration on degassing of aluminum alloys, three experimental systems have been designed and built: one for ultrasonic degassing in open air, one for ultrasonic degassing under reduced pressure, and one for ultrasonic degassing with a purging gas. Experiments were first carried out in air to test degassing using ultrasonic vibration alone. The limitations with ultrasonic degassing were outlined. Further experiments were then performed under reduced pressures and in combination with purging argon gas. Experimental results suggest that ultrasonic vibration alone is efficient for degassing a small volume of melt. Ultrasonic vibration can be used for assisting vacuum degassing, making vacuum degassing much faster than that without using ultrasonic vibration. Ultrasonically assisted argon degassing is the fastest method for degassing among the three methods tested in this research. More importantly, dross formation during ultrasonically assisted argon degassing is much less than that during argon degassing. The mechanisms of ultrasonic degassing are discussed.

  3. An evaluation of soluble cations and anions on the conductivity and rate of flocculation of kaolins (United States)

    Fulton, Deborah Lee


    The focus of this project was to learn how ionic concentrations and their contributions to electric conductivity influence the flocculation behavior of kaolin/water suspensions. Sodium silicate, calcium chloride, and magnesium sulfate were used as chemical additives. The specific surface areas, particle size distributions, and methylene blue indices for two kaolins were measured. The SSA and MBI for these kaolins indicated that they possessed inherent differences in SSA and flocculation behaviors. Rheological studies were also performed. Testing included simultaneous gelation, deflocculation, and pH tests. Viscosity, pH, temperature, and chemical additive concentrations were monitored at each point. Testing was performed at 45/55 wt% solids. Effects of additions of various levels of deflocculant and flocculant to each of the kaolin/water suspensions were studied by making several suspensions from each kaolin. The concentrations of dispersant, and flocculant levels and types were varied to produce suspensions with different chemical additive "histories," but all with similar final apparent viscosities. Slurry filtrates were analyzed for conductivity, pH, temperature, and ion concentrations of (Al3+, Fe2+,3+, Ca 2+, Mg+, Na+, SO4 2--, and Cl--). Plastic properties were calculated to determine how variations in suspension histories affected conductivities, pH, and detectable ion contents of the suspensions. These analyses were performed on starting slurries which were under-, completely-, and over-deflocculated before further additions of flocculants and deflocculant were added to tune the slurries to the final, constant, target viscosity. Results showed that rates of flocculation and conductivities increased as concentrations of ions increased. By increasing conductivity correlations with increases in flocculation occurs, which yields higher rates of buildup, or RBU [1]. This is the single most important slip control property in the whitewares industry. Shear

  4. Impact degassing of water and noble gases from silicates (United States)

    Azuma, S.; Hiyagon, H.; Iijima, Y.; Syono, Y.


    Previous shock experiments by Ahrens and his colleagues show that degassing of H2O and CO2 occurs at 8-65GPa from hydrous minerals such as serpentine. In early solar system, the impact degassing would have played an important part in the formation of primary-atmospheres of the terrestrial planets. However, degassing conditions of noble gases are not well-known because there are few experiments for them. We conducted some shock recovery experiments to investigate the degassing condition and to understand the degassing mechanisms of water and noble gases. We used natural richterites (Ri), amphibolites (Am), serpentines (Sep) and orthoclases (or) as target samples. These, except Sep, contain radiogenic noble gases such as (40)Ar. The samples were put in stainless steel containers, and were show by a rail gun at ISAS or single-stage powder guns at Nagoya or Tohoku University, Japan. We used two kinds of containers: 'open' type containers having a ventilating path for released volatiles for most of samples and 'closed' type ones for some samples for comparison. On Ri and Sep, we made shock experiments for pre-heated (at 400-500 C) and unheated targets, and for powdered and uncrushed samples. Water and noble gases were analyzed both for the recovered shocked samples and the unshocked original samples, and the fractions of the degassed volatiles were calculated by comparing them. Water content in the sample was analyzed by thermo-gravimetry. Noble gases were extracted by heating the samples under high vacuum and analyzed with a sector-type mass spectrometer.

  5. Impact degassing of water and noble gases from silicates (United States)

    Azuma, S.; Hiyagon, H.; Iijima, Y.; Syono, Y.

    Previous shock experiments by Ahrens and his colleagues show that degassing of H2O and CO2 occurs at 8-65GPa from hydrous minerals such as serpentine. In early solar system, the impact degassing would have played an important part in the formation of primary-atmospheres of the terrestrial planets. However, degassing conditions of noble gases are not well-known because there are few experiments for them. We conducted some shock recovery experiments to investigate the degassing condition and to understand the degassing mechanisms of water and noble gases. We used natural richterites (Ri), amphibolites (Am), serpentines (Sep) and orthoclases (or) as target samples. These, except Sep, contain radiogenic noble gases such as (40)Ar. The samples were put in stainless steel containers, and were show by a rail gun at ISAS or single-stage powder guns at Nagoya or Tohoku University, Japan. We used two kinds of containers: 'open' type containers having a ventilating path for released volatiles for most of samples and 'closed' type ones for some samples for comparison. On Ri and Sep, we made shock experiments for pre-heated (at 400-500 C) and unheated targets, and for powdered and uncrushed samples. Water and noble gases were analyzed both for the recovered shocked samples and the unshocked original samples, and the fractions of the degassed volatiles were calculated by comparing them. Water content in the sample was analyzed by thermo-gravimetry. Noble gases were extracted by heating the samples under high vacuum and analyzed with a sector-type mass spectrometer.

  6. Suppression of lattice thermal conductivity by mass-conserving cation mutation in multi-component semiconductors (United States)

    Shibuya, Taizo; Skelton, Jonathan M.; Jackson, Adam J.; Yasuoka, Kenji; Togo, Atsushi; Tanaka, Isao; Walsh, Aron


    In semiconductors almost all heat is conducted by phonons (lattice vibrations), which is limited by their quasi-particle lifetimes. Phonon-phonon interactions represent scattering mechanisms that produce thermal resistance. In thermoelectric materials, this resistance due to anharmonicity should be maximised for optimal performance. We use a first-principles lattice-dynamics approach to explore the changes in lattice dynamics across an isostructural series where the average atomic mass is conserved: ZnS to CuGaS2 to Cu2ZnGeS4. Our results demonstrate an enhancement of phonon interactions in the multernary materials and confirm that lattice thermal conductivity can be controlled independently of the average mass and local coordination environments.

  7. Effect of the alkaline cation size on the conductivity in gel polymer electrolytes and their influence on photo electrochemical solar cells. (United States)

    Bandara, T M W J; Fernando, H D N S; Furlani, M; Albinsson, I; Dissanayake, M A K L; Ratnasekera, J L; Mellander, B-E


    The nature and concentration of cationic species in the electrolyte exert a profound influence on the efficiency of nanocrystalline dye-sensitized solar cells (DSSCs). A series of DSSCs based on gel electrolytes containing five alkali iodide salts (LiI, NaI, KI, RbI and CsI) and polyacrylonitrile with plasticizers were fabricated and studied, in order to investigate the dependence of solar cell performance on the cation size. The ionic conductivity of electrolytes with relatively large cations, K(+), Rb(+) and Cs(+), was higher and essentially constant, while for the electrolytes containing the two smaller cations, Na(+) and Li(+), the conductivity values were lower. The temperature dependence of conductivity in this series appears to follow the Vogel-Tamman-Fulcher equation. The sample containing the smallest cation shows the lowest conductivity and the highest activation energy of ∼36.5 meV, while K(+), Rb(+) and Cs(+) containing samples show an activation energy of ∼30.5 meV. DSSCs based on the gel electrolyte and a TiO2 double layer with the N719 dye exhibited an enhancement in the open circuit voltage with increasing cation size. This can be attributed to the decrease in the recombination rate of electrons and to the conduction band shift resulting from cation adsorption by TiO2. The maximum efficiency value, 3.48%, was obtained for the CsI containing cell. The efficiencies shown in this study are lower compared to values reported in the literature, and this can be attributed to the use of a single salt and the absence of other additives, since the focus of the present study was to analyze the cation effect. The highest short circuit current density of 9.43 mA cm(-2) was shown by the RbI containing cell. The enhancement of the solar cell performance with increasing size of the cation is discussed in terms of the effect of the cations on the TiO2 anode and ion transport in the electrolyte. In liquid electrolyte based DSSCs, the short circuit current density

  8. Degassing of Aluminum Alloys Using Ultrasonic Vibration

    Energy Technology Data Exchange (ETDEWEB)

    Meek, T. T.; Han, Q.; Xu, H.


    The research was intended to lead to a better fundamental understanding of the effect of ultrasonic energy on the degassing of liquid metals and to develop practical approaches for the ultrasonic degassing of alloys. The goals of the project described here were to evaluate core principles, establish a quantitative basis for the ultrasonic degassing of aluminum alloy melts, and demonstrate the application of ultrsaonic processing during ingot casting and foundry shape casting.

  9. Degassing of Bioliquids in Low Electromagnetic Fields

    CERN Document Server

    Shatalov, Vladimir; Zinchenko, Alina


    A similarity of changes in physical-chemical properties of pure water induced by low electromagnetic fields (EMF) and by degassing treatment brought us to a conclusion that EMF produces some degassing of water. Degassing in turn gives rise to some biological effects by increasing the surface tension and activity of dissolved ions. In such a way the degassing can modify conformations of proteins and others biomolecules in bioliquids. That was confirmed in our observation of changes in the erythrocyte sedimentation rate and the prothrombinase activity in blood clotting processes.

  10. Minimization and identification of conducted emission bearing current in variable speed induction motor drives using PWM inverter

    Indian Academy of Sciences (India)

    A Ramachandran; M Channa Reddy; Ranjan Moodithaya


    The recent increase in the use of speed control of ac induction motor for variable speed drive using pulse width modulation (PWM) inverter is due to the advent of modern power electronic devices and introduction of microprocessors. There are many advantages of using ac induction motor for speed control applicatons in process and aerospace industries, but due to fast switching of the modern power electronic devices, the parasitic coupling produces undesirable effects. The undesirable effects include radiated and conducted electromagnetic interference (EMI) which adversely affect nearby computers, electronic/electrical instruments and give rise to the flow of bearing current in the induction motor. Due to the flow of bearing current in the induction motor, electrical discharge machining takes place in the inner race of the bearing which reduces the life of the bearing. In high power converters and inverters, the conducted and radiated emissions become a major concern. In this paper, identification of bearing current due to conducted emission, the measurement of bearing current in a modified induction motor and to minimize the bearing current are discussed. The standard current probe, the standard line impedance stabilization network (LISN)), the electronics interface circuits are used to measure high frequency common mode current, bearing current and to minimize the conducted noise from the system. The LISN will prevent the EMI noise entering the system from the supply source by conductive methods, at the same time prevents the EMI generated if any due to PWM, fast switching in the system, will not be allowed to enter the supply line. For comparing the results with Federal Communications Commission (FCC) and Special Committee on Radio Interference (CISPR) standards, the graphs are plotted with frequency Vs, line voltage in $dB{_\\mu} V$, common mode voltage in $dB{_\\mu} V$ and the bearing current in $dB_{\\mu} A$ with out and with minimizing circuits.

  11. Update estimate emissions degassing inland tank vessels

    Energy Technology Data Exchange (ETDEWEB)

    De Buck, A.; Hoen, M. ' t; Den Boer, E.


    At the exchange of cargos of petroleum or chemical products, ships can be degassed, resulting in emissions of VOCs (volatile organic compounds). CE Delft investigated the current size of degassing in the Netherlands. Results can serve as a basis for feasible and effective policies.

  12. A solid phase extraction-ion chromatography with conductivity detection procedure for determining cationic surfactants in surface water samples. (United States)

    Olkowska, Ewa; Polkowska, Żaneta; Namieśnik, Jacek


    A new analytical procedure for the simultaneous determination of individual cationic surfactants (alkyl benzyl dimethyl ammonium chlorides) in surface water samples has been developed. We describe this methodology for the first time: it involves the application of solid phase extraction (SPE-for sample preparation) coupled with ion chromatography-conductivity detection (IC-CD-for the final determination). Mean recoveries of analytes between 79% and 93%, and overall method quantification limits in the range from 0.0018 to 0.038 μg/mL for surface water and CRM samples were achieved. The methodology was applied to the determination of individual alkyl benzyl quaternary ammonium compounds in environmental samples (reservoir water) and enables their presence in such types of waters to be confirmed. In addition, it is a simpler, less time-consuming, labour-intensive, avoiding use of toxic chloroform and significantly less expensive methodology than previously described approaches (liquid-liquid extraction coupled with liquid chromatography-mass spectrometry). Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Spontaneous and CRH-Induced Excitability and Calcium Signaling in Mice Corticotrophs Involves Sodium, Calcium, and Cation-Conducting Channels. (United States)

    Zemkova, Hana; Tomić, Melanija; Kucka, Marek; Aguilera, Greti; Stojilkovic, Stanko S


    Transgenic mice expressing the tdimer2(12) form of Discosoma red fluorescent protein under control of the proopiomelanocortin gene's regulatory elements are a useful model for studying corticotrophs. Using these mice, we studied the ion channels and mechanisms controlling corticotroph excitability. Corticotrophs were either quiescent or electrically active, with a 22-mV difference in the resting membrane potential (RMP) between the 2 groups. In quiescent cells, CRH depolarized the membrane, leading to initial single spiking and sustained bursting; in active cells, CRH further facilitated or inhibited electrical activity and calcium spiking, depending on the initial activity pattern and CRH concentration. The stimulatory but not inhibitory action of CRH on electrical activity was mimicked by cAMP independently of the presence or absence of arachidonic acid. Removal of bath sodium silenced spiking and hyperpolarized the majority of cells; in contrast, the removal of bath calcium did not affect RMP but reduced CRH-induced depolarization, which abolished bursting electrical activity and decreased the spiking frequency but not the amplitude of single spikes. Corticotrophs with inhibited voltage-gated sodium channels fired calcium-dependent action potentials, whereas cells with inhibited L-type calcium channels fired sodium-dependent spikes; blockade of both channels abolished spiking without affecting the RMP. These results indicate that the background voltage-insensitive sodium conductance influences RMP, the CRH-depolarization current is driven by a cationic conductance, and the interplay between voltage-gated sodium and calcium channels plays a critical role in determining the status and pattern of electrical activity and calcium signaling.

  14. Influence of anionic and cationic polyelectrolytes on the conductivity and morphology of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) films

    Energy Technology Data Exchange (ETDEWEB)

    Valtakari, Dimitar, E-mail: [Abo Akademi University, Laboratory of Paper Coating and Converting, Center for Functional Materials at Biological Interfaces (FUNMAT), Porthansgatan 3, FI-20500 Åbo/Turku (Finland); Bollström, Roger [Omya International AG, CH 4665 Oftringen (Switzerland); Toivakka, Martti; Saarinen, Jarkko J. [Abo Akademi University, Laboratory of Paper Coating and Converting, Center for Functional Materials at Biological Interfaces (FUNMAT), Porthansgatan 3, FI-20500 Åbo/Turku (Finland)


    Conductivity of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) strongly depends on the film morphology, which can be altered by the presence of polyelectrolytes. Aqueous dispersion of PEDOT:PSS was studied with anionic sodium polyacrylate (PA) and cationic poly(dimethyldiallylammonium chloride) (pDADMAC) polyelectrolytes that are typically used in papermaking as retention aids and dispersing agents in the paper pigment coating formulations. Spin-coated PEDOT:PSS films on a PA coated glass formed non-uniform layers with lowered conductivity compared to the reference PEDOT:PSS films on a clean glass substrate. On contrary, spin-coated PEDOT:PSS on a pDADMAC coated glass formed uniform layers with good conductivity. These results point out the importance of surface chemistry when using renewable and recyclable paper-based substrates with the PEDOT:PSS films. - Highlights: • PEDOT:PSS polymer was studied in the presence of polyelectrolytes. • Uniform layers of PEDOT:PSS and polyelectrolytes were spin-coated on glass. • Cationic polyelectrolyte was found to be more susceptible to humidity. • Cationic polyelectrolyte improves the conductivity of PEDOT:PSS. • PEDOT:PSS forms non-uniform layers on anionic polyelectrolyte coated glass.

  15. Pinatubo Lake Chemistry and Degassing 1991-2010 (United States)

    Schwandner, F. M.; Newhall, C. G.; Christenson, B. W.; Apfelbeck, C. A.; Arpa, M. C. B.; Vaquilar, R.; Bariso, E.


    We review the history of degassing, bathymetry and water chemistry of the crater lake of Mt. Pinatubo (Philippines) using data obtained during 1991-2001, and 2010. In late 1992, the initial small lake had a significant acid-sulfate component from a volcanic degassing through a hydrothermal system and the lake, and anhydrite dissolution. Subsequently, this component was "drowned" by rainfall (2-4 m/y), meteoric groundwater draining from the crater walls into the lake, and a few neutral chloride crater wall springs. Conductivity-Temperature-Depth (CTD) measurements in August 2000 found a strong inverted thermal gradient below 20m depth, reaching over 70°C at 50-60 m depth. By January 2001 the lake had homogenized and was much cooler (27°C at all depths), and it was again well-mixed and still cool when re-surveyed in June 2001 and November 2010. By 2010, the lake was well mixed, at neutral pH, with no significant vertical or horizontal structure. Bubbling of a predominantly carbon dioxide (CO2) gas phase persists throughout the lake's history, some from 1991-92 magma and some from degassing of the long-standing (pre-1991) hydrothermal system fed from a deeper magmatic or mantle source. Crater wall fumaroles emit boiling-point hydrothermal gases dominated by water, air, and CO2.

  16. Ion transport with charge-protected and non-charge-protected cations using the compensated Arrhenius formalism. Part 2. Relationship between ionic conductivity and diffusion. (United States)

    Petrowsky, Matt; Fleshman, Allison; Bopege, Dharshani N; Frech, Roger


    Temperature-dependent ionic conductivities and cation/anion self-diffusion coefficients are measured for four electrolyte families: TbaTf-linear primary alcohols, LiTf-linear primary alcohols, TbaTf-n-alkyl acetates, and LiTf-n-alkyl acetates. The Nernst-Einstein equation does not adequately describe the data. Instead, the compensated Arrhenius formalism is applied to both conductivity and diffusion data. General trends based on temperature and alkyl chain length are observed when conductivity is plotted against cation or anion diffusion coefficient, but there is no clear pattern to the data. However, plotting conductivity exponential prefactors against those for diffusion results in four distinct curves, one each for the alcohol and acetate families described above. Furthermore, the TbaTf-alcohol and TbaTf-acetate data are "in line" with each other. The conductivity prefactors for the LiTf-alcohol data are smaller than those for the TbaTf data. The LiTf-acetate data have the lowest conductivity prefactors. This trend in prefactors mirrors the observed trend in degree of ionic association for these electrolytes.

  17. A cell shrinkage-induced non-selective cation conductance with a novel pharmacology in Ehrlich-Lettre-ascites tumour cells

    DEFF Research Database (Denmark)

    Lawonn, Peter; Hoffmann, Else K; Hougaard, Charlotte


    In whole-cell recordings on Ehrlich-Lettre-ascites tumour (ELA) cells, the shrinkage-induced activation of a cation conductance with a selectivity ratio P(Na):P(Li):P(K):P(choline):P(NMDG) of 1.00:0.97:0.88:0.03:0.01 was observed. In order of potency, this conductance was blocked by Gd(3+)=benzam......-sensitive and -insensitive channels. In addition, because of its pharmacological profile, it may possibly be related to epithelial Na+ channels (ENaCs)....

  18. Decoupling free-carriers contributions from oxygen-vacancy and cation-substitution in extrinsic conducting oxides. (United States)

    Lin, Y H; Liu, Y S; Lin, Y C; Wei, Y S; Liao, K S; Lee, K R; Lai, J Y; Chen, H M; Jean, Y C; Liu, C Y


    The intrinsic oxygen-vacancies and the extrinsic dopants are two major fundamental free-carrier sources for the extrinsic conducting oxides, such as Sn-doped In(2)O(3). Yet, the individual contributions of the above two free-carrier sources to the total carrier concentrations have never been unraveled. A carrier-concentration separation model is derived in this work, which can define the individual contributions to the total carrier concentration from the intrinsic oxygen-vacancies and the extrinsic dopants, separately. The individual contributions obtained from the present carrier-concentration separation model are verified by the two-state trapping model, photoluminescence, and positron annihilation lifetime (PAL) spectroscopy. In addition, the oxygen-vacancy formation energy of the Sn:In(2)O(3) thin film is determined to be 0.25 eV by PAL spectroscopy.

  19. Structure and properties of Li-ion conducting polymer gel electrolytes based on ionic liquids of the pyrrolidinium cation and the bis(trifluoromethanesulfonyl)imide anion (United States)

    Pitawala, Jagath; Navarra, Maria Assunta; Scrosati, Bruno; Jacobsson, Per; Matic, Aleksandar


    We have investigated the structure and physical properties of Li-ion conducting polymer gel electrolytes functionalized with ionic liquid/lithium salt mixtures. The membranes are based on poly(vinylidene fluoride-co-hexafluoropropylene) copolymer, PVdF-HFP, and two ionic liquids: pyrrolidinium cations, N-butyl-N-methylpyrrolidinium (PyR14+), N-butyl-N-ethylpyrrolidinium (PyR24+), and bis(trifluoromethanesulfonyl)imide anion (TFSI). The ionic liquids where doped with 0.2 mol kg--1 LiTFSI. The resulting membranes are freestanding, flexible, and nonvolatile. The structure of the polymer and the interactions between the polymer and the ionic liquid electrolyte have been studied using Raman spectroscopy. The ionic conductivity of the membranes has been studied using dielectric spectroscopy whereas the thermal properties were investigated using differential scanning caloriometry (DSC). These results show that there is a weak, but noticeable, influence on the physical properties of the ionic liquid by the confinement in the membrane. We observe a change in the Li-ion coordination, conformation of the anion, the fragility and a slight increase of the glass transition temperatures for IL/LiTFSI mixtures in the membranes compared to the neat mixtures. The effect can be related to the confinement of the liquid in the membrane and/or to interactions with the PVdF-HFP polymer matrix where the crystallinity is decreased compared to the starting polymer powder.

  20. Quasi-one-dimensional hopping conductivity of the spin-ladder CaCu2O3 single crystals: Influence of the cation and oxygen nonstoichiometry (United States)

    Lisunov, K. G.; Wizent, N.; Waske, A.; Werner, J.; Tristan, N.; Sekar, C.; Krabbes, G.; Behr, G.; Arushanov, E.; Büchner, B.


    The resistivity ρ(T) of the spin-ladder compound CaCu2O3 measured along the Cu-O-Cu leg (j ∥b) exhibits a strongly activated character. It increases from ˜104 to ˜109 Ωm if T decreases from 350 to 100 K. The charge transfer above T ˜200 K is governed by a quasi-one-dimensional (1D) nearest-neighbor hopping (NNH) conductivity mechanism characterized by the law ρ(T )˜exp(Ea/kT). Below 200 K a novel quasi-1D variable-range hopping (VRH) conductivity law ρ(T )˜exp[(T0/T)3/4] is observed, predicted recently by Fogler, Teber, and Shklovskii [Phys. Rev. B 69, 035413 (2004)]. The NNH activation energy Ea and the VRH characteristic temperature T0 exhibit high sensitivity to the cation (Ca, Cu) content, decreasing by 2.3-2.5 times and by 3.0-3.2 times, respectively, when the composition of Ca is changed from 0.854 to 0.786-0.798 and the composition of Cu from 2.039 to 2.159-2.163. The behavior of Ea and T0 can be attributed to a corresponding variation of the concentration of intrinsic defects associated with Cu vacancies. On the other hand, no direct dependence of Ea and T0 to the excess oxygen concentration is observed.

  1. Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects (United States)

    Pastor, María Jesús; Cuerva, Cristián; Campo, José A.; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes


    Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOOR(n)pyH]+ and BF4−, ReO4−, NO3−, CF3SO3−, CuCl42− counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOOR(12)pyH][ReO4] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl42− salts exhibit the best LC properties followed by the ReO4− ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO4−, and CuCl42− families, and for the solid phase in one of the non-mesomorphic Cl− salts. The highest ionic conductivity was found for the smectic mesophase of the ReO4− containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure. PMID:28773485

  2. A fixed cations and low Tg polymer: the poly(4-vinyl-pyridine) quaternized by poly(ethylene oxide) links. Conductivity study; Un electrolyte polymere a cations fixes et bas Tg: les poly(4-vinylpyridine) quaternisees par des chainons de poly(oxyde d`ethylene). Etude de la conductivite

    Energy Technology Data Exchange (ETDEWEB)

    Gramain, Ph. [Ecole Nationale Superieure de Chimie de Montpellier, 34 (France); Frere, Y. [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France). Institut Charles Sadron


    The spontaneous ionic polymerization of 4-vinyl-pyridine in presence of mono-tosylated or bromated short chains of poly(ethylene oxide)-(PEO) is used to prepare amorphous comb-like poly-cations with low Tg. The polymer electrolyte properties of these new structures have been studied without any addition of salts. The ionic conductivity of these fixed cation poly-electrolytes depends on the length of the grafted PEO and varies from 10{sup -7} to 10{sup -4} S/cm between 25 and 80 deg. C. It is only weakly dependent on the nature of the cation but it is controlled by the movements of the pyridinium cation which are facilitated by the plastifying effect of the POE chains which do not directly participate to the ionic transport. (J.S.) 17 refs.

  3. Degassing and differentiation in subglacial volcanoes, Iceland (United States)

    Moore, J.G.; Calk, L.C.


    Within the neovolcanic zones of Iceland many volcanoes grew upward through icecaps that have subsequently melted. These steep-walled and flat-topped basaltic subglacial volcanoes, called tuyas, are composed of a lower sequence of subaqueously erupted, pillowed lavas overlain by breccias and hyaloclastites produced by phreatomagmatic explosions in shallow water, capped by a subaerially erupted lava plateau. Glass and whole-rock analyses of samples collected from six tuyas indicate systematic variations in major elements showing that the individual volcanoes are monogenetic, and that commonly the tholeiitic magmas differentiated and became more evolved through the course of the eruption that built the tuya. At Herdubreid, the most extensively studies tuya, the upward change in composition indicates that more than 50 wt.% of the first erupted lavas need crystallize over a range of 60??C to produce the last erupted lavas. The S content of glass commonly decreases upward in the tuyas from an average of about 0.08 wt.% at the base to crystallization that generates the more evolved, lower-temperature melts during the growth of the tuyas, apparently results from cooling and degassing of magma contained in shallow magma chambers and feeders beneath the volcanoes. Cooling may result from percolation of meltwater down cracks, vaporization, and cycling in a hydrothermal circulation. Degassing occurs when progressively lower pressure eruption (as the volcanic vent grows above the ice/water surface) lowers the volatile vapour pressure of subsurface melt, thus elevating the temperature of the liquidus and hastening liquid-crystal differentiation. ?? 1991.

  4. Actinide cation-cation complexes

    Energy Technology Data Exchange (ETDEWEB)

    Stoyer, Nancy Jane [Univ. of California, Berkeley, CA (United States)


    The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO2+) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO2+; therefore, cation-cation complexes indicate something unique about AnO2+ cations compared to actinide cations in general. The first cation-cation complex, NpO2+•UO22+, was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO2+ species, the cation-cation complexes of NpO2+ have been studied most extensively while the other actinides have not. The only PuO2+ cation-cation complexes that have been studied are with Fe3+ and Cr3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO2+•UO22+, NpO2+•Th4+, PuO2+•UO22+, and PuO2+•Th4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ~0.8 M-1.

  5. 75 FR 67100 - Superalloy Degassed Chromium From Japan (United States)


    ... COMMISSION Superalloy Degassed Chromium From Japan AGENCY: United States International Trade Commission... chromium from Japan. SUMMARY: The Commission hereby gives notice that it has instituted a review pursuant... revocation of the antidumping duty order on superalloy degassed chromium from Japan would be likely to lead...

  6. Surface Modification of Multiwall Carbon Nanotubes with Cationic Conjugated Polyelectrolytes: Fundamental Interactions and Intercalation into Conductive Poly(methyl-methacrylate) Composites

    KAUST Repository

    Ezzeddine, Alaa


    This research investigates the modification and dispersion and of pristine multiwalled carbon nanotubes (MWCNTs) through a simple solution mixing technique based on noncovalent interactions between poly(phenylene ethynylene) based conjugated polyelectrolytes functionalized with cationic imidazolium solubilizing groups (PIM-2 and PIM-4) and MWCNTs. Spectroscopic studies demonstrated the ability of PIMs to strongly interact with and efficiently disperse MWCNTs in different solvents mainly due to π-interactions between the PIMs and MWCNTs. Transmission electron microscopy and atomic force microscopy revealed the coating of the polyelectrolytes on the walls of the nanotubes. Scanning electron microscopy (SEM) studies confirm the homogenous dispersion of PIM modified MWCNTs in poly(methyl methacrylate) (PMMA) matrix. The addition of 1 wt% PIM modified MWCNTs to the matrix has led to a significant decrease in DC resistivity of the composite (13 orders of magnitude). The increase in electrical conductivity and the improvement in thermal and mechanical properties of the membranes containing the PIM modified MWCNTs is ascribed to the formation of MWCNTs networks and cross-linking sites that provided channels for the electrons to move in throughout the matrix and reinforced the interface between MWCNTs and PMMA.

  7. Carbon dioxide degassing in fresh and saline water I: Degassing performance of a cascade column

    DEFF Research Database (Denmark)

    Moran, Damian


    A study was undertaken to measure carbon dioxide degassing in a cascade column operating with both fresh (0‰) and saline water (35‰ NaCl) at 15 °C. The cascade column contained bio-block type packing material, was 1.7 m long in each dimension, and was tested both with and without countercurrent air......) and the CO2 stripping efficiency (the difference in CO2 concentration between the influent water and the effluent water that has re-established chemical equilibria approximately 1 min after exiting the column). Mass transfer coefficients were similar between fresh and saline water. Countercurrent air flow...... exchange. The CO2 concentration of the influent and effluent water was measured using submersible infrared CO2 probes over an influent range of 10-60 mg L−1 CO2. Carbon dioxide degassing was quantified in terms of the mass transfer coefficient (kLa, log concentration driving force divided by packing height...

  8. Ion transport with charge-protected and non-charge-protected cations in alcohol-based electrolytes using the compensated Arrhenius formalism. Part I: ionic conductivity and the static dielectric constant. (United States)

    Petrowsky, Matt; Fleshman, Allison; Frech, Roger


    The temperature dependence of ionic conductivity and the static dielectric constant is examined for 0.30 m TbaTf- or LiTf-1-alcohol solutions. Above ambient temperature, the conductivity increases with temperature to a greater extent in electrolytes whose salt has a charge-protected cation. Below ambient temperature, the dielectric constant changes only slightly with temperature in electrolytes whose salt has a cation that is not charge-protected. The compensated Arrhenius formalism is used to describe the temperature-dependent conductivity in terms of the contributions from both the exponential prefactor σo and Boltzmann factor exp(-Ea/RT). This analysis explains why the conductivity decreases with increasing temperature above 65 °C for the LiTf-dodecanol electrolyte. At higher temperatures, the decrease in the exponential prefactor is greater than the increase in the Boltzmann factor.

  9. Influence of starting material on the degassing behavior of trachytic and phonolitic melts (United States)

    Preuss, Oliver; Marxer, Holger; Nowak, Marcus


    The dynamic magmatic processes beneath volcanic systems, occurring during magma ascent, cannot be observed directly in nature. Simulation of magma ascent in the lab realized by continuous decompression (CD) of a volatile containing melt is essential to understand these processes that may lead to potentially catastrophic eruptions threatening millions of people in highly populated areas like Naples located between the Campi Flegrei Volcanic Field and the Monte Somma-Vesuvio strato-volcano. In this project, experimental simulations of Campanian Ignimbrite (CI) magma ascent will give insight to the mechanisms of the CI super eruption, thus providing tools for volcanic hazard assessment at the high risk Campanian Volcanic District and other comparable volcanic systems. Additionally, comparable experiments with the same conditions using the 'white pumice' composition of the catastrophic Vesuvius AD 79 (VAD79) eruption, have been conducted. So far, the experiments were performed in an internally heated argon pressure vessel coupled with a high-pressure low-flow metering valve and a piezoelectric nano-positioning system using a starting pressure of 200 MPa, H2O content of about 5 wt% and two different decompression rates (0.024 and 0.17 MPa/s) at a superliquidus temperature of 1050 ° C to ensure a crystal free melt and a homogeneous bubble nucleation. Experiments were conducted with both, glass powder and cylinders, subsequently decompressed to 75 and 100 MPa and rapidly quenched. Beside the results that e.g. decompression rate, volatile content, fluid solubility and target pressure affect the degassing behavior of the melt, the influence of the starting material on the degassing processes is significant. Analyses of BSE- and transmitted light microscopy images revealed a different degassing behavior of glass cylinder experiments compared to powders. Nitrogen has a very low solubility in hydrous silicate melts, supporting our suggestion that preexisting nitrogen rich

  10. Degassing Processes at Persistently Active Explosive Volcanoes (United States)

    Smekens, Jean-Francois

    Among volcanic gases, sulfur dioxide (SO2) is by far the most commonly measured. More than a monitoring proxy for volcanic degassing, SO 2 has the potential to alter climate patterns. Persistently active explosive volcanoes are characterized by short explosive bursts, which often occur at periodic intervals numerous times per day, spanning years to decades. SO 2 emissions at those volcanoes are poorly constrained, in large part because the current satellite monitoring techniques are unable to detect or quantify plumes of low concentration in the troposphere. Eruption plumes also often show high concentrations of ash and/or aerosols, which further inhibit the detection methods. In this work I focus on quantifying volcanic gas emissions at persistently active explosive volcanoes and their variations over short timescales (minutes to hours), in order to document their contribution to natural SO2 flux as well as investigate the physical processes that control their behavior. In order to make these measurements, I first develop and assemble a UV ground-based instrument, and validate it against an independently measured source of SO2 at a coal-burning power plant in Arizona. I establish a measurement protocol and demonstrate that the instrument measures SO 2 fluxes with explosions with periods of minutes to hours for the past several decades. Semeru produces an average of 21-71 tons of SO2 per day, amounting to a yearly output of 8-26 Mt. Using the Semeru data, along with a 1-D transient numerical model of magma ascent, I test the validity of a model in which a viscous plug at the top of the conduit produces cycles of eruption and gas release. I find that it can be a valid hypothesis to explain the observed patterns of degassing at Semeru. Periodic behavior in such a system occurs for a very narrow range of conditions, for which the mass balance between magma flux and open-system gas escape repeatedly generates a viscous plug, pressurizes the magma beneath the plug, and

  11. Behavior of halogens during the degassing of felsic magmas (United States)

    Balcone-Boissard, H.; Villemant, B.; Boudon, G.


    Residual concentrations of halogens (F, Cl, Br, I) and H2O in glass (matrix glass and melt inclusions) have been determined in a series of volcanic clasts (pumice and lava-dome fragments) of plinian, vulcanian and lava dome-forming eruptions. Felsic magmas from calc-alkaline, trachytic and phonolitic systems have been investigated: Montagne Pelée and Soufrière Hills of Montserrat (Lesser Antilles), Santa Maria-Santiaguito (Guatemala), Fogo (Azores) and Vesuvius (Italy). The behavior of halogens during shallow H2O degassing primarily depends on their incompatible character and their partitioning between melt and exsolved H2O vapor. However, variations in pre-eruptive conditions, degassing kinetics, and syn-eruptive melt crystallization induce large variations in the efficiency of halogen extraction. In all systems studied, Cl, Br and I are not fractionated from each other by differentiation or by degassing processes. Cl/Br/I ratios in melt remain almost constant from the magma reservoir to the surface. The ratios measured in erupted clasts are thus characteristic of pre-eruptive magma compositions and may be used to trace deep magmatic processes. F behaves as an incompatible element and, unlike the other halogens, is never significantly extracted by degassing. Cl, Br and I are efficiently extracted from melts at high pressure by H2O-rich fluids exsolved from magmas or during slow effusive magma degassing, but not during rapid explosive degassing. Because H2O and halogen mobility depends on their speciation, which strongly varies with pressure in both silicate melts and exsolved fluids, we suggest that the rapid pressure decrease during highly explosive eruptions prevents complete equilibrium between the diverse species of the volatiles and consequently limits their degassing. Conversely, degassing in effusive eruptions is an equilibrium process and leads to significant halogen output in volcanic plumes.

  12. The effect of degassing on morphology and space charge


    Chong, Y L; Chen, G; Ho, Y F F


    It is believed that space charge buildup in cross-linked polyethylene (XLPE) insulation is the main cause for premature failure of underground power cables. The space charge activities in XLPE depend on many factors such as additives, material treatment, ambient temperature, insulator/electrode interface, etc. Degassing is one of the material treatment process commonly employ in cable manufacturing to improve insulation performance. In this paper, investigation on the effect of degassing peri...

  13. Volcanism, Earth Degassing and Replenished Lithosphere Mantle (United States)

    Bailey, D. K.


    Volcanism that pierces plate interiors is characteristically rich in alkalis and volatiles, and its cause and persistence are essentially expressions of the Earth's outgassing. The general balance of mobile elements (such as H, C, F and Cl) rules out recycling of sea floor, hydrosphere, sediments or atmosphere: furthermore, it is not in accord with accepted planet degassing budgets. The typical eruptive mode of volatile-rich magmatism means that the observed regional chemical variations, and even differences between adjacent volcanoes, must largely reflect source heterogeneity. In a broader context, this magmatism is also at odds with a concept of continental crust underlain by strongly depleted (refractory) mantle. Repetition of activity along crustal zones of weakness shows that the lithosphere mantle (a) is structurally complex and (b) still holds continuing (or continual) rich reserves of mobile elements. Unbroken lithosphere muffles the evolutionary escape of volatiles from the deep mantle: any lesion that appears then offers easy escape channels, whereby volatiles are drained from a large mantle region and funnelled through the plate. Horizontal movement of thick continental lithosphere releases volatiles from deep sources, imparting some of the special chemical characteristics of the stable continental magmatism. Present evidence requires consideration of the continental lithosphere as a site of primordial heterogeneity that has been accentuated rather than diminished by geological processes.

  14. Synthesis and characterization of sodium cation-conducting Nax(MyL1-yO2 (M = Ni2+, Fe3+; L = Ti4+, Sb5+

    Directory of Open Access Journals (Sweden)

    Marques, F. M. B.


    Full Text Available The Na+-conducting ceramics of layered Na0.8Ni0.4Ti0.6O2, Na0.8Fe0.8Ti0.2O2, Na0.8Ni0.6Sb0.4O2 (structural type O3 and Na0.68Ni0.34Ti0.66O2 (P2 type with density higher than 91% were prepared via the standard solid-state synthesis route and characterized by the impedance spectroscopy, thermal analysis, scanning electron microscopy, structure refinement using X-ray powder diffraction data, measurements of Na+ concentration cell e.m.f., and dilatometry. The conductivity of antimonate Na0.8Ni0.6Sb0.4O2, synthesized first time, was found lower than that of isostructural Na0.8Ni0.4Ti0.6O2 due to larger ion jump distance between Na+ sites. At temperatures above 420 K, transport properties of sodium cationconducting materials are essentially independent of partial water vapor pressure. In the low-temperature range, the conductivity reversibly increases with water vapor pressure varied in the range from approximately 0 (dry air up to 0.46 atm. The sensitivity to air humidity is influenced by the ceramic microstructure, being favored by increasing boundary area. The average thermal expansion coefficients of layered materials at 300-1173 K are in the range (13.7-16.0×10-6 K-1.Se han preparado cerámicas conductoras conteniendo Na+ de composición Na0.8Ni0.4Ti0.6O2, Na0.8Fe0.8Ti0.2O2, Na0.8Ni0.6Sb0.4O2 (tipo estructural O3 y Na0.68Ni0.34Ti0.66O2 (tipo P2 con densidad mayor del 91%. Las vía de preparación fu la ruta de estandard de síntesis en estado sólido. Las composiciones se caracterizaron mediante espectroscopía de impedancia, análisis térmico, microscopía electrónica de barrido, refinamiento de la estructura usando datos de difracción de rayos X en polvo, medidas de concentración de Na+, f.e.m. de la célula y dilatometría. La conductividad del antimoniate, sintetizado por primera vez, Na0.8Ni0.6Sb0.4O2, era menor que la del compuesto isoestructural Na0.8Ni0.4Ti0.6O2 debido a la mayor distancia de salto iónico entre las posiciones de Na

  15. Activation of a Ca(2+)-dependent cation conductance with properties of TRPM2 by reactive oxygen species in lens epithelial cells. (United States)

    Keckeis, Susanne; Wernecke, Laura; Salchow, Daniel J; Reichhart, Nadine; Strauß, Olaf


    Ion channels are crucial for maintenance of ion homeostasis and transparency of the lens. The lens epithelium is the metabolically and electrophysiologically active cell type providing nutrients, ions and water to the lens fiber cells. Ca(2+)-dependent non-selective ion channels seem to play an important role for ion homeostasis. The aim of the study was to identify and characterize Ca(2+)- and reactive oxygen species (ROS)-dependent non-selective cation channels in human lens epithelial cells. RT-PCR revealed gene expression of the Ca(2+)-activated non-selective cation channels TRPC3, TRPM2, TRPM4 and Ano6 in both primary lens epithelial cells and the cell line HLE-B3, whereas TRPM5 mRNA was only found in HLE-B3 cells. Using whole-cell patch-clamp technique, ionomycin evoked non-selective cation currents with linear current-voltage relationship in both cell types. The current was decreased by flufenamic acid (FFA), 2-APB, 9-phenanthrol and miconazole, but insensitive to DIDS, ruthenium red, and intracellularly applied spermine. H2O2 evoked a comparable current, abolished by FFA. TRPM2 protein expression in HLE-B3 cells was confirmed by means of immunocytochemistry and western blot. In summary, we conclude that lens epithelial cells functionally express Ca(2+)- and H2O2-activated non-selective cation channels with properties of TRPM2. Copyright © 2017. Published by Elsevier Ltd.

  16. Stoichiometry gradient, cation interdiffusion, and band alignment between a nanosized TiO2 blocking layer and a transparent conductive oxide in dye-sensitized solar cell front contacts. (United States)

    Salvinelli, Gabriele; Drera, Giovanni; Baratto, Camilla; Braga, Antonio; Sangaletti, Luigi


    An angle-resolved photoemission spectroscopy study allowed us to identify cation interdiffusion and stoichiometry gradients at the interface between a nanosized TiO2 blocking layer and a transparent conductive Cd-Sn oxide substrate. A stoichiometry gradient for the Sn cations is already found in the bare Cd-Sn oxide layer. When TiO2 ultrathin layers are deposited by RF sputtering on the Cd-Sn oxide layer, Ti is found to partially replace Sn, resulting in a Cd-Sn-Ti mixed oxide layer with a thickness ranging from 0.85 to 3.3 nm. The band gap profile across the junction has been reconstructed for three TiO2 layers, resulting in a valence band offset decrease (and a conduction band offset increase) with the blocking layer thickness. The results are related to the cell efficiencies in terms of charge injection and recombination processes.

  17. Characteristics of mantle degassing and deep-seated geological structures in different typical fault zones of China

    Institute of Scientific and Technical Information of China (English)

    TAO; Mingxin; XU; Yongchang; SHI; Baoguang; JIANG; Zhongt


    In this paper a comprehensive tracing study is conducted on mantle degassing and deep-seated geological structures in different types of fault zones in the continent of China based on the helium isotope data, coupled with some indices such as CO2/3He, CH4/3He and 40Ar/36Ar,and geological tectonics data. There are four representative types of fault zones: (1) Lithospheric fault zones in the extensional tectonic environment are characterized by a small Earth's crust thickness, a lower CH4/3He-high R and lower CO2/3He-high R system, the strongest mantle degassing, and the dominance of mantle fluid, as is represented by the Tancheng-Lujiang fault zone.(2) The lithospheric fault zones or the subduction zone in the strongly compresso-tectonic environment, for instance, the Bangonghu-Nujiang fault zone, are characterized by a huge thick Earth's crust, with the R/Ra values within the range of 0.43-1.13, and weak mantle degassing with mantle-source helium accounting for 5%-14% of the total. (3) The deep-seated fault zones at the basinal margins of an orogenic belt are characterized by R values being on order of magnitude of 10-7, and the CH4/3He values, 109-1010, CO2/3He values, 106-108; as well as much weak mantle degassing. (4) The crustal fault zones in the orogenic belt, such as the Yaojie fault zone (F19), possess a high CH4/3He-low R (10-8) and high CO2/3He-low R system, with no obvious sign of mantle degassing. Studies have shown that the deep-seated huge fault zones are the major channel ways for mantle degassing, the main factors controlling the intensity of mantle degassing are fault depth, tectonic environment and crust thickness; the intensity of mantle degassing can reflect the depth and the status of deep-seated tectonic environment of fault, while the geochemical tracing studies of gases can open up a new research approach; upwelling activity of hydrothermal fluids from the deep interior of the Earth may be one of the driving forces for the formation and

  18. Trivalent Cation Substitution Effect into Layered Double Hydroxides Co 2Fe y Al 1- y(OH) 6Cl· nH 2O: Study of the Local Order . Ionic Conductivity and Magnetic Properties (United States)

    Intissar, Mourad; Segni, Rachid; Payen, Christophe; Besse, Jean-Pierre; Leroux, Fabrice


    A series of layered double hydroxide materials of composition Co 2Fe yAl 1- y(OH) 6Cl· nH 2O (0≤ y≤1) was prepared via chimie douce. The crystalline parameter related to the cation to cation distance obeys the expected variation, showing that the substitution is effective over the entire range. Local order around Co and Fe cations is studied by X-ray absorption spectroscopy. Moduli of the Fourier transform at the Fe K-edge are superimposable, in agreement with an ordered model, although present in small domains since no superlattice is depicted. The ionic resistivity of the samples is highly dependent on the water molecule content. The conductivity is found to be thermally assisted, and the variation of the slope in the Arrhenius diagram is explained by a Vogel-Tamman-Fulcher-type behavior. Magnetic susceptibility measurements support the proposed cation composition and indicate the onset of local magnetic order at low temperature (below 10 K). The inter-sheet distance influences the magnetic response at low temperature, showing the presence of weak interactions between lamellae.

  19. Dynamics of degassing at Kilauea Volcano, Hawaii (United States)

    Vergniolle, Sylvie; Jaupart, Claude


    At Kilauea volcano, Hawaii, the recent long-lived eruptions of Mauna Ulu and Pu'u O'o have occurred in two major stages, defining a characteristic eruptive pattern. The first stage consists of cyclic changes of activity between episodes of "fire fountaining" and periods of quiescence or effusion of vesicular lava. The second stage consists only of continuous effusion of lava. We suggest that these features reflect the dynamics of magma degassing in a chamber which empties into a narrow conduit. In the volcano chamber, gas bubbles rise through magma and accumulate at the roof in a foam layer. The foam flows toward the conduit, and its shape is determined by a dynamic balance between the input of bubbles from below and the output into the conduit. The foam thickness is proportional to (μlQ/ɛ2 ρl g)1/4, where μ l and ρl are the viscosity and density of magma, ɛ is the gas volume fraction in the foam, g is the acceleration of gravity, and Q is the gas flux. The bubbles in the foam deform under the action of buoyancy, and the maximum permissible foam thickness is hc = 2σ/ɛρlgR, where σ is the coefficient of surface tension and R is the original bubble radius. If this critical thickness is reached, the foam collapses into a large gas pocket which erupts into the conduit. Foam accumulation then resumes, and a new cycle begins. The attainment of the foam collapse threshold requires a gas flux in excess of a critical value which depends on viscosity, surface tension, and bubble size. Hence two different eruption regimes are predicted: (1) alternating regimes of foam buildup and collapse leading to the periodic eruption of large gas volumes and (2) steady foam flow at the roof leading to continuous bubbly flow in the conduit. The essential result is that the continuous process of degassing can lead to discontinuous eruptive behavior. Data on eruption rates and repose times between fountaining phases from the 1969 Mauna UIu and the 1983-1986 Pu'u O'o eruptions yield

  20. Determination of Morpholinium Ionic Liquid Cations by Ion Chromatography with Direct Conductivity Detection%离子色谱-直接电导检测法分离测定吗啉离子液体阳离子

    Institute of Scientific and Technical Information of China (English)

    孙晓娇; 于泓; 张仁庆


    An ion chromatographic method with direct conductivity detection for the determination of N-methyl,ethyl morpholinium cation([MEMo] +),N-methyl,propyl morpholinium cation([MP-Mo] +) two morpholinium ionic liquid cations was developed using a cation-exchange column and ethylenediamine-acetonitrile as mobile phase.The effects of column type,mobile phase and column temperature on retention and separation of the cations were investigated.The retention rules of the cations under different chromatographic conditions were formulated.The results indicated that the retention process of morpholinium cations retained in line with the ion-exchange mode,wihich was an exothermic process.The successful separation of the two morpholinium ionic liquid cations was achieved using the optimized mobile phase of 0.1 mmol/L ethylenediamine-0.5% acetonitrile (adjusted to pH 5.0 with hydrochloric acid) at a flow rate of 1.0 mL/min and a column temperature of 30 ℃.Under the optimal conditions,the two morpholinium ionic liquid cations could be successfully separated in 4 min.The detection limits(S/N =3) for [MEMo] + and [MPMo] + were 0.08 mg/L and 0.13 mg/L,respectively.The relative standard deviations(RSDs,n =5) of the chromatographic peak areas for the cations were no more than 1.5%.The method was successfully applied in the determination of morpholinium bromide ionic liquid samples synthesized by chemistry laboratory.The recoveries of morpholinium cations after spiked were in the range of 94.0%-106.0%.The method was proved to be accurate,reliable and rapid,and could meet the requirements for quantitative analysis of morpholinium ionic liquid samples.%建立了离子色谱-直接电导检测法分析N-甲基乙基吗啉([MEMo]+)、N-甲基丙基吗啉([MPMo]+)2种吗啉离子液体阳离子的方法.采用磺酸型阳离子交换色谱柱,以乙二胺-乙腈为流动相,研究了色谱柱、流动相、色谱柱温度对吗啉阳离子保留的影响,并讨论了保留规律.结

  1. Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in the Phosphonium Cation. (United States)

    Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F


    A series of room-temperature ionic liquids (ILs) composed of triethyl(alkyl)phosphonium cations paired with three different aprotic heterocyclic anions (AHAs) (alkyl = butyl ([P2224](+)) and octyl ([P2228](+))) were prepared to investigate the effect of cationic alkyl chain length on transport properties. The transport properties and density of these ILs were measured from 283.15 to 343.15 K at ambient pressure. The dependence of the transport properties (viscosity, ionic conductivity, diffusivity, and molar conductivity) on temperature can be described by the Vogel-Fulcher-Tamman (VFT) equation. The ratio of the molar conductivity obtained from the molar concentration and ionic conductivity measurements to that calculated from self-diffusion coefficients (measured by pulsed gradient spin-echo nuclear magnetic resonance spectroscopy) using the Nernst-Einstein equation was used to quantify the ionicity of these ILs. The molar conductivity ratio decreases with increasing number of carbon atoms in the alkyl chain, indicating that the reduced Coulombic interactions resulting from lower density are more than balanced by the increased van der Waals interactions between the alkyl chains. The results of this study may provide insight into the design of ILs with enhanced dynamics that may be suitable as electrolytes in lithium ion batteries and other electrochemical applications.

  2. Changes in magmatic oxidation state induced by degassing (United States)

    Brounce, M. N.; Stolper, E. M.; Eiler, J. M.


    Temporal variations in the oxygen fugacity (fO2) of the mantle may have been transmitted to Earth's atmosphere and oceans by volcanic degassing. However, it is unclear how redox states of volatiles relate to their source magmas because degassing and assimilation can impact fO2 before or during eruption. To explore this, we present µ-XANES measurements of the oxidation states of Fe and S and laser fluorination measurements of 18O/16O ratios in submarine glasses from two settings where degassing is recorded: 1) submarine glasses from the Reykjanes Ridge as it shoals to Iceland, including subglacial glasses from the Reykjanes Peninsula; and 2) submarine glasses from Mauna Kea recovered by the Hawaii Shield Drilling Program (HSDP). Glasses from both settings are basalts with 5.5-9.9 wt% MgO and 350-1790 ppm S. Submarine Reykjanes glasses are sulfide saturated. Subglacial Reykjanes and HSDP glasses are not sulfide saturated, and S and H2O contents are consistent with S+H2O degassing. Submarine Reykjanes glasses have 18O/16O indistinguishable from MORB and become progressively 18O-depleted as MgO decreases. Subglacial glasses have lower 18O/16O than submarine glasses at a given MgO, but both sample types project to a common 18O/16O near 10 wt% MgO, suggesting that 18O-depletion in these lavas is generated by fractional crystallization and assimilation of an 18O-depleted crustal component. The oxidation state of Fe increases only slightly as 18O/16O decrease, suggesting that the assimilant is not oxidized enough to change magmatic fO2. Fe and S do not oxidize or reduce with decreasing S or H2O, suggesting that relatively reduced magmas at depth degassed S+H2O without changing magmatic fO2, and that the fO2 of these lavas reflect the fO2of their mantle source. The oxidation states of Fe and S in HSDP glasses are broadly correlated and samples with the highest S concentrations are the most oxidized. Both Fe and S reduce with decreasing S and H2O contents. This suggests

  3. The effect of dissolve gas concentration in the initial growth stage of multi cavitation bubbles. Differences between vacuum degassing and ultrasound degassing. (United States)

    Yanagida, Hirotaka


    The sonochemical luminescence intensity from luminol was measured at a sampling rate of several kilohertz. This was noted at three different periods: first, the latent period in which no light emission occurs at all; second, the increased emission period from the start of light emission to the time when a steady state is reached; and third, the steady state period in which light emission occurs at the steady state value. When irradiated with ultrasound of different intensities, the times of the latent period and increased emission period are shorter for higher ultrasound intensities. To know how the dissolved oxygen content is involved in early-stage cavitation growth, an experiment was conducted using solutions with varying dissolved oxygen contents from 100% to 37%. For dissolved air content of 50% or less, it was found that the latent period was 30 times longer in a saturated condition. It was also found that the increased emission period was 10 times longer. However, the emission intensity in the steady state did not change at all even when the initial dissolved gas concentration of the sample was changed. From this, it was found that the reuse of collapsed bubbles takes place efficiently in the steady state. Dissolved oxygen was reduced by the use of a vacuum pump and by the degassing action of ultrasound, and it was discovered that the behavior of transient emission differed for the two ways of degassing.

  4. Effect of aliovalent-cation substitution on the oxygen-ion conductivity of Bi[sub 4]V[sub 2]O[sub 11

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, V.; Shukla, A.K.; Gopalakrishnan, J. (Solid State and Structural Chemistry Unit, Indian Inst. of Science, Bangalore (India))


    Up to 10 atom.% of Li[sup +], Zn[sup 2+], Al[sup 3+], Ti[sup 4+] and Ge[sup 4+] readily substitute for vanadium in Bi[sub 4]V[sub 2]O[sub 11] stabilizing [alpha]/[gamma] structures. The [gamma]-phases are good oxygen-ion conductors, the Ti-substituted [gamma]-phase, Bi[sub 4]V[sub 1.8]Ti[sub 0.2]O[sub 10.9], being the best ionic conductor among all the substituted bismuth vanadates investigated. It is conjectured that a high ionic potential of the dopand cation facilities oxygen-ion mobility in the disordered phase of the substituted bismuth vanadate. (orig.).

  5. Technology and means of a coal seam interval hydraulic fracturing for the seam degassing intensification (United States)

    Klishin, VI; Opruk, GY; Tatsienko, AL


    Interval hydraulic fracturing use for the seam degassing intensification actuality is explained. The known methods of degassing are reviewed. Technological scheme of the interval coal seam hydraulic fracturing implementation is worked out. The equipment to fulfill degassing intensification measures is suggested.

  6. Dating degassed groundwater with 3H/3He

    NARCIS (Netherlands)

    Visser, A.; Broers, H.P.; Bierkens, M.F.P.


    The production of gases in groundwater under contaminated locations by geochemical and biological processes is not uncommon. Degassing of these gases from groundwater and repartitioning of noble gases between water and gas phase distorts groundwater dating by 3H/3He. We observed noble gas concentrat

  7. 76 FR 8773 - Superalloy Degassed Chromium From Japan (United States)


    ... From the Federal Register Online via the Government Publishing Office INTERNATIONAL TRADE COMMISSION Superalloy Degassed Chromium From Japan AGENCY: United States International Trade Commission... Japan would be likely to lead to continuation or recurrence of material injury. On December 22, 2010...

  8. Dating degassed groundwater with 3H/3He

    NARCIS (Netherlands)

    Visser, A.; Broers, H.P.; Bierkens, M.F.P.


    The production of gases in groundwater under contaminated locations by geochemical and biological processes is not uncommon. Degassing of these gases from groundwater and repartitioning of noble gases between water and gas phase distorts groundwater dating by 3H/3He. We observed noble gas

  9. Decomposition of Transformer Oil Under Ultrasonic Irradiation During Degassing Process

    Institute of Scientific and Technical Information of China (English)


    In the degassing process of transformer oil with ultrasonic waves, decomposition of the oil was observed. Light hydrocarbons, including methane, ethane, ethylene, acetylene, propane etc, were found to be released continuously from the oil into headspace within a closed vial placed in an ultrasonic field. The gases came from decomposition of hydrocarbon molecules under cavitation effect.

  10. Sponge Cake or Champagne? Bubbles, Magmatic Degassing and Volcanic Eruptions (United States)

    Cashman, K.; Pioli, L.; Belien, I.; Wright, H.; Rust, A.


    Vesiculation is an unavoidable consequence of magma decompression; the extent to which bubbles travel with ascending magma or leave the system by separated or permeable flow will determine the nature of the ensuing eruption. Bubbles travel with the melt from which they exsolve if the rise time of bubbles through the melt (the 'drift velocity') is much less than the rise rate of the magma (sponge cake). This condition is most likely to be met in viscous melts (where bubble rise velocities are low) and in melts that experience rapid decompression (high ascent velocities). Under these conditions, bubble expansion within the melt continues until sufficient bubble expansion causes coalescence and the development of a permeable network. Typical pumice vesicularities of 70-80% and permeabilities of 10-12 m2 constrain this limit under conditions appropriate for subplinian to plinian eruptions (mass fluxes > 106 kg/s). Slower rise rates (and lower mass fluxes) that characterize effusive eruptions produce silicic lavas with a wider range of vesicularities. In general, permeability decreases with decreasing sample vesicularity as bubbles deform (as evidenced by anisotropy in permeability and electrical conductivity) and pore apertures diminish. Degassing efficiency (and resulting densification of magma within the conduit) under these conditions is determined by permeability and the time allowed for gas escape. Bubbles rise through the melt if the drift velocity exceeds the velocity of magma ascent (champagne). This condition is most easily met in volatile-rich, low viscosity (mafic) melts at low to moderate fluxes. At very low magma flux, magma eruption rate is determined by the extent to which magma is entrained and ejected by rising gases (strombolian eruptions); when bubbles are too small, or are rising too slowly, they may not break the surface at all, but instead may be concentrated in a near-surface layer (surface foam). As the magma flux increases, segregation of

  11. Groundwater degassing in fractured rock: Modelling and data comparison

    Energy Technology Data Exchange (ETDEWEB)

    Jarsjoe, J.; Destouni, G. [Royal Inst. of Tech., Stockholm (Sweden). Water Resources Engineering


    Dissolved gas may be released from deep groundwater in the vicinity of open boreholes and drifts, where the water pressures are relatively low. Degassing of groundwater may influence observations of hydraulic conditions made in drifts, interpretation of experiments performed close to drifts, and buffer mass and backfill performance, particularly during emplacement and repository closure. Under certain conditions, considerable fracture inflow and transmissivity reductions have been observed during degassing experiments in the field and in the laboratory; such reductions affect the outcome and interpretation of both hydraulic and tracer tests. We develop models for the estimation of the resulting degree of fracture gas saturation and the associated transmissivity reduction due to groundwater degassing in fractured rock. Derived expressions for bubble trapping probability show that fracture aperture variability and correlation length influence the conditions for capillary bubble trapping and gas accumulation. The laboratory observations of bubble trapping in an Aespoe fracture replica are consistent with the prediction of a relatively high probability of bubble trapping in this fracture. The prediction was based on the measured aperture distribution of the Aespoe fracture and the applied hydraulic gradient. Results also show that the conceptualisation of gas and water occupancy in a fracture greatly influences model predictions of gas saturation and relative transmissivity. Images from laboratory degassing experiments indicate that tight apertures are completely filled with water, whereas both gas and water exist in wider apertures under degassing conditions; implementation of this relation in our model resulted in the best agreement between predictions and laboratory observations. Model predictions for conditions similar to those prevailing in field for single fractures at great depths indicate that degassing effects in boreholes should generally be small, unless the

  12. Preparation and characterization of electrically conducting polypyrrole Sn(IV phosphate cation-exchanger and its application as Mn(II ion selective membrane electrode

    Directory of Open Access Journals (Sweden)

    A.A. Khan


    Full Text Available Polypyrrole Sn(IV phosphate, an organic–inorganic composite cation-exchanger was synthesized via sol-gel mixing of an organic polymer, polypyrrole, into the matrices of the inorganic precipitate of Sn(IV phosphate. The physico-chemical properties of the material were determined using Atomic Absorption Spectrometry (AAS, CHN elemental analysis (inductively coupled plasma mass spectrometry, ICP-MS, UV–VIS spectrophotometry, FTIR (Fourier Transform Infra-Red, SEM (Scanning Electron Microscopy, TGA–DTA (Thermogravimetric Analysis–Differential Thermal Analysis, and XRD (X-ray diffraction. Ion-exchange behavior was observed to characterize the material. On the basis of distribution studies, the material was found to be highly selective for toxic heavy metal ion Mn2+. Due to its selective nature, the material was used as an electroactive component for the construction of an ion-selective membrane electrode. The proposed electrode shows fairly good discrimination of mercury ion over several other inorganic ions. The analytical utility of this electrode was established by employing it as an indicator electrode in electrometric titrations for Mn(II in water.

  13. High-speed ion-exclusion chromatography of dissolved carbon dioxide on a small weakly acidic cation-exchange resin column with ion-exchange enhancement columns of conductivity detection. (United States)

    Mori, Masanobu; Ikedo, Mikaru; Hu, Wenzhi; Helaleh, Murad I H; Xu, Qun; Itabashi, Hideyuki; Tanaka, Kazuhiko


    The high-speed ion-exclusion chromatographic determination of dissolved carbon dioxide, i.e., carbonic acid, hydrogencarbonate or carbonate, with conductivity detection was obtained using a small column packed with a weakly acidic cation-exchange resin in the H+-form (40 mm long x 4.6 mm i.d., 3 microm-particle and 0.1 meq./ml-capacity). Two different ion-exchange resin columns, which were a strongly acidic cation-exchange resin in the K+-form and a strongly basic anion-exchange resin in the OH- -form, were connected after the separation column. The sequence of columns could convert dissolved carbon dioxide to KOH having high conductivity response. The enhancement effect for dissolved carbon dioxide could retain even on the vast chromatographic runs, by using the enhancement columns with high ion-exchange capacity above 1.0 meq./ml. The retention time was in 60 s at flow-rate of 1.2 ml/min. The calibration graph of dissolved carbon dioxide estimated as H2CO3- was linear in the range of 0.005-10 mM. The detection limit at signal to noise of 3 was 0.15 microM as H2CO3-. This method was applicable to several rainwater and tap water samples.

  14. Mantle Degassing and Diamond Genesis:A Carbon Isotope Perspective

    Institute of Scientific and Technical Information of China (English)



    The effect of Co2 and CH4 degassing from the mantle on the carbon isotopic composition of diamond has been quantitatively modeled in terms of the principles of Rayleigh distillation.Assuming the δ13 C value of -5‰ for the mantle,the outgassing of CO2 can result in the large negative δ13 C values of diamond,whereas the outgassing of CH4 can drive the δ13C values of diamond in the positive direction.The theoretical expectations can be used to explain the full range of δ13 C values from-34.4‰5 to+5‰ observed for natural diamonds.It is possible that diamond formation was triggered by the degassing of Co2 and/or CH4 from the mantle and the associated fractional crystallization of carbonate-bearing melt.

  15. Large vesicles record pathways of degassing at basalic volcanoes

    Energy Technology Data Exchange (ETDEWEB)

    Polacci, M.; Baker, D.R.; Bai, L.; Mancini, L. (McGill); (Istituto Nazionale di Geofisica e Vulcanologia); (SYRMEP Group, Sincrotrone Trieste S.C.p.A.,)


    Volcanic degassing is directly linked to magma dynamics and controls the style of eruptive activity. To better understand how gas is transported within basaltic magma we perform a 3D investigation of vesicles preserved in scoria from the 2005 activity at Stromboli volcano (Italy). We find that clasts are characterized by the ubiquitous occurrence of one to a few large vesicles, exhibiting mostly irregular, tortuous, channel-like textures, orders of magnitude greater in volume than all the other vesicles in the sample. We compare observations on natural samples with results from numerical simulations and experimental investigations of vesicle size distributions and demonstrate that this type of vesicle invariably forms in magmas with vesicularities > 0.30 (and possibly > 0.10). We suggest that large vesicles represent pathways used by gas to flow non-explosively to the surface and that they indicate the development of an efficient system that sustains persistent degassing in basaltic systems.

  16. Geophysical imaging of shallow degassing in a Yellowstone hydrothermal system (United States)

    Pasquet, S.; Holbrook, W. S.; Carr, B. J.; Sims, K. W. W.


    The Yellowstone Plateau Volcanic Field, which hosts over 10,000 thermal features, is the world's largest active continental hydrothermal system, yet very little is known about the shallow "plumbing" system connecting hydrothermal reservoirs to surface features. Here we present the results of geophysical investigations of shallow hydrothermal degassing in Yellowstone. We measured electrical resistivity, compressional-wave velocity from refraction data, and shear wave velocity from surface-wave analysis to image shallow hydrothermal degassing to depths of 15-30 m. We find that resistivity helps identify fluid pathways and that Poisson's ratio shows good sensitivity to saturation variations, highlighting gas-saturated areas and the local water table. Porosity and saturation predicted from rock physics modeling provide critical insight to estimate the fluid phase separation depth and understand the structure of hydrothermal systems. Finally, our results show that Poisson's ratio can effectively discriminate gas- from water-saturated zones in hydrothermal systems.

  17. Diffuse soil CO_2 degassing from Linosa island

    Directory of Open Access Journals (Sweden)

    Dario Cellura


    Full Text Available Normal 0 14 false false false MicrosoftInternetExplorer4 Normal 0 14 false false false IT X-NONE X-NONE MicrosoftInternetExplorer4 Herein, we present and discuss the result of 148 measurements of soil CO2 flux performed for the first time in Linosa island (Sicily Channel, Italy, a Plio-Pleistocene volcanic complex no longer active but still of interest owing to its location within a seismically active portion of the Sicily Channel rift system. The main purpose of this survey was to assess the occurrence of CO2 soil degassing, and compare flux estimations from this island with data of soil degassing from worldwide active volcanic as well as non-volcanic areas. To this aim soil CO2 fluxes were measured over a surface of about 4.2 km2 covering ~80% of the island. The soil CO2 degassing was observed to be mainly concentrated in the eastern part of the island likely due to volcano-tectonic lineaments, the presence of which is in good agreement with the known predominant regional faults system. Then, the collected data were interpreted using sequential Gaussian simulation that allowed estimating the total CO2 emissions of the island. Results show low levels of CO2 emissions from the soil of the island (~55 ton d-1 compared with CO2 emissions of currently active volcanic areas, such as Miyakejima (Japan and Vulcano (Italy. Results from this study suggest that soil degassing in Linosa is mainly fed by superficial organic activity with a moderate contribution of a deep CO2 likely driven by NW-SE trending active tectonic structures in the eastern part of the island.

  18. Influence of Non-Newtonian rheology on magma degassing

    CERN Document Server

    Divoux, Thibaut; Ripepe, Maurizio; Géminard, Jean-Christophe


    Many volcanoes exhibit temporal changes in their degassing process, from rapid gas puffing to lava fountaining and long-lasting quiescent passive degassing periods. This range of behaviors has been explained in terms of changes in gas flux and/or magma input rate. We report here a simple laboratory experiment which shows that the non- Newtonian rheology of magma can be responsible, alone, for such intriguing behavior, even in a stationary gas flux regime. We inject a constant gas flow-rate Q at the bottom of a non-Newtonian fluid column, and demonstrate the existence of a critical flow rate Q* above which the system spontaneously alternates between a bubbling and a channeling regime, where a gas channel crosses the entire fluid column. The threshold Q* depends on the fluid rheological properties which are controlled, in particular, by the gas volume fraction (or void fraction) {\\phi}. When {\\phi} increases, Q* decreases and the degassing regime changes. Non-Newtonian properties of magma might therefore play a...

  19. Hand drawing of pencil electrodes on paper platforms for contactless conductivity detection of inorganic cations in human tear samples using electrophoresis chips. (United States)

    Chagas, Cyro L S; Costa Duarte, Lucas; Lobo-Júnior, Eulício O; Piccin, Evandro; Dossi, Nicolò; Coltro, Wendell K T


    This paper describes for the first time the fabrication of pencil drawn electrodes (PDE) on paper platforms for capacitively coupled contactless conductivity detection (C(4) D) on electrophoresis microchips. PDE-C(4) D devices were attached on PMMA electrophoresis chips and used for detection of K(+) and Na(+) in human tear samples. PDE-C(4) D devices were produced on office paper and chromatographic paper platforms and their performance were thoroughly investigated using a model mixture containing K(+) , Na(+) , and Li(+) . In comparison with chromatographic paper, PDE-C(4) D fabricated on office paper has exhibited better performance due to its higher electrical conductivity. Furthermore, the detector response was similar to that recorded with electrodes prepared with copper adhesive tape. The fabrication of PDE-C(4) D on office paper has offered great advantages including extremely low cost (< $ 0.004 per unit), reduced fabrication time (< 5 min), and minimal instrumentation (pencil and paper). The proposed electrodes demonstrated excellent analytical performance with good reproducibility. For an inter-PDE comparison (n = 7), the RSD values for migration time, peak area, and separation efficiency were lower than 2.5, 10.5, and 14%, respectively. The LOD's achieved for K(+) , Na(+) , and Li(+) were 4.9, 6.8, and 9.0 μM, respectively. The clinical feasibility of the proposed approach was successfully demonstrated with the quantitative analysis of K(+) and Na(+) in tear samples. The concentration levels found for K(+) and Na(+) were, respectively, 20.8 ± 0.1 mM and 101.2 ± 0.1 mM for sample #1, and 20.4 ± 0.1 mM and 111.4 ± 0.1 mM for sample #2.

  20. Synthetic cation-selective nanotube: Permeant cations chaperoned by anions (United States)

    Hilder, Tamsyn A.; Gordon, Dan; Chung, Shin-Ho


    The ability to design ion-selective, synthetic nanotubes which mimic biological ion channels may have significant implications for the future treatment of bacteria, diseases, and as ultrasensitive biosensors. We present the design of a synthetic nanotube made from carbon atoms that selectively allows monovalent cations to move across and rejects all anions. The cation-selective nanotube mimics some of the salient properties of biological ion channels. Before practical nanodevices are successfully fabricated it is vital that proof-of-concept computational studies are performed. With this in mind we use molecular and stochastic dynamics simulations to characterize the dynamics of ion permeation across a single-walled (10, 10), 36 Å long, carbon nanotube terminated with carboxylic acid with an effective radius of 5.08 Å. Although cations encounter a high energy barrier of 7 kT, its height is drastically reduced by a chloride ion in the nanotube. The presence of a chloride ion near the pore entrance thus enables a cation to enter the pore and, once in the pore, it is chaperoned by the resident counterion across the narrow pore. The moment the chaperoned cation transits the pore, the counterion moves back to the entrance to ferry another ion. The synthetic nanotube has a high sodium conductance of 124 pS and shows linear current-voltage and current-concentration profiles. The cation-anion selectivity ratio ranges from 8 to 25, depending on the ionic concentrations in the reservoirs.

  1. Cold Model-Based Investigations to Study the Effects of Operational and Nonoperational Parameters on the Ruhrstahl-Heraeus Degassing Process (United States)

    Mukherjee, Deepjyoti; Shukla, Ajay Kumar; Senk, Dieter G.


    The circulation rate of steel is known to play a vital role in the superlative performance of the Ruhrstahl-Heraeus (RH) degasser. Numerous experiments were conducted on a physical model for the RH degassing process, which was established at IEHK, RWTH-Aachen University. The model was developed with a scale ratio of 1:3 to study the RH process. This study is conducted to show the effects of operational and nonoperational parameters on the circulation rate of liquid water in the model. The effects of lift gas flow rate, submerged depth of snorkels, water level in vessel, etc. on the circulation rate are studied. The mixing characteristics are studied with the help of current conductivity experiments for different lift gas flow rates and water levels in the vacuum vessel. Finally, the relationship between dimensionless numbers is derived with the help of the experimental data obtained from the cold model.

  2. Halogen behaviours during andesitic magma degassing: from magma chamber to volcanic plume (United States)

    Balcone-Boissard, H.; Villemant, B.; Boudon, G.; Michel, A.


    Halogen (F, Cl, Br and I) behaviours during degassing of H2O-rich silicic magmas are investigated using volatile content analysis in glass (matrix glass and melt inclusions) of volcanic clasts (pumice and lava-dome fragments) in a series of plinian, vulcanian and lava dome-forming eruptions. Examples are taken from andesitic systems in subduction zones: Montagne Pelée and Soufrière Hills of Montserrat (Lesser Antilles) and Santa Maria-Santiaguito (Guatemala). Halogens behaviour during shallow degassing primarily depends on their incompatible character in melts and on H2O solubility. But variations in pre-eruptive conditions, degassing kinetics and syn-eruptive melt crystallisation, induce large variations in halogen extraction efficiency during H2O degassing, up to prevent halogen loss. In all studied systems, Cl, Br and I are not fractionated neither by differentiation nor by degassing processes: thus Cl/Br/I ratios remain well preserved in melts from reservoirs to eruption. These ratios measured in erupted clasts are characteristic of pre-eruptive magma compositions and may be used to trace deep magmatic processes. Moreover, during plinian eruptions, Cl, Br and I are extracted by H2O degassing but less efficiently than predicted by available experimental fluid-melt partition coefficients, by a factor as high as 5. F behaves as an incompatible element and, contrary to other halogens, is never significantly extracted by degassing. Degassing during lava dome-forming eruptions of andesitic magmas occurs mainly at equilibrium and is more efficient at extracting halogens and H2O than explosive degassing. The mobility of H2O and halogens depends on their speciation in both silicate melts and exsolved fluids which strongly varies with pressure. We suggest that the rapid pressure decrease during highly explosive eruptions prevents complete volatile speciation at equilibrium and consequently strongly limits halogen degassing.

  3. The Influence of Phenocrysts on Magma Degassing in Rhyolitic Systems (United States)

    deGraffenried, R.; Larsen, J. F.; Lindoo, A. N.


    The kinetics of volatile exsolution and magma degassing control volcanic eruption styles, but the role of phenocrysts in the degassing process is poorly understood. The focus of this study is two series of decompression experiments examining how phenocrysts may or may not influence vesicle structures leading to permeability development and degassing in magmas with rhyolitic matrix melts. Powdered rhyolite obsidian (75 SiO2 wt. %; Mono Craters, CA) was seeded with 20 and 40 vol. % euhedral corundum crystals (350 μm) to approximate phenocrysts. Experiments were run using TZM (Ti-Zr-Mo alloy) vessels fitted with a water-cooled rapid quench top in a vertical Deltech furnace. Each run was held at 110 MPa and 900OC for 24 hours then decompressed continuously at a rate of 0.25 MPa/s to a final pressure (Pf) between 75 and 15 MPa. Permeability was measured using a bench-top permeameter constructed for the small experimental samples. Porosity was obtained from reflected light images using NIH Image J. The porosity of the samples increased from 11.0±1.7 to 73.3±3.1 vol % at Pf of 75 to 15 MPa for crystal free samples, 30.1±6.9 to 62.2±2.6 vol % at Pf of of 75 to 25 MPa for 20 vol % crystal samples, and 13.3±2.5 to 41.2±9.6 vol % at Pf of 75 to 50 MPa for 40 vol % crystal samples. The 20 vol % samples are impermeable up to at least 50 MPa Pf. The 40 vol % samples are impermeable up to 25 MPa Pf, with one sample having a measured Darcian permeability of -13.93±0.05 m2 at 25 MPa Pf. Comparatively, the crystal free samples were mostly impermeable up to 15 MPa, with one sample having a measured Darcian permeability of -14.41±0.04 m2 at 15 MPa Pf and 73.3 vol % porosity. Although preliminary, our permeable 40 vol % experiment suggests the phenocrysts help the samples develop permeability at a higher ending pressure and potentially lower porosity. Differences in the porosity curve as a function of pressure between the 20 and 40 vol % series indicate phenocrysts influence

  4. CO2 degassing at Papandayan and Kelud volcanoes, Java island, Indonesia (United States)

    Mazot, A.; Bernard, A.


    Papandayan volcano (2665 m a.s.l) is located in the western part of the island of Java. The last magmatic eruption of this volcano occurred in 1772. At that time, the NE sector of the volcano collapsed, producing a large avalanche of debris and creating a horseshoe shaped crater. The most recent activity of Papandayan occurred in November 2002 when the volcano erupted ash clouds to altitudes of about 5 km. Before this event, the volcano was in a state of passive degassing with solfatara, sulfur-pools and hot springs. Since 1994, the geochemistry of these hot springs is monitored. These springs are acid sulfate-chloride waters with pH between 1.5 and 2.5. Sulfur isotopic composition (delta 34: 8-14.5 per mil) clearly suggest the injection of magmatic volatiles (SO2) to the hydrothermal system present at depth.A survey of diffuse CO2 degassing using the accumulation chamber method was performed in August 2001. 420 uniformly distributed points were measured in the main crater (Kawah Emas) covering an area of 58,000 m2. At least, two distinct populations of values are present. Diffuse CO2 degassing show a wide range of values from background values up to fluxes as high as 6,190 g/m2/day. The total degassing flux of CO2 estimated for this area is 7,410 t/year. This survey was completed in September 2002 with measurements of soil CO2 concentrations (at 50 cm depth). Concentrations as high as 30 vol. % were measured in some areas and clearly revealed the position of active faults on the crater floor. Kelud volcano (1650 m a.s.l.) is located in the eastern part of Java island and contains a crater lake. The Kelud historical eruption consisted mainly of pyroclastic flow and surges. Kelud volcano is known for its devastating lahars and a system of drainage was build in 1920 in order to keep the volume of the lake to 2 million m3.The last magmatic eruption occurred in 1990. Periodical geochemical surveys were carried out at the lake waters since 1993 to understand the

  5. Atmospheric oxygenation caused by a change in volcanic degassing pressure. (United States)

    Gaillard, Fabrice; Scaillet, Bruno; Arndt, Nicholas T


    The Precambrian history of our planet is marked by two major events: a pulse of continental crust formation at the end of the Archaean eon and a weak oxygenation of the atmosphere (the Great Oxidation Event) that followed, at 2.45 billion years ago. This oxygenation has been linked to the emergence of oxygenic cyanobacteria and to changes in the compositions of volcanic gases, but not to the composition of erupting lavas--geochemical constraints indicate that the oxidation state of basalts and their mantle sources has remained constant since 3.5 billion years ago. Here we propose that a decrease in the average pressure of volcanic degassing changed the oxidation state of sulphur in volcanic gases, initiating the modern biogeochemical sulphur cycle and triggering atmospheric oxygenation. Using thermodynamic calculations simulating gas-melt equilibria in erupting magmas, we suggest that mostly submarine Archaean volcanoes produced gases with SO(2)/H(2)S atmosphere.

  6. Phenocryst compositional diversity as a consequence of degassing induced crystallization (United States)

    Frey, H. M.; Lange, R. A.


    the plagioclase crystallized. The range in dissolved water content (~6 to 0.5 wt%) in the crystal-poor lavas recorded by the plagioclase is the result of magma degassing upon ascent through the upper crust to the surface. The rapid loss of volatiles during ascent decreases the dissolved water content in the magma and induces crystallization. This is entirely consistent with the lack of zoning, euhedral shapes, and rapid-growth textures seen in the plagioclase. Degassing-induced crystallization is also supported by the compositions and textures of the pyroxene phenocrysts. In the crystal-poor lavas, the orthopyroxene and clinopyroxene phenocrysts have euhedral shapes, with compositional variation of .15 KD^{Fe-Mg} ((Fe/Mg)pyx/(Fe/Mg)liq) (e.g. 0.30-0.45), with each sample following a continuum in composition. Like the plagioclase, the compositional variation is typically not within individual pyroxene phenocrysts, which display little zoning, but the entire population. Several of the pyroxene crystals have serrated edges, a texture consistent with rapid growth. By looking in detail at the phenocrysts in less complex, crystal-poor lavas, we have recognized a process not previously considered to explain phenocryst compositional diversity in lavas. The results of this work have implications for studies of more crystal-rich lavas, typical of stratovolcanoes. Much of the compositional diversity previously attributed to magma mingling/mixing may simply be a consequence of volatile loss and degassing induced crystallization.

  7. Carbon dioxide degassing from Tuscany and Northern Latium (Italy) (United States)

    Frondini, Francesco; Caliro, Stefano; Cardellini, Carlo; Chiodini, Giovanni; Morgantini, Nicola; Parello, Franco


    The CO 2 degassing process from a large area on the Tyrrhenian side of central Italy, probably related to the input into the upper crust of mantle fluids, was investigated in detail through the geochemical study of gas emissions and groundwater. Mass-balance calculations and carbon isotopes show that over 50% of the inorganic carbon in regional groundwater is derived from a deep source highlighting gas-liquid separation processes at depth. The deep carbonate-evaporite regional aquifer acts as the main CO 2 reservoir and when total pressure of the reservoir fluid exceeds hydrostatic pressure, a free gas phase separates from the parent liquid and escapes toward the surface generating gas emissions which characterise the study area. The distribution of the CO 2 flux anomalies and the location of high PCO 2 springs and gas emissions suggest that the storage and the expulsion of the CO 2 toward the atmosphere are controlled by the geological and structural setting of the shallow crust. The average CO 2 flux and the total amount of CO 2 discharged by the study area were computed using surface heat flow, enthalpy and CO 2 molality of the liquid phase circulating in the deep carbonate-evaporite aquifer. The results show that the CO 2 flux varies from 1 × 10 4 mol y - 1 km - 2 to 5 × 10 7 mol y - 1 km - 2 , with an average value of 4.8 × 10 6 mol y - 1 km - 2 , about five times higher than the value of 1 × 10 6 mol y - 1 derived by Kerrick et al. [Kerrick, D.M., McKibben, M.A., Seward, T.M., Caldeira, K., 1995. Convective hydrothermal CO 2 emission from high heat flow regions. Chem. Geol. 121, 285-293] as baseline for terrestrial CO 2 emissions. The total CO 2 discharged from the study area is 0.9 × 10 11 mol y - 1 , confirming that Earth degassing from Tyrrhenian central Italy is a globally relevant carbon source.

  8. Process And Monitor Degasser Systems For The Sno Heavy Water System

    CERN Document Server

    Grant, D R


    The ability of the SNO detector to measure the flavour independent solar neutrino rate depends heavily on the removal of background sources like $\\sp{222}$Rn. Two degassing systems have been designed for this task in the D$\\sb2$O water system. The first is a high efficiency process degasser designed to reduce the radon load, while the second, monitor degasser, is designed to assay the D$\\sb2$O for residual radon at extremely low concentrations. The final designs are based on membrane contactor technology. These were tested and found to have good degassing efficiency ($>$97 0.000000or O$\\sb2$) with low vapour losses ($\\approx$1 ml/min). The components have been redesigned to meet the low background criteria for SNO. Two vapour recovery systems have been designed to minimize D$\\sb2$O losses. The Rn assay system has demonstrated its ability to measure ultralow Rn levels ($<

  9. Development and Application of High-Performance Magnesia-Chrome Bricks for RH Degasser

    Institute of Scientific and Technical Information of China (English)

    ZHAO Huimin; BI Yubao; LIU Xiongzhang; CHU Xuetian


    The paper analyses the wear mechanism of magnesiachrome bricks for snorkel of RH degasser. High-performance magnesia-chrome bricks with good resistance to molten slag and infiltration resistance have been manufactured by means of reasonable fabricating technology. The application results of the developed magnesia-chrome bricks at 300t RH degasser of Baosteel indicate that the lining life has been increased up to 150 heats.

  10. A new high shear degassing technology and mechanism for 7032 alloy

    Directory of Open Access Journals (Sweden)

    Yu-bo Zuo


    Full Text Available Degassing is very important for aluminum alloys especially for 7xxx series alloys. In the present study, a high shear technology was used to degas 7032 aluminum alloy in order to study its degassing efficiency. The experimental results showed that the high shear technology can significantly degas 7032 aluminum alloy. By applying intensive melt shearing and an Ar injection of 60 seconds, the density index, Di, was reduced from 13.25% to 0.28% and the hydrogen concentration was significantly reduced from 0.31 to 0.10 mL/100g Al. Compared with the conventional rotary degassing, high shear technology showed a much higher degassing efficiency, achieving a lower concentration of hydrogen in a shorter time. The water simulation experiment was used to study the mechanism of the high degassing efficiency. The small bubble size and the uniform distribution of Ar bubbles with the application of high shear technology are believed to be the main cause for the high degassing efficiency.

  11. Conduit degassing and thermal controls on eruption styles at Mount St. Helens (United States)

    Schneider, Andrew; Rempel, Alan W.; Cashman, Katharine V.


    The explosivity of silicic eruptions depends on the interplay between magma rheology, exsolution kinetics, and degassing. Magma degassing is governed by the competing effects of vertical transport within the conduit and the lateral flux of gas out of the conduit (Diller et al., 2006; Jaupart and Allegre, 1991). We combine a simplified treatment of these degassing processes with thermodynamic modeling to examine the conditions present at Mount St. Helens during the spine extruding eruption from 2004 to 2008. We find that two parameters are primarily responsible for controlling the eruptive style: the magma chamber temperature, and a dimensionless parameter that gauges the efficiency of lateral degassing. Together, these parameters determine whether and where magma can solidify at depth to form a dense solid plug that is gradually extruded as a volcanic spine. We show that the small (50 oC) decrease in magma chamber temperature between eruptive activity in the 1980s and that of 2004-2008, combined with a modest increase in degassing efficiency associated with lower volumetric flux, can explain the observed change in erupted material from viscous lava flows to solidified spines. More generally, we suggest that similar threshold behavior may explain observed abrupt transitions in effusive eruptive styles at other intermediate composition volcanoes. Finally, we extrapolate our results to suggest that the increase in degassing efficiency accompanying decreasing magma supply rates may have caused the transition from explosive to effusive activity in late 1980.

  12. Development of anammox reactor equipped with a degassing membrane to improve biomass retention. (United States)

    Matsunaga, Kosuke; Kindaichi, Tomonori; Ozaki, Noriatsu; Ohashi, Akiyoshi; Nakahara, Yoshihito; Sasakawa, Manabu


    In up-flow anammox reactors, one of the contributing factors to biomass wash-out is the adherence of nitrogen gas produced by the anammox reaction to biomass. In this study, we operated an up-flow anammox reactor equipped with a degassing membrane to minimize the biomass wash-out from the reactor by separating the produced gas from the biomass. In addition, both the effect of degassing on the anammox reactor performance and the durability of the membrane submerged in the anammox reactor were investigated. The results show that the use of the degassing membrane in the anammox reactor could (1) improve the biomass retention ability (by separating the produced gas from the biomass), and (2) increase the component ratio of anammox bacteria in the reactor. In addition, degassing could reduce the N(2)O emission produced in the reactor (for the gas selectivity of the degassing membrane). No membrane fouling was observed even after 2 months of operation without washing, indicating an advantage to the use of the degassing membrane.

  13. Vesicularity, bubble formation and noble gas fractionation during MORB degassing

    CERN Document Server

    Aubry, G; Guillot, B


    The objective of this study is to use molecular dynamics simulation (MD) to evaluate the vesicularity and noble gas fractionation, and to shed light on bubble formation during MORB degassing. A previous simulation study (Guillot and Sator (2011) GCA 75, 1829-1857) has shown that the solubility of CO2 in basaltic melts increases steadily with the pressure and deviates significantly from Henry's law at high pressures (e.g. 9.5 wt% CO2 at 50 kbar as compared with 2.5 wt% from Henry's law). From the CO2 solubility curve and the equations of state of the two coexisting phases (silicate melt and supercritical CO2), deduced from the MD simulation, we have evaluated the evolution of the vesicularity of a MORB melt at depth as function of its initial CO2 contents. An excellent agreement is obtained between calculations and data on MORB samples collected at oceanic ridges. Moreover, by implementing the test particle method (Guillot and Sator (2012) GCA 80, 51-69), the solubility of noble gases in the two coexisting pha...

  14. Chlorine and hydrogen degassing in Vesta's magma ocean (United States)

    Sarafian, Adam R.; John, Timm; Roszjar, Julia; Whitehouse, Martin J.


    The hydrophilic nature of halogens makes these elements ideal for probing potential hydrous geologic processes. Generally, in magmatic settings the stable isotopes of Cl may fractionate when H is in low concentrations and little fractionation occurs when the H concentration is high. We determined the Cl isotope composition and halogen content (F, Cl, Br, and I) of apatite and merrillite in seven basaltic eucrites, which are meteorites linked to the asteroid 4-Vesta, by using secondary ion mass spectrometry. We compare our halogen results with H isotope data, existing bulk rock concentrations, and petrologic models. The inferred Cl isotope composition of eucrites from this study, expressed in standard δ37 Cl notation, which ranges from -3.8 to 7.7‰, correlates with the bulk major- and trace-element content, e.g., the Cl isotope composition positively correlates with Mg and Sc, while Cl isotope composition negatively correlates with K, V, and Cr. Here we suggest that eucrites preserve evidence of a degassing magma ocean as evidenced by the decreasing bulk rock K content with increasing δ37 Cl . If the eucrite parent body, 4-Vesta, accreted with a negative δ37 Cl of - 3.8 ± 1.1 ‰, at least some parts of the solar nebula would have been isotopically light compared to most estimates of the Earth, which on average is close to 0‰.

  15. Infrared remote sensing of Earth degassing - Ground study

    Directory of Open Access Journals (Sweden)

    P. Strobl


    Full Text Available Geodynamical processes e.g., volcanoes, often cause degassing at the Earth surface. The geogas emanates via mineral springs, water mofettes, or dry mofettes. It is assumed that the emerging gas influences the temperature of the spring or mofette water, respectively and the surface temperature of the soil at and around the dry gas vents. This causes a thermal anomaly in comparison to the close vicinity. Under specific conditions this effect should be extractable from remotely acquired infrared images allowing detection, mapping and monitoring of gas vents/springs within large areas and short times. This article describes preparatory investigations for which emanating Earth gas was simulated by leading compressed air into the ground and releasing it in some depth via a metal lance. The thermal effect at the surface was observed from a nearby thermovision camera in summer and winter under varying meteorological conditions. A procedure was developed to reliably identify gas release areas within the recorded thermal images of the scene. The investigations are aiming at studies to be performed later in the Western Bohemia (Czech Republic earthquake swarm region where especially CO2 of magmatic origin from European SubContinental Mantle (ESCM emanates.

  16. Exposing nanobubble-like objects to a degassed environment

    CERN Document Server

    Berkelaar, Robin P; Kip, Gerard A M; Kooij, E Stefan; Zandvliet, Harold J W; Lohse, Detlef


    The primary attribute of interest of surface nanobubbles is their unusual stability and a number of theories trying to explain this have been put forward. Interestingly, the dissolution of nanobubbles is a topic that did not receive a lot of attention yet. In this work we applied two different experimental procedures which should cause gaseous nanobubbles to completely dissolve. In our experiments we nucleated nanobubble-like objects by putting a drop of water on HOPG using a plastic syringe and disposable needle. In method A, the nanobubble-like objects were exposed to a flow of degassed water (1.17 mg/l) for 96 hours. In method B, the ambient pressure was lowered in order to degas the liquid and the nanobubble-like objects. Interestingly, the nanobubble-like objects remained stable after exposure to both methods. After thorough investigation of the procedures and materials used during our experiments, we found that the nanobubble-like object were induced by the use of disposable needles in which PDMS contam...

  17. Volatile heavy metal mobility in silicate liquids: Implications for volcanic degassing and eruption prediction (United States)

    MacKenzie, Jason M.; Canil, Dante


    The volatilization of Cd, Re, Tl, Pb, Sb and Te from melts in the system CaO-MgO-Al 2O 3-SiO 2 (CMAS) and Na 2O-MgO-Al 2O 3-SiO 2 (NMAS) has been investigated at 0.1 MPa and 1200-1350 °C. Experiments were conducted in air using metal-doped melts in Pt crucibles. Analysis of quenched glasses by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) normal to the melt/gas interface produced concentration profiles for Cd, Re, Tl, Pb, Sb and Te to which a semi-infinite one-dimensional diffusion model could be applied to extract diffusion coefficients ( D). The melt was also doped with Cu, Zn, In, Mo, Sn and W but concentration profiles for these metals did not develop. In the CMAS composition at 1300 °C, the fastest diffusing element was Cd having a log DCd = - 6.5 ± 0.2. The slowest element was Re with log DRe = - 7.5 ± 0.3. Diffusivities of Sb, Te, Pb and Tl have intermediate values where log DSb = - 7.1 ± 0.1, log DTe = - 7.2 ± 0.3, log DPb = - 7.1 ± 0.2, log DTl = - 7.0 ± 0.2 cm 2/s. In the NMAS composition, log DRe = - 6.5 ± 0.2, log DSb = - 6.0 ± 0.2, log DPb = - 6.1 ± 0.1, log DTl = - 5.8 ± 0.2 cm 2/s (values for Cd and Te were not determined). Differences in diffusivity of volatile heavy metal ions to a melt-gas interface lead to significant fractionation between these metals in magmas during degassing. Given the observed differences in Cd and Re diffusivities in the CMAS composition, we predict an increase in the normalized Cd/Re ratio in the gas phase with increasing bubble growth rate. Monitoring of the Cd/Re ratios in aerosols from degassing volcanoes may provide a tool for predicting volcanic eruption.

  18. In situ baking method for degassing of a kicker magnet in accelerator beam line

    Energy Technology Data Exchange (ETDEWEB)

    Kamiya, Junichiro, E-mail:; Ogiwara, Norio; Yanagibashi, Toru; Kinsho, Michikazu [Japan Atomic Energy Agency, J-PARC Center, Ooaza Shirakata 2-4, Tokai, Naka, Ibaraki 319-1195 (Japan); Yasuda, Yuichi [SAKAGUCHI E.H VOC CORP., Sakura Dai-san Kogyodanchi 1-8-6, Osaku, Sakura, Chiba 285-0802 (Japan)


    In this study, the authors propose a new in situ degassing method by which only kicker magnets in the accelerator beam line are baked out without raising the temperature of the vacuum chamber to prevent unwanted thermal expansion of the chamber. By simply installing the heater and thermal radiation shield plates between the kicker magnet and the chamber wall, most of the heat flux from the heater directs toward the kicker magnet. The result of the verification test showed that each part of the kicker magnet was heated to above the target temperature with a small rise in the vacuum chamber temperature. A graphite heater was selected in this application to bake-out the kicker magnet in the beam line to ensure reliability and easy maintainability of the heater. The vacuum characteristics of graphite were suitable for heater operation in the beam line. A preliminary heat-up test conducted in the accelerator beam line also showed that each part of the kicker magnet was successfully heated and that thermal expansion of the chamber was negligibly small.

  19. Pool boiling heat transfer of deionized and degassed water in packed-perforated copper beads (United States)

    Wen, Mao-Yu; Jang, Kuang-Jang; Ho, Ching-Yen


    Nucleate pool boiling with porous media made of perforated copper beads as the enhanced structure is conducted in saturated, deionized and degassed water. Data are taken at an atmospheric pressure (saturation temperature of 100 °C) and at heat fluxes from 4500 to 72,300 W/m2 while increasing the heat flux. The bead-packed structure is heated on the bottom. The layer of loose particles on the heated surface is free to move under the action of bulk liquid convection and vapor nucleation. The effects of the weight (number), size and layers of the free particles are experimentally explored using copper particles for different copper bead diameters which were 2, 3, 4 and 5 mm. The boiling enhancement is closely related to the particle weight, size and layers, and the heat flux applied. The results show that free particles are presented to have a distinct advantage in boiling heat transfer, resulting in an average increase in the heat transfer coefficient of 126 % relative to the flat plate without particles. In order to obtain insight into the fluid boiling phenomena, flow visualization is also made to observe the detailed fluid boiling characteristics of the copper particles present. The visualizations show that bubble nucleation preferentially occurs at the narrow corner cavities formed between the free particles and the heated surface.

  20. Effects of solution degassing on solubility, crystal growth and dissolution-Case study: Salicylic acid in methanol (United States)

    Seidel, J.; Ulrich, J.


    The influence of dissolved gases on the crystallization parameter solubility, MZW, growth and dissolution rates was investigated experimentally using degassed and non-degassed (air-saturated) solutions. The results of this study show that degassing has no effect on the solubility curve of the used model substance salicylic acid (SA) in methanol (MeOH). This reveals in the assumption that a thermodynamic effect of dissolved gases can be excluded. Growth rates were measured by means of a desupersaturation method and the results indicate that the growth rates of SA are not affected by degassing. The results of the dissolution rate measurements reveal a distinct decrease in dissolution rates for non-degassed solutions compared to degassed solutions, especially, at low temperature (10 °C). To explain this phenomenon the gas solubility, represented by oxygen, in MeOH in dependence on the SA concentration was estimated by means of Hansen Solubility Parameters (HSP) [1]. It was found that the oxygen solubility decreases with increasing SA content which explains the inhibition of crystal dissolution in non-degassed solution compared to degassed solution. Moreover, this kind of 'drowing-out' mechanism would not appear in growth rate measurements, where indeed no effect of degassing could be observed.

  1. Poás volcano: Relationships between diffuse vs active CO degassing and long term volcanic activity. (United States)

    Epiard, Matthieu; Avard, Geoffroy; de Moor, Marteen; Martinez Cruz, Maria; Bakkar, Henriette


    Active volcanoes exhibit diffuse gas emanations through the ground. Carbon dioxide is one of the most abundant species, in addition to the gases actively released through channelized vents. CO₂ diffuse degassing is not always correlated to volcanic activity but CO₂ diffuse vs active degassing ratios appears to show interesting behavior regarding fluctuations in volcanic activity. CO₂ diffuse degassing data were obtained at Poás volcano (Costa Rica) in 2011 using the accumulation chamber method with the aim of estimating the total diffuse CO₂ budget. This result was compared to active degassing data, as well as to previous CO₂ diffuse degassing data measured between 2000 and 2004, when Poás entered in a stage of enhanced volcanic activity. Results show a dramatic decrease in CO₂ diffuse degassing rate between 2000 and 2011 of more than 500t/d, following an increasing trend in total gas emission and power output between September 1995 and the end of 2001. Thus, the ratio of diffuse to active degassing has dramatically decreased with the increase of volcanic activity and occurrence of phreatic eruption. Two main hypothesis could explain those results: 1) Either the rising of magma to shallower levels allows the gas to be better channelized due to enhanced permeability and conduit opening, or 2) Poás volcano might experience a periodic pattern of hydrothermal sealing/overpressure/eruption that allows the system to shift from a regimen of passive degassing to active degassing.

  2. Reprint of: Effects of solution degassing on solubility, crystal growth and dissolution-Case study: Salicylic acid in methanol (United States)

    Seidel, J.; Ulrich, J.


    The influence of dissolved gases on the crystallization parameter solubility, MZW, growth and dissolution rates was investigated experimentally using degassed and non-degassed (air-saturated) solutions. The results of this study show that degassing has no effect on the solubility curve of the used model substance salicylic acid (SA) in methanol (MeOH). This reveals in the assumption that a thermodynamic effect of dissolved gases can be excluded. Growth rates were measured by means of a desupersaturation method and the results indicate that the growth rates of SA are not affected by degassing. The results of the dissolution rate measurements reveal a distinct decrease in dissolution rates for non-degassed solutions compared to degassed solutions, especially, at low temperature (10 °C). To explain this phenomenon the gas solubility, represented by oxygen, in MeOH in dependence on the SA concentration was estimated by means of Hansen Solubility Parameters (HSP) [1]. It was found that the oxygen solubility decreases with increasing SA content which explains the inhibition of crystal dissolution in non-degassed solution compared to degassed solution. Moreover, this kind of 'drowing-out' mechanism would not appear in growth rate measurements, where indeed no effect of degassing could be observed.

  3. Depth of volcanic basalt degassing forecasted from CO2 fluid inclusions

    Institute of Scientific and Technical Information of China (English)


    Fluid inclusions have recorded the history of degassing in basalt. Some fluid inclusions in olivine and pyroxene phenocrysts of basalt were analyzed by micro-thermometry and Raman spectroscopy in this paper. The experimental results showed that many inclusions are present almost in a pure CO2 system. The densities of some CO2 inclusions were computed in terms of Raman spectroscopic characteristics of CO2 Fermi resonance at room temperature. Their densities change over a wide range, but mainly between 0.044 g/cm3 and 0.289 g/cm3. Their micro-thermometric measurements showed that the CO2 inclusions examined reached homogenization between 1145.5℃ and 1265℃. The mean value of homogenization temperatures of CO2 inclusions in basalts is near 1210℃. The trap pressures (depths) of inclusions were computed with the equation of state and computer program. Distribution of the trap depths makes it know that the degassing of magma can happen over a wide pressure (depth) range, but mainly at the depth of 0.48 km to 3.85 km. This implicates that basalt magma experienced intensive degassing and the CO2 gas reservoir from the basalt magma also may be formed in this range of depths. The results of this study showed that the depth of basalt magma degassing can be forecasted from CO2 fluid inclusions, and it is meaningful for understanding the process of magma degassing and constraining the inorganogenic CO2 gas reservoir.

  4. Geophysical Images of the Shallow Hydrothermal Degassing at Solfatara (Phlegrean Fields, Italy) (United States)

    Byrdina, S.; Vandemeulebrouck, J.; Cardellini, C.; Chiodini, G.; Legaz, A.; Camerlynck, C.; Lebourg, T.


    We present the results of an electric resistivity tomography (ERT) survey, combined with mappings of diffuse carbon dioxide flux, ground temperature and self-potential (SP) at Solfatara, the most active crater of Phlegrean Fields. Solfatara is characterized by an intense carbon dioxide degassing, fumarole activity, and ground deformation. This ensemble of methods is applied to image the hydrothermal system of Solfatara, to understand the geometry of the fluid circulation, and to define the extension of the hydrothermal plume at a high enough resolution for a quantitative modeling. ERT inversion results show Solfatara as a globally conductive structure, with resistivity in the range 1-200 Ohmm. Broad negative anomaly of self-potential in the inner part of Solfatara with a minimum in the area of Bocca Grande suggests a significant downward flow of condensing liquid water. Comparison between spatial variations of resistivity and gas flux indicates that resistivity changes at depth are related to gas saturation and fluid temperature. These variations delineate two plume structures: a liquid-dominated conductive plume below Fangaia mud-pool and a gas-dominated plume below Bocca Grande fumarole. The geometry of the Fangaia liquid-saturated plume is also imaged by a high resolution 3-D resistivity model. In order to estimate the permeability, we propose a 2-D axis-symmetric numerical model coupling Richards's equation for fluid flow in conditions of partial saturation with the resistivity calculation as function of saturation only. Alternatively, we apply the Dupuit equation to estimate the permeability of the shallow layer. Using these two approaches, we obtain the permeability of the shallow layer below Fangaia which ranges between (2 - 4) 10-14 m 2.

  5. Cation-cation interaction in neptunyl(V) compounds

    Energy Technology Data Exchange (ETDEWEB)

    Krot, N.N. [Russian Academy of Sciences, Institute of Physical Chemistry (Russian Federation); Saeki, Masakatsu [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment


    The original manuscript was prepared by Professor N.N. Krot of Institute of Physical Chemistry, Russian Academy of Sciences, in 1997. Saeki tried to translate that into Japanese and to add some new data since 1997. The contents include the whole picture of cation-cation interactions mainly in 5-valence neptunium compounds. Firstly, characteristic structures of neptunium are summarized of the cation-cation bonding in compounds. Secondly, it is mentioned how the cation-cation bonding affects physical and chemical properties of the compounds. Then, characterization-methods for the cation-cation bonding in the compounds are discussed. Finally, the cation-cation interactions in compounds of other actinide-ions are shortly reviewed. (author)

  6. Long-term explosive degassing and debris flow activity at West Mata submarine volcano (United States)

    Dziak, R. P.; Bohnenstiehl, D. R.; Baker, E. T.; Matsumoto, H.; Caplan-Auerbach, J.; Embley, R. W.; Merle, S. G.; Walker, S. L.; Lau, T.-K.; Chadwick, W. W.


    West Mata is a 1200 m deep submarine volcano where explosive boninite eruptions were observed in 2009. The acoustic signatures from the volcano's summit eruptive vents Hades and Prometheus were recorded with an in situ (~25 m range) hydrophone during ROV dives in May 2009 and with local (~5 km range) moored hydrophones between December 2009 and August 2011. The sensors recorded low frequency (1-40 Hz), short duration explosions consistent with magma bubble bursts from Hades, and broadband, 1-5 min duration signals associated with episodes of fragmentation degassing from Prometheus. Long-term eruptive degassing signals, recorded through May 2010, preceded a several month period of declining activity. Degassing episodes were not recorded acoustically after early 2011, although quieter effusive eruption activity may have continued. Synchronous optical measurements of turbidity made between December 2009 and April 2010 indicate that turbidity maxima resulted from occasional south flank slope failures triggered by the collapse of accumulated debris during eruption intervals.

  7. CO2, SO2, and H2S Degassing Related to the 2009 Redoubt Eruption, Alaska (United States)

    Werner, C. A.; Kelly, P. J.; Evans, W.; Doukas, M. P.; McGimsey, R. G.; Neal, C. A.


    The 2009 eruption of Redoubt Volcano, Alaska was particularly well monitored for volcanic gas emissions with 35 airborne measurements of CO2, SO2, and H2S that span from October 2008 to August 2010. Increases in CO2 degassing were detected up to 5 months prior to the eruption and varied between 3630 and 9020 tonnes per day (t/d) in the 6 weeks prior to the eruption. Increased pre-eruptive CO2 degassing was accompanied by comparatively low S emission, resulting in molar C/S ratios that ranged between 30-60. However, the C/S ratio dropped to 2.4 coincident with the first phreatic explosion on March 15, 2009, and remained steady during the explosive (March 22 - April 4, 2009), effusive dome-building (April 5 - July 1, 2009), and waning phases (August 2009 onward) of the eruption. Observations of ice-melt rates, melt water discharge, and water chemistry in the months leading up to the eruption suggested that surface waters represented drainage from surficial, perched reservoirs of condensed magmatic steam and glacial meltwater. While the surface waters were capable of scrubbing many thousands of t/d of SO2, sampling of these fluids revealed that only a few hundred tonnes of SO2 was reacting to a dissolved component each day. This is also much less than the ~ 2100 t/d SO2 expected from degassing of magma in the upper crust (3-6.5 km), where petrologic analysis shows the final magma equilibration occurred. Thus, the high pre-eruptive C/S ratios observed could reflect bulk degassing of upper-crustal magma followed by nearly complete loss of SO2 in a magmatic-hydrothermal system. Alternatively, high C/S ratios could be attributed to degassing of low silica andesitic magma that intruded into the mid-crust in the 5 months prior to eruption; modeling suggests that mixing of this magma with pre-existing high silica andesite magma or mush would have caused a reduction of the C/S ratio to a value consistent with that measured during the eruption. Monitoring emissions regularly

  8. Pretreatment of Process Condensate with Ammonia Degassing in CAN Fertilizer Production

    Directory of Open Access Journals (Sweden)

    Leaković, S.


    Full Text Available In the production process of calcium ammonium nitrate (CAN fertilizer, process-condensate is generated with a high content of ammonium nitrogen. Such high mass concentration of ammonium nitrogen (approximately 2 g L-1 significantly burdens the operation of the wastewater treatment plant, where the process condensate is treated by method of ion exchange. At CAN 1 Plant, a degassing system for process condensate was built. After pretreatment, the concentration of ammonium nitrogen in the process condensate was reduced to less than 500 mg L-1.Before upgrading with degassing system, the process condensate from CAN 1 Plant was collected in tank TK 17 301, from which it was pumped to the wastewater treatment plant to be treated by the method of ion exchange. When CAN 1 Plant is in normal operation, 10 m3h-1 of process condensate is formed with pH around 10, and temperatures around 50 °C. The degassing system of process condensate consists of a new tank, TK 17 504, which is connected with new pipeline to the tank TK 17 301. The process condensate input was transferred from the old to the new tank, TK 17 504. A new pump was installed for regulation of process condensate and bursting above the condensate level.Additional stimulation for ammonia degassing followed, after the return of 12 bar steam condensate into the tank TK 17 504. Consequently, the process condensate temperature increased to 80 C. Degassed ammonia is introduced into the existing system for washing gases and returns into the process of fertilizer production.By degassing ammonia from the process condensate at CAN 1 Plant, 10.7 kg h-1of ammonia returns into the fertilizer production process.Additionally, there has been an improved performance of the wastewater treatment plant, so that in December 2010, the volume of treated wastewater was almost 80 000 m3 which is an increase of 86 %.

  9. Groundwater degassing and two-phase flow in fractured rock: Summary of results and conclusions achieved during the period 1994-2000

    Energy Technology Data Exchange (ETDEWEB)

    Jarsjoe, J.; Destouni, G. [Royal Inst. of Technology, Stockholm (Sweden). Water Resources Engineering; Gale, J. [Fracflow Consultants Inc., (Canada)


    drifts, by summarising and systematically interpreting all available laboratory and field investigations that have been conducted within the SKB degassing and two-phase flow programme. Data from various sites in Sweden show that the volumetric percent gas coming out of solution as the pressure of deep groundwater is lowered down to atmospheric pressure is generally less than 5%. Laboratory experiments and an analytical expression showed that conditions often are favourable for trapping and accumulation of gas bubbles in the fracture pore space (once bubbles are formed), implying that local fracture gas saturation degrees may become considerable, even though the evolved percent gas per unit volume flowing water is relatively low. For instance, a saturation degree of 40% was observed in a laboratory fracture for 7% evolved gas. However, degassing effects such as inflow reductions to boreholes and drifts will not be considerable unless the potential degassing zone (where the water pressure is lower than the gas bubble pressure) is sufficiently large in relation to the total length of the fracture. A series of borehole test conducted at Aespoe HRL between 300 and 450 meters depth indicated that degassing only causes considerable flow reductions for gas contents that are well above the normal ones in Swedish granitic bedrock. This field result was reproduced by a predictive degassing model, developed considering independent degassing observations in the laboratory. Since the model predictions were shown to be robust with regard to plausible variable ranges for rock fractures intersecting boreholes at depths between 20 and 600 metres, we conclude more generally that groundwater degassing will not cause considerable inflow reductions in fractures intersecting open boreholes under conditions normal for Swedish granitic bedrock. We also considered the relatively large drift inflow reductions observed in the Stripa simulated drift experiment. These reductions were hypothesised to

  10. Cation locations and dislocations in zeolites (United States)

    Smith, Luis James

    The focus of this dissertation is the extra-framework cation sites in a particular structural family of zeolites, chabazite. Cation sites play a particularly important role in the application of these sieves for ion exchange, gas separation, catalysis, and, when the cation is a proton, acid catalysis. Structural characterization is commonly performed through the use of powder diffraction and Rietveld analysis of powder diffraction data. Use of high-resolution nuclear magnetic resonance, in the study of the local order of the various constituent nuclei of zeolites, complements well the long-range order information produced by diffraction. Recent developments in solid state NMR techniques allow for increased study of disorder in zeolites particularly when such phenomena test the detection limits of diffraction. These two powerful characterization techniques, powder diffraction and NMR, offer many insights into the complex interaction of cations with the zeolite framework. The acids site locations in SSZ-13, a high silica chabazite, and SAPO-34, a silicoaluminophosphate with the chabazite structure, were determined. The structure of SAPO-34 upon selective hydration was also determined. The insensitivity of X-rays to hydrogen was avoided through deuteration of the acid zeolites and neutron powder diffraction methods. Protons at inequivalent positions were found to have different acid strengths in both SSZ-13 and SAPO-34. Other light elements are incorporated into zeolites in the form of extra-framework cations, among these are lithium, sodium, and calcium. Not amenable by X-ray powder diffraction methods, the positions of such light cations in fully ion-exchanged versions of synthetic chabazite were determined through neutron powder diffraction methods. The study of more complex binary cation systems were conducted. Powder diffraction and solid state NMR methods (MAS, MQMAS) were used to examine cation site preferences and dislocations in these mixed-akali chabazites

  11. Volatile Solubilities in Mt. Somma-Vesuvius Phonolite Melt and New Insights on Degassing of Sulfur, Chlorine, and Water (United States)

    Webster, J. D.; Sintoni, M. F.; de Vivo, B.; Lima, A.


    To better understand volatile exsolution, degassing, and eruptive processes in subduction-related magmas, we have conducted thirty H2O plus S plus Cl solubility experiments with phonolite melt at 905 to 1000 deg. C, 200 MPa, and relatively oxidizing conditions. The experiments include an 8000-year old Mt. Somma-Vesuvius phonolite, distilled H2O, NaCl, KCl, and CaSO4, and they involve a new method of constraining the concentration of S in the run-product fluids. Unlike prior S-solubility experiments, the S concentration in fluid is determined as proportional to the mass loss of the anhydrite crystals in the starting charges of the experiments. This method provides accurate S contents of fluids. The H2O, Cl, and S concentrations of the phonolitic glasses of our experiments range from 4 to 8, 0.38 to 0.84, and 0.01 to 0.19 wt.%, respectively. Sulfur solubility increases with increasing CaO and FeO (total iron) in melt, decreasing Cl and K2O in melt, decreasing Cl in fluid(s), and with increasing oxygen fugacity values greater than NNO. Chlorine solubility in melt increases with decreasing S content of melt and decreasing S and H2O in the coexisting fluid(s). Water solubility in melt shows no systematic variation with melt composition, but varies strongly with the composition of fluids. The partition coefficients (wt.% of X in fluid[s]/wt.% of X in phonolitic melt) range from 40 to > 200 for S and from 12 to 87 for Cl. At pressure-temperature-oxygen fugacity conditions similar to those of this study, these partition coefficients are equivalent to those determined previously for natural equilibria involving andesite melt plus Cl-free, S-bearing aqueous fluid (Scaillet and Pichavant, 2003) and experimental equilibria with andesite melt plus S-free, Cl-bearing aqueous fluid (Webster et al., 1999), respectively. Our research also shows that these partition coefficients for S and Cl are inversely proportional to one another. Silicate melt inclusions in pyroxene phenocrysts

  12. Constraining the sulfur dioxide degassing flux from Turrialba volcano, Costa Rica using unmanned aerial system measurements (United States)

    Xi, Xin; Johnson, Matthew S.; Jeong, Seongeun; Fladeland, Matthew; Pieri, David; Diaz, Jorge Andres; Bland, Geoffrey L.


    Observed sulfur dioxide (SO2) mixing ratios onboard unmanned aerial systems (UAS) during March 11-13, 2013 are used to constrain the three-day averaged SO2 degassing flux from Turrialba volcano within a Bayesian inverse modeling framework. A mesoscale model coupled with Lagrangian stochastic particle backward trajectories is used to quantify the source-receptor relationships at very high spatial resolutions (i.e., < 1 km). The model shows better performance in reproducing the near-surface meteorological properties and observed SO2 variations when using a first-order closure non-local planetary boundary layer (PBL) scheme. The optimized SO2 degassing fluxes vary from 0.59 ± 0.37 to 0.83 ± 0.33 kt d- 1 depending on the PBL scheme used. These fluxes are in good agreement with ground-based gas flux measurements, and correspond to corrective scale factors of 8-12 to the posteruptive SO2 degassing rate in the AeroCom emission inventory. The maximum a posteriori solution for the SO2 flux is highly sensitive to the specification of prior and observational errors, and relatively insensitive to the SO2 loss term and temporal averaging of observations. Our results indicate relatively low degassing activity but sustained sulfur emissions from Turrialba volcano to the troposphere during March 2013. This study demonstrates the utility of low-cost small UAS platforms for volcanic gas composition and flux analysis.

  13. Volcanic degassing at Somma-Vesuvio (Italy) inferred by chemical and isotopic signatures of groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Caliro, S. [Osservatorio Vesuviano sezione di Napoli dell' Istituto, Nazionale Geofisica Vulcanologia, Via Diocleziano 328, 80124 Naples (Italy)]. E-mail:; Chiodini, G. [Osservatorio Vesuviano sezione di Napoli dell' Istituto, Nazionale Geofisica Vulcanologia, Via Diocleziano 328, 80124 Naples (Italy); Avino, R. [Osservatorio Vesuviano sezione di Napoli dell' Istituto, Nazionale Geofisica Vulcanologia, Via Diocleziano 328, 80124 Naples (Italy); Cardellini, C. [Dipartimento di Scienze della Terra, Universita di Perugia (Italy); Frondini, F. [Dipartimento di Scienze della Terra, Universita di Perugia (Italy)


    A geochemical model is proposed for water evolution at Somma-Vesuvio, based on the chemical and isotopic composition of groundwaters, submarine gas emission and chemical composition of the dissolved gases. The active degassing processes, present in the highest part of the volcano edifice, strongly influence the groundwater evolution. The geological-volcanological setting of the volcano forces the waters infiltrating at Somma-Vesuvio caldera, enriched in volcanic gases, to flow towards the southern sector to an area of high pCO{sub 2} groundwaters. Reaction path modelling applied to this conceptual model, involving gas-water-rock interaction, highlights an intense degassing process in the aquifer controlling the chemical and isotopic composition of dissolved gases, total dissolved inorganic C (TDIC) and submarine gas emission. Mapping of TDIC shows a unique area of high values situated SSE of Vesuvio volcano with an average TDIC value of 0.039 mol/L, i.e., one order of magnitude higher than groundwaters from other sectors of the volcano. On the basis of TDIC values, the amount of CO{sub 2} transported by Vesuvio groundwaters was estimated at about 150 t/d. This estimate does not take into account the fraction of gas loss by degassing, however, it represents a relevant part of the CO{sub 2} emitted in this quiescent period by the Vesuvio volcanic system, being of the same order of magnitude as the CO{sub 2} diffusely degassed from the crater area.

  14. Process-time Optimization of Vacuum Degassing Using a Genetic Alloy Design Approach

    NARCIS (Netherlands)

    Dilner, D.; Lu, Q.; Mao, H.; Xu, W.; Van der Zwaag, S.; Selleby, M.


    This paper demonstrates the use of a new model consisting of a genetic algorithm in combination with thermodynamic calculations and analytical process models to minimize the processing time during a vacuum degassing treatment of liquid steel. The model sets multiple simultaneous targets for final S,

  15. Halogen degassing during ascent and eruption of water-poor basaltic magma (United States)

    Edmonds, M.; Gerlach, T.M.; Herd, Richard A.


    A study of volcanic gas composition and matrix glass volatile concentrations has allowed a model for halogen degassing to be formulated for K??lauea Volcano, Hawai'i. Volcanic gases emitted during 2004-2005 were characterised by a molar SO2/HCl of 10-64, with a mean of 33; and a molar HF/HCl of 0-5, with a mean of 1.0 (from approximately 2500 measurements). The HF/HCl ratio was more variable than the SO2/HCl ratio, and the two correlate weakly. Variations in ratio took place over rapid timescales (seconds). Matrix glasses of Pele's tears erupted in 2006 have a mean S, Cl and F content of 67, 85 and 173??ppm respectively, but are associated with a large range in S/F. A model is developed that describes the open system degassing of halogens from parental magmas, using the glass data from this study, previously published results and parameterisation of sulphur degassing from previous work. The results illustrate that halogen degassing takes place at pressures of pressure, virtually at the top of the magma column. This model reproduces the volcanic gas data and other observations of volcanic activity well and is consistent with other studies of halogen degassing from basaltic magmas. The model suggests that variation in volcanic gas halogen ratios is caused by exsolution and gas-melt separation at low pressures in the conduit. There is no evidence that either diffusive fractionation or near-vent chemical reactions involving halogens is important in the system, although these processes cannot be ruled out. The fluxes of HCl and HF from K??lauea during 2004-5 were ~ 25 and 12??t/d respectively. ?? 2008 Elsevier B.V.

  16. Degassing history of water, sulfur, and carbon in submarine lavas from Kilauea Volcano, Hawaii

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, J.E.; Stolper, E.M. (California Institute of Technology, Pasadena (USA)); Clague, D.A. (Geological Survey, Menlo Park, CA (USA))


    Major, minor, and dissolved volatile element concentrations were measured in tholeiitic glasses from the submarine portion (Puna Ridge) of the east rift zone of Kilauea Volcano, Hawaii. Dissolved H{sub 2}O and S concentrations display a wide range relative to nonvolatile incompatible elements at all depths. This range cannot be readily explained by fractional crystallization, degassing of H{sub 2}O and S during eruption on the seafloor, or source region heterogeneities. Dissolved CO{sub 2} concentrations, in contrast, show a positive correlation with eruption depth and typically agree within error with the solubility at that depth. The authors propose that most magmas along the Puna Ridge result from (1) mixing of a relatively volatile-rich, undegassed component with magmas that experienced low pressure (perhaps subaerial) degassing during which substantial H{sub 2}O, S, and CO{sub 2} were lost, followed by (2) fractional crystallization of olivine, clinopyroxene, and plagioclase from this mixture to generate a residual liquid; and (3) further degassing, principally of CO{sub 2} for samples erupted deeper than 1,000 m, during eruption on the seafloor. They predict that average Kilauean primary magmas with 16% MgO contain {approximately}0.47 wt % H{sub 2}0, {approximately}900 ppm S, and have {delta}D values of {approximately}{minus}30 to {minus}40%. The model predicts that submarine lavas from wholly submarine volcanoes (i.e., Loihi), for which there is no opportunity to generate the degassed end member by low pressure degassing, will be enriched in volatiles relative to those from volcanoes whose summits have breached the sea surface (i.e., Kilauea and Mauna Loa).

  17. Geochemical and Textural Evidence for Transitions in Degassing Regimes at Merapi Volcano, Java, Indonesia (United States)

    Genareau, K. D.; Cronin, S. J.; Lube, G.


    Transitions in degassing regimes at erupting volcanoes can cause significant changes in magma rheology and the intensity of eruptive activity. The October/November 2010 events at Merapi Volcano, Java, Indonesia began with an intrusive stage (Phase 1), followed by an explosion on October 26th (Phase 2) that removed the pre-existing dome causing deadly pyroclastic density currents (PDCs). This led to rapid ascent of juvenile magma that progressively degassed and crystallized until a large-scale collapse (Phase 3) of the new lava dome on November 5th and associated explosions produced even larger PDCs, killed more citizens, and destroyed several more distal villages. PDC deposits from the two main surge events on October 26th and November 5th, in addition to tephras generated by intermediate explosions, were sampled from numerous locations on the edifice. Secondary ion mass spectrometer (SIMS) depth profiling analyses were performed on free feldspar phenocrysts from the PDC deposits to examine the behavior of volatile elements during the eruptive events of 2010. Phenocrysts were mounted in indium and depth profiled with an O2+ primary ion beam for 2-14 hours. Profiles encounter glass and groundmass on the surface of the crystals before the feldspar is reached, determined from the point at which the B/Si and F/Si signals fall below detection limits. For all samples, the H/Si signal decreases from the glass into the crystal, but the Li/Si signal behaves differently between samples from Phase 2 and Phase 3. In Phase 2 samples, Li/Si ratios are higher in the glass compared to the crystal, revealing a build-up of Li in the groundmass not observed in Phase 3 samples. These observations suggest that Li was able to successfully diffuse out of both the feldspar and the surrounding groundmass in the Phase 3 products, but remained trapped in the groundmass of the Phase 2 products. The build-up of Li in the groundmass, coupled with textural evidence of a late-stage vesiculation

  18. Multiparametric Experiment at Mt. Etna: Investigation on Both Degassing and Eruptive Dynamics (United States)

    Cannata, A.; Privitera, E.


    In the framework of the MED-SUV project, a multi-parametric experiment to investigate degassing, explosive and effusive dynamics was performed at Mt. Etna volcano in July 2014. The experiment has involved the so-called "Scientific Team of NEC multi-parametric experiment" composed of researchers/technicians from different institutions in Italy, Germany and France: D. Andronico, T. Barnie, A. Boselli, M. Burton, T. Caltabiano, A. Cannata, D. Carbone, A. Chiarugi, F. Ciancitto, D. Contrafatto, S. Corradini, F. D'Amato, E. Del Bello, F. Donnadieu, F. Ferrari, A. Ferro, S. Gambino, F. Greco, A. Harris, U. Kueppers, A. La Spina, P. Labazuy, G. Leto, L. Lodato, R. Maugeri, L. Merucci, S. Moune, R. Paris, J.J. Pena Fernandez, E. Privitera, M. Queisser, T. Ricci, G. Salerno, R. Z. Sanchez, P. Scarlato, M. Sciotto, S. Scollo, L. Scuderi, J. Sesterhenn, L. Spampinato, L. Spina, J. Taddeucci, X. Wang, L. Zuccarello. The aim was two-fold: first, to study degassing processes at Etna's NE Crater (NEC); second, to investigate the activity at the eruptive fissure (EF) that opened at the base of the NEC in early-July 2014. Indeed, NEC is the main contributor to Etna's gas release, and continuously generates infrasonic events: a result of its impulsive degassing regime. Moreover, the opening of the EF offered a unique opportunity to investigate the partitioning of energy and geophysical signals between degassing, explosive and effusive sources. The field campaign involved coupled deployment of seismometers, microphones, thermopiles, a mini-UV scanner, FTIR spectrometer, SO2 camera systems, high-speed video cameras, thermal and visible cameras, gravimeters, tiltmeters, drones, laser HCl sensor, Lidar and satellite data. Moreover, this experiment gave the opportunity to test the prototype of a DIAL for volcanic CO2 sensing the first time in a volcanic environment. Gathered information were integrated with data simultaneously recorded by the permanent networks run by Istituto Nazionale

  19. Migration of Cations and Anions in Amorphous Polymer Electrolytes

    Institute of Scientific and Technical Information of China (English)

    N.A.Stolwijk; S.H.Obeidi; M.Wiencierz


    1 Results Polymer electrolytes are used as ion conductors in batteries and fuel cells.Simple systems consist of a polymer matrix complexing an inorganic salt and are fully amorphous at the temperatures of interest.Both cations and anions are mobile and contribute to charge transport.Most studies on polymer electrolytes use the electrical conductivity to characterize the ion mobility.However,conductivity measurements cannot discriminate between cations and anions.This paper reports some recent results fr...

  20. Degassing measurement for beryllium exposed to D{sub 2} atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Markin, A.V.; Zakharov, A.P. [Russian Academy of Sciences, Moscow (Russian Federation). Inst. of Physical Chemistry


    A possibility of the correct determination of deuterium solubility and diffusivity in Be on the basis of degassing experiments is demonstrated. It has been found that the main fraction (above 90%) of deuterium retained under D{sub 2} exposure is removed under slight electropolishing (descaling of {approx} 2-5 {mu}m) of the samples before TDS measurement. This deuterium seems to be located in the near surface oxide layers formed during the exposure as a result of interaction of beryllium with oxygen containing molecules of residual gas. In all degassing runs the diffusion of deuterium in the bulk of beryllium samples was not a limited-stage of gas release. (author)

  1. Integrative device and process of oxidization, degassing, acidity adjustment of 1BP from APOR process

    Energy Technology Data Exchange (ETDEWEB)

    Zuo, Chen; Zheng, Weifang, E-mail:; Yan, Taihong; He, Hui; Li, Gaoliang; Chang, Shangwen; Li, Chuanbo; Yuan, Zhongwei


    Graphical abstract: Previous (left) and present (right) device of oxidation, degassing, acidity adjustment of 1BP. - Highlights: • We designed an integrative device and process. • The utilization efficiency of N{sub 2}O{sub 4} is increased significantly. • Our work results in considerable simplification of the device. • Process parameters are determined by experiments. - Abstract: Device and process of oxidization, degassing, acidity adjustment of 1BP (The Pu production feed from U/Pu separation section) from APOR process (Advanced Purex Process based on Organic Reductants) were improved through rational design and experiments. The device was simplified and the process parameters, such as feed position and flow ratio, were determined by experiments. Based on this new device and process, the reductants N,N-dimethylhydroxylamine (DMHAN) and methylhydrazine (MMH) in 1BP solution could be oxidized with much less N{sub 2}O{sub 4} consumption.

  2. Analysis of Ruptured Heater Tube of Degasser Condenser in Wolsong Unit 4

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hong Pyo; Kim, J. S.; Lim, Y. S.; Kim, S. S.; Hwang, S. S.; Kim, D. J.; Kim, S. W.; Jeong, M. K.; Hong, J. H


    In a degasser condenser in Wolsong unit 4, the cracks were found in the heater tube no. 6 and no. 7. To avoid additional damages in the specimen during a decontamination process for the previous analysis, the cracks were analyzed without any decontamination process in this work. We performed the investigation of the ruptured surface morphology, the EDS analysis of the ruptured surface, the microstructural analysis of Alloy 800H sheath tube and literature survey to find the failure mechanism. From the results, it was expected that the sheath tube has been exposed in a steam condition as the coolant level was decreased in the degasser condenser, leading to the rupture of the sheath tube.

  3. Infrasonic harmonic tremor and degassing bursts from Halema'uma'u Crater, Kilauea Volcano, Hawaii (United States)

    Fee, David; Garcés, Milton; Patrick, Matt; Chouet, Bernard; Dawson, Phil; Swanson, Donald A.


    The formation, evolution, collapse, and subsequent resurrection of a vent within Halema'uma'u Crater, Kilauea Volcano, produced energetic and varied degassing signals recorded by a nearby infrasound array between 2008 and early 2009. After 25 years of quiescence, a vent-clearing explosive burst on 19 March 2008 produced a clear, complex acoustic signal. Near-continuous harmonic infrasonic tremor followed this burst until 4 December 2008, when a period of decreased degassing occurred. The tremor spectra suggest volume oscillation and reverberation of a shallow gas-filled cavity beneath the vent. The dominant tremor peak can be sustained through Helmholtz oscillations of the cavity, while the secondary tremor peak and overtones are interpreted assuming acoustic resonance. The dominant tremor frequency matches the oscillation frequency of the gas emanating from the vent observed by video. Tremor spectra and power are also correlated with cavity geometry and dynamics, with the cavity depth estimated at ~219 m and volume ~3 x 106 m3 in November 2008. Over 21 varied degassing bursts were observed with extended burst durations and frequency content consistent with a transient release of gas exciting the cavity into resonance. Correlation of infrasound with seismicity suggests an open system connecting the atmosphere to the seismic excitation process at depth. Numerous degassing bursts produced very long period (0.03-0.1 Hz) infrasound, the first recorded at Kilauea, indicative of long-duration atmospheric accelerations. Kilauea infrasound appears controlled by the exsolution of gas from the magma, and the interaction of this gas with the conduits and cavities confining it.

  4. Degassing of primordial hydrogen and helium as the major energy source for internal terrestrial processes

    Directory of Open Access Journals (Sweden)

    Arie Lev Gilat


    Full Text Available Examples of the mightiest energy releases by great earthquakes and volcanic eruptions and hypotheses providing explanations for them are analyzed along with the results of some recently published researches and visualizations. The emerging conclusions are that the mechanism of the strong earthquake is a chemical explosion; that volcanic eruption is a special type of earthquake wherein the hypocenter rises to the earth-surface; and that there is an association between the seismic-volcanic processes and mantle “fluids” and the lack of energy for mantle plumes. A conceptual system of hypotheses is put forward to explain the conservation of energy during Earth’s accretion, its quasi-stable release by primordial H- and He-degassing and of the crucial role of the energy of degassing-comprising-reactions in endogenic processes. Specific mechanisms and chemical processes are proposed for the gas-liquid mantle plumes melting through the solid mantle using heat-energy released in reactions of their metamorphic and chemical transformation under gradual decrease of pressure and temperature; volcanic gases are put forward as energy carriers. 3He performance as a unique measuring transformer correlative to the internal heat flow was used for calculation of energy release by degassing; it equals to 5.12 × 1020 J/yr, an amount of energy five-fold greater than the entire energy loss involved in earthquake and volcanic activity. The hypotheses proposed are objectively testable.

  5. Porous aerosol in degassing plumes of Mt. Etna and Mt. Stromboli (United States)

    Shcherbakov, Valery; Jourdan, Olivier; Voigt, Christiane; Gayet, Jean-Francois; Chauvigne, Aurélien; Schwarzenboeck, Alfons; Minikin, Andreas; Klingebiel, Marcus; Weigel, Ralf; Borrmann, Stephan; Jurkat, Tina; Kaufmann, Stefan; Schlage, Romy; Gourbeyre, Christophe; Febvre, Guy; Lapyonok, Tatyana; Frey, Wiebke; Molleker, Sergej; Weinzierl, Bernadett


    Aerosols of the volcanic degassing plumes from Mt. Etna and Mt. Stromboli were probed with in situ instruments on board the Deutsches Zentrum für Luft- und Raumfahrt research aircraft Falcon during the contrail, volcano, and cirrus experiment CONCERT in September 2011. Aerosol properties were analyzed using angular-scattering intensities and particle size distributions measured simultaneously with the Polar Nephelometer and the Forward Scattering Spectrometer probes (FSSP series 100 and 300), respectively. Aerosols of degassing plumes are characterized by low values of the asymmetry parameter (between 0.6 and 0.75); the effective diameter was within the range of 1.5-2.8 µm and the maximal diameter was lower than 20 µm. A principal component analysis applied to the Polar Nephelometer data indicates that scattering features of volcanic aerosols of different crater origins are clearly distinctive from angular-scattering intensities of cirrus and contrails. Retrievals of aerosol properties revealed that the particles were "optically spherical" and the estimated values of the real part of the refractive index are within the interval from 1.35 to 1.38. The interpretation of these results leads to the conclusion that the degassing plume aerosols were porous with air voids. Our estimates suggest that aerosol particles contained about 18 to 35 % of air voids in terms of the total volume.

  6. Impact vesiculation – a new trigger for volcanic bubble growth and degassing

    Directory of Open Access Journals (Sweden)

    D. B. Dingwell


    Full Text Available We highlight a potentially important trigger for bubble growth and degassing in volcanic bombs. We have successfully triggered bubble growth in previously unvesiculated samples of silicate melt during experiments to simulate volcanic bomb impact, by firing pellets at, and dropping weights onto, melt samples. We call this phenomenon "impact vesiculation". Further work is required on real volcanic bombs to establish the extent to which impact vesiculation occurs in nature. However, our experiments are sufficient to demonstrate that impact vesiculation is a viable processes and should be borne in mind in analysis of bubble populations and degassing histories of bombs and spatter-fed lava flows. Degassing caused by impact vesiculation can occur only at ground-level, so any attempt to calculate the amount of erupted gas available for transport high into the atmosphere by convection above the source of a fountain-fed lava flow that is based on subtracting the volatile content of fluid inclusions from the volatile content of the resulting lava flow would be an overestimate if significant impact vesiculation has occurred.

  7. Electrical Resistivity Monitoring of an Active Hydrothermal Degassing Area at Solfatara, Phlegrean Fields. (United States)

    Vandemeulebrouck, J.; Byrdina, S.; Grangeon, J.; Lebourg, T.; Bascou, P.; Mangiacapra, A.


    Campi Flegrei caldera (CFc) is an active volcanic complex covering a ~100 km² densely populated area in the western part of Naples (Italy) that is presently showing clear signs of unrest. Solfatara volcano, a tuff cone crater formed ~4000 yrs B.P. ago by phreato-magmatic eruptions represents the main degassing outflow of CFc. Magmatic gases which are exsolved from a ~8 km deep magmatic reservoir mix at 4 km depth with meteoric hydrothermal fluids then reach the surface in the Solfatara area. These hydrothermal and magmatic gases, mainly H2O and CO2, are released through both diffuse degassing structures and fumaroles. In the frame of the MedSuv (Mediterranean Supervolcanoes) FP7 european project , we are performing a time-lapse electrical resistivity monitoring of an active degassing area of Solfatara. Using a 500-m-long cable and 48 electrodes, an electrical resistivity tomography (ERT) is performed on a two-day basis since May 2013. The time-lapse inversion of the ERT gives an image of the temporal variations of resistivity up to 100 m depth that can be compared with the variations of ground deformation, CO2 flux, soil temperature and seismic ambient noise. Resistivity variations can originate from fluid composition, gas ratio and temperature. For example, the abrupt change of resistivity that was observed mid-2014 during a period of uplift and gas flux increase, could be associated with the rise of hydrothermal fluids.

  8. Diffuse degassing at Longonot volcano, Kenya: Implications for CO2 flux in continental rifts (United States)

    Robertson, Elspeth; Biggs, Juliet; Edmonds, Marie; Clor, Laura; Fischer, Tobias P.; Vye-Brown, Charlotte; Kianji, Gladys; Koros, Wesley; Kandie, Risper


    Magma movement, fault structures and hydrothermal systems influence volatile emissions at rift volcanoes. Longonot is a Quaternary caldera volcano located in the southern Kenyan Rift, where regional extension controls recent shallow magma ascent. Here we report the results of a soil carbon dioxide (CO2) survey in the vicinity of Longonot volcano, as well as fumarolic gas compositions and carbon isotope data. The total non-biogenic CO2 degassing is estimated at < 300 kg d- 1, and is largely controlled by crater faults and fractures close to the summit. Thus, recent volcanic structures, rather than regional tectonics, control fluid pathways and degassing. Fumarolic gases are characterised by a narrow range in carbon isotope ratios (δ13C), from - 4.7‰ to - 6.4‰ (vs. PDB) suggesting a magmatic origin with minor contributions from biogenic CO2. Comparison with other degassing measurements in the East African Rift shows that records of historical eruptions or unrest do not correspond directly to the magnitude of CO2 flux from volcanic centres, which may instead reflect the current size and characteristics of the subsurface magma reservoir. Interestingly, the integrated CO2 flux from faulted rift basins is reported to be an order of magnitude higher than that from any of the volcanic centres for which CO2 surveys have so far been reported.

  9. Mantle to surface degassing of alkalic magmas at Erebus volcano, Antarctica (United States)

    Oppenheimer, C.; Moretti, R.; Kyle, P.R.; Eschenbacher, A.; Lowenstern, J. B.; Hervig, R.L.; Dunbar, N.W.


    Continental intraplate volcanoes, such as Erebus volcano, Antarctica, are associated with extensional tectonics, mantle upwelling and high heat flow. Typically, erupted magmas are alkaline and rich in volatiles (especially CO2), inherited from low degrees of partial melting of mantle sources. We examine the degassing of the magmatic system at Erebus volcano using melt inclusion data and high temporal resolution open-path Fourier transform infrared (FTIR) spectroscopic measurements of gas emissions from the active lava lake. Remarkably different gas signatures are associated with passive and explosive gas emissions, representative of volatile contents and redox conditions that reveal contrasting shallow and deep degassing sources. We show that this unexpected degassing signature provides a unique probe for magma differentiation and transfer of CO2-rich oxidised fluids from the mantle to the surface, and evaluate how these processes operate in time and space. Extensive crystallisation driven by CO2 fluxing is responsible for isobaric fractionation of parental basanite magmas close to their source depth. Magma deeper than 4kbar equilibrates under vapour-buffered conditions. At shallower depths, CO2-rich fluids accumulate and are then released either via convection-driven, open-system gas loss or as closed-system slugs that ascend and result in Strombolian eruptions in the lava lake. The open-system gases have a reduced state (below the QFM buffer) whereas the closed-system gases preserve their deep oxidised signatures (close to the NNO buffer). ?? 2011 Elsevier B.V.

  10. Cation disorder and epitaxial strain modulated Drude-Smith type terahertz conductivity and Hall-carrier switching in Ca1-x Ce x RuO3 thin films (United States)

    Das, Sarmistha; Eswara Phanindra, V.; Santhosh Kumar, K.; Agarwal, Piyush; Dhaker, K. C.; Rana, D. S.


    The CaRuO3 is a non-Fermi liquid pseudo-cubic perovskite with a magnetic ground state on the verge of phase transition and it lies in the vicinity of the quantum critical point. To understand the sensitivity of its ground state, the effects of subtle aliovalent chemical disorder on the static and high frequency dynamic conductivity in the coherently strained structures were explored. The Ce-doped Ca1-x Ce x RuO3 (0  ⩽  x  ⩽  0.1) thin films were deposited on LaAlO3 (1 0 0) and SrTiO3 (1 0 0) substrates and studies for low-energy terahertz (THz) carrier dynamics, dc transport and Hall effect. These compositions exhibited a very effective and unusual Hall-carrier switching in both compressive and tensile strain induced epitaxial thin films. The dc resistivity depicts a switching from a non-Fermi liquid to a Fermi liquid behavior without any magnetic phase transition. A discernible and gradual crossover from Drude to Drude-Smith THz dynamic optical conductivity was observed while traversing from pure to 10% Ce-doped CaRuO3 films. Overall, a nearly Fermi liquid behavior, effective carrier switching and unusual features in THz conductivity, were all novel features realized for the first time in physically and/or chemically modified CaRuO3. These new phases highlight the novel subtleties and versatility of the systems lying near the quantum critical point.

  11. Enhanced volcanic CO2 degassing at oceanic hotspots and mid-ocean ridges in response to falling sea level (United States)

    Hasenclever, Jörg; Knorr, Gregor; Rüpke, Lars; Köhler, Peter; Morgan, Jason; Garofalo, Kristin; Barker, Stephen; Lohmann, Gerrit; Hall, Ian


    Evidence from paleo-climate proxy data as well as results from geodynamical and biogeochemical modelling point to complex interactions between sea level variations, pressure-release melting of oceanic mantle, associated volcanic degassing, and atmospheric CO2 concentrations. Ice core data shows that the orbital component in global temperature records gradually declined between ˜85,000-70,000 yr BP, while atmospheric CO2 - instead of continuing its long-term correlation with Antarctic temperatures - remained relatively stable for several thousand years. Based on 2-D and 3-D geodynamical models we show that the massive (60-100 m) sea level drop during this period of Earth history led to a significant increase in magma and possibly CO2 fluxes along mid-ocean ridges (MOR) and especially oceanic hotspot volcanoes. We assess the MOR magma and CO2 fluxes using 2-D thermo-mechanical models that solve for wet melting of the mantle and the partitioning of highly incompatible carbon dioxide into the melt. These models have been run at various MOR opening rates, and we integrate these results with the global distribution of spreading rates to compute baseline fluxes as well as enhanced fluxes during the sea level fall. Furthermore we conducted more than 120 3-D simulations of rising and melting mantle plumes to construct a four-dimensional parameter space that covers a wide range of plume buoyancy fluxes, plume excess temperatures, lithosphere thicknesses and plate speeds. Using published data on 43 oceanic hotspots and locating them in the parameter space we derive a global hotspot-melting model that predicts magma and CO2 fluxes before and during the sea level drop. We find that, during a 80 m sea level drop over 10 kyr, global degassing at MOR and oceanic hotspots increases by 26 % and 36 %, respectively. Biogeochemical carbon cycle modelling further shows that the combined predicted increase in volcanic emissions along the global mid-ocean ridge system and at oceanic

  12. Melt fracturing and healing: A mechanism for degassing and origin of silicic obsidian (United States)

    Cabrera, A.; Weinberg, R.F.; Wright, H.M.N.; Zlotnik, S.; Cas, Ray A.F.


    We present water content transects across a healed fault in pyroclastic obsidian from Lami pumice cone, Lipari, Italy, using synchrotron Fourier transform infrared spectroscopy. Results indicate that rhyolite melt degassed through the fault surface. Transects define a trough of low water content coincident with the fault trace, surrounded on either side by high-water-content plateaus. Plateaus indicate that obsidian on either side of the fault equilibrated at different pressure-temperature (P-T) conditions before being juxtaposed. The curves into the troughs indicate disequilibrium and water loss through diffusion. If we assume constant T, melt equilibrated at pressures differing by 0.74 MPa before juxtaposition, and the fault acted as a low-P permeable path for H2O that diffused from the glass within time scales of 10 and 30 min. Assuming constant P instead, melt on either side could have equilibrated at temperatures differing by as much as 100 ??C, before being brought together. Water content on the fault trace is particularly sensitive to post-healing diffusion. Its preserved value indicates either higher temperature or lower pressure than the surroundings, indicative of shear heating and dynamic decompression. Our results reveal that water contents of obsidian on either side of the faults equilibrated under different P-T conditions and were out of equilibrium with each other when they were juxtaposed due to faulting immediately before the system was quenched. Degassing due to faulting could be linked to cyclical seismic activity and general degassing during silicic volcanic activity, and could be an efficient mechanism of producing low-water-content obsidian. ?? 2011 Geological Society of America.

  13. Previous degassing of coal beds in the Jiu Valley coalfield - energy source for local community

    Energy Technology Data Exchange (ETDEWEB)

    Lupu, C.; Jurca, L. [National Institute for Safety in Mine and Explosion Protection, Petrosani (Romania)


    The restructuring process of the Romanian mining industry required by transition to the market economy aims at raising of the labour productivity in a safe environment. This paper presents the systems and methods for degassing the coal beds employed in the coalfield of the Jiu Valley, in accordance with the specific geological conditions and the used mining methods. Researches were carried out aiming to determine the fissuring amplitude and permeability of the neighbouring rock mass, and the coal beds. These researches showed raises of methane emissions when the rocks in the roof or in the floor of the coal beds were sandstones or sandstone marls. A previous degassing of the coal beds is put into practice in the coalfield of the Jiu Valley. This process is accomplished both in a 'central' system with equipment placed outside the mine and in a 'local' system, using ejectors to catch methane. These ejectors are placed at the level of the underground mining works. The caught methane is discharged either into air when the aspiration equipment are placed outside the mine or trough discharge air flows of the polluted air from underground when underground ejectors are used. The caught methane amounts the values between 4.5 and 6 m{sub 3}/min, for the aspiration equipment placed outside the mine and 0.8-1.5 m{sub 3}/min, when the 'local' degassing system is employed. Taking into account the fact that methane caught in underground is an energy source and the greenhouse effect is increased when methane is discharged into the fresh air, there has been considered to be a good thing both for the needs of the producing units and for the local community that methane should be submitted to an industrial exploitation. 10 refs., 1 fig.

  14. The impact of persistent volcanic degassing on vegetation: A case study at Turrialba volcano, Costa Rica (United States)

    Tortini, R.; van Manen, S. M.; Parkes, B. R. B.; Carn, S. A.


    Although the impacts of large volcanic eruptions on the global environment have been frequently studied, the impacts of lower tropospheric emissions from persistently degassing volcanoes remain poorly understood. Gas emissions from persistent degassing exceed those from sporadic eruptive activity, and can have significant long-term (years to decades) effects on local and regional scales, both on humans and the environment. Here, we exploit a variety of high temporal and high spatial resolution satellite-based time series and complementary ground-based measurements of element deposition and surveys of species richness, to enable a comprehensive spatio-temporal assessment of sulfur dioxide (SO2) emissions and their associated impacts on vegetation at Turrialba volcano (Costa Rica) from 2000 to 2013. We observe increased emissions of SO2 coincident with a decline in vegetation health downwind of the vents, in accordance with the prevalent wind direction at Turrialba. We also find that satellite-derived vegetation indices at various spatial resolutions are able to accurately define the vegetation kill zone, the extent of which is independently confirmed by ground-based sampling, and monitor its expansion over time. In addition, ecological impacts in terms of vegetation composition and diversity and physiological damage to vegetation, all spatially correspond to fumigation by Turrialba's plume. This study shows that analyzing and relating satellite observations to conditions and impacts on the ground can provide an increased understanding of volcanic degassing, its impacts in terms of the long-term vegetation response and the potential of satellite-based monitoring to inform hazard management strategies related to land use.

  15. Effect of high shear mixing parameters and degassing temperature on the morphology of epoxy-clay nanocomposites

    KAUST Repository

    Al-Qadhi, Muneer


    Epoxy-clay nanocomposites were prepared by high shear mixing method using Nanomer I.30E nanoclay as nano-reinforcement in diglycidyl ether of bisphenol A (DGEBA). The effect of mixing speed and time on the nature and degree of clay dispersion were investigated by varying the mixing speed in the range of 500-8000 RPM and mixing time in the range of 15-90 minutes. The effect of degassing temperature on the morphology of the resultant nanocomposites was also studied. Scanning and transmission microscopy (SEM and TEM) along with x-ray diffraction (XRD) have been used to characterize the effect of shear mixing speed, mixing time and degassing temperature on the structure of the resultant nanocomposites. The SEM, TEM and XRD examinations demonstrated that the degree of clay dispersion was improved with increasing the high shear mixing speed and mixing time. The results showed that the optimum high shear mixing speed and mixing time were 6000 rpm and 60 min, respectively. It was observed that the structure of the nanocomposites that have been degassed at 65°C was dominated by ordered intercalated morphology while disordered intercalated with some exfoliated morphology was found for the sample degassed at 100°C for the first 2 hours of the degassing process. © (2013) Trans Tech Publications, Switzerland.

  16. Degassing developments

    Energy Technology Data Exchange (ETDEWEB)

    Fenderson, S.; Allison, T. [Goar, Allison and Associates, Inc., (United States)


    The sulfur degasification process named D'GAASS is described. By operating under pressure, the advantages of air stripping are maximised. The process (essentially for removing hydrogen sulfide) has major advantages and these are listed. The process is well well-suited for retrofitting to existing SRUs (sulfur recovery units) both in terms of time and mechanical operations.

  17. [Mechanism of the biological impact of weak electromagnetic fields and in vitro effects of degassing of blood]. (United States)

    Shatalov, V M


    The physical validity of the mechanism proposed by the author is discussed. According to the theory a prolonged exposure to weak electromagnetic fields leads to an enlargement of the micro-bubbles and degassing of bioliquid. Degassing alters the physical and chemical properties of bioliquid that affect some medical and biological indicators. The following changes in some blood parameters during degassing in vitro were analyzed: a decrease in the glucose concentration, an abnormal activation of blood clotting, an increase in the rate of blood cell aggregation, a decrease in the effectiveness of aspirin as an inhibitor of platelet aggregation and the slowing of indirect anticoagulants. All of this evidences a possible correlation between the increasing electromagnetic pollution and the risk of cardiovascular disease.

  18. Shallow-ocean methane leakage and degassing to the atmosphere: Triggered by offshore oil-gas and methane hydrate explorations

    Directory of Open Access Journals (Sweden)

    Yong eZHANG


    Full Text Available Both offshore oil-gas exploration and marine methane hydrate recovery can trigger massive CH4 release from seafloor. During upward transportation of CH4 plume through water column, CH4 is subjected to dissolution and microbial consumption despite the protection of hydrate and oil coating on bubbles surface. The ultimate CH4 degassing to the atmosphere appears to be water-depth dependent. In shallow oceans with water depth less than 100 m, the natural or human-induced leakages or both lead to significant sea-to-air CH4 degassing from 3.00 to 1.36 × 105 μmol m-2 d-1. To quantify the human-perturbation induced CH4 degassing, the combination of top-down modeling and bottom-up calculations is essential due to spatial and temporal variability of diffusion and ebullition at water-air interface.

  19. Cationic polymers and porous materials

    KAUST Repository

    Han, Yu


    According to one or more embodiments, cationic polymers may be produced which include one or more monomers containing cations. Such cationic polymers may be utilized as structure directing agents to form mesoporous zeolites. The mesoporous zeolites may include micropores as well as mesopores, and may have a surface area of greater than 350 m2/g and a pore volume of greater than 0.3 cm3/g. Also described are core/shell zeolites, where at least the shell portion includes a mesoporous zeolite material.

  20. Volcanic gas composition changes during the gradual decrease of the gigantic degassing activity of Miyakejima volcano, Japan, 2000-2015 (United States)

    Shinohara, Hiroshi; Geshi, Nobuo; Matsushima, Nobuo; Saito, Genji; Kazahaya, Ryunosuke


    The composition of volcanic gases discharged from Miyakejima volcano has been monitored during the intensive degassing activity that began after the eruption in 2000. During the 15 years from 2000 to 2015, Miyakejima volcano discharged 25.5 Mt of SO2, which required degassing of 3 km3 of basaltic magma. The SO2 emission rate peaked at 50 kt/day at the end of 2000 and quickly decreased to 5 kt/day by 2003. During the early degassing period, the volcanic gas composition was constant with the CO2/SO2 = 0.8 (mol ratio), H2O/SO2 = 35, HCl/SO2 = 0.08, and SO2/H2S = 15. The SO2 emission rate decreased gradually to 0.5 kt/day by 2012, and the gas composition also changed gradually to CO2/SO2 = 1.5, H2O/SO2 = 150, HCl/SO2 = 0.15, and SO2/H2S = 6. The compositional changes are not likely caused by changes in degassing pressure or volatile heterogeneity of a magma chamber but are likely attributed to an increase of hydrothermal scrubbing caused by large decrease of the volcanic gas emission rate, suggesting a supply of gases with constant composition during the 15 years. The intensive degassing was modeled based on degassing of a convecting magma conduit. The gradual SO2 emission rate that decrease without changes in volcanic gas composition is attributed to a reduction of diameter of the convecting magma conduit.

  1. Passive degassing at Nyiragongo (D.R. Congo and Etna (Italy volcanoes

    Directory of Open Access Journals (Sweden)

    Sergio Calabrese


    Full Text Available Volcanoes are well known as an impressive large natural source of trace elements into the troposphere. Etna (Italy and Nyiragongo (D.R. Congo are two stratovolcanoes located in different geological settings, both characterized by persistent passive degassing from their summit craters. Here, we present some results on trace element composition in volcanic plume emissions, atmospheric bulk deposition (rainwater and their uptake by the surrounding vegetation, with the aim to compare and identify differences and similarities between these two volcanoes. Volcanic emissions were sampled by using active filter-packs for acid gases (sulfur and halogens and specific teflon filters for particulates (major and trace elements. The environmental impact of the volcanogenic deposition in the area surrounding of the crater rims was investigated by using different sampling techniques: bulk rain collectors’ gauges were used to collect atmospheric bulk deposition, and biomonitoring was carried out to collect gases and particulates by using endemic plant species. The estimates of the trace element fluxes confirm that Etna and Nyiragongo are large sources of metals into the atmosphere, especially considering their persistent state of passive degassing. The large amount of emitted trace elements is clearly reflected on the chemical composition of rainwater collected at the summit areas both for Etna and Nyiragongo. Moreover, the biomonitoring results highlight that bioaccumulation of trace elements is extremely high in the proximity of the crater rim and de- creases with the distance from the active craters.  

  2. Low-energy degassing mechanisms for a fluid-based radioxenon detection system

    Energy Technology Data Exchange (ETDEWEB)

    Russ, W.R.; Stuenkel, D.O.; Valentine, J.D. [Univ. of Cincinnati, OH (United States). Dept. of Mechanical, Industrial and Nuclear Engineering; Gross, K.C. [Argonne National Lab., IL (United States). Reactor Analysis Div.


    A method to concentrate heavy noble gases from the atmosphere using certain organic fluids is being developed. To use this technique in a system to monitor the atmosphere for important noble gas fission products (Xe-131, Xe-131m, Xe-133, Xe-133m, and Xe-135) generated by nuclear testing, the radionuclides captured in the fluid must either be detected in the fluid or degassed. This study presents experimental results for a number of possible degassing methods, including heating bubbling with a purge gas, ultrasonic agitation, vacuum, and combinations thereof. Methods were evaluated for energy and time requirements and dilution of the degas product. Initial experiments indicate that in addition to overcoming the standard desorption process dictated by partial pressures per Henry`s Law, a capture mechanism must also be overcome to degas. Some type of agitation, thermal or mechanical, can be used to release weakly trapped gas atoms from the fluid, while diffusional mass transfer can be enhanced through entrainment with a purge gas or use of a vacuum. Ultrasonic agitation of a thin film in a strong vacuum has been shown to be the most effective method of those tested. Implementation of an efficient degas system, along with an absorption system and radioxenon detector could result in an ultrasensitive fluid-based radioxenon measurement system that is more portable, less expensive, and simpler than charcoal-based systems which use cryogenic techniques.

  3. Quiescent hydrogen sulfide and carbon dioxide degassing from Mount Baker, Washington (United States)

    McGee, K.A.; Doukas, M.P.; Gerlach, T.M.


    Volcanic H2S emission rate data are scant despite their importance in understanding magma degassing. We present results from direct airborne plume measurements of H2S and CO2 on a 21-orbit survey at eleven different altitudes around Mount Baker volcano in September 2000 utilizing instrumentation mounted in a light aircraft. Measured emission rates of H2S and CO2 were 5.5 td-1 and 187 td-1 respectively. Maximum concentrations of H2S and CO2 encountered within the 4-km-wide plume were 75 ppb and 2 ppm respectively. Utilizing the H2S signal as a marker for the plume allows the corresponding CO2 signal to be more easily and accurately distinguished from ambient CO2 background. This technique is sensitive enough for monitoring weakly degassing volcanoes in a pre-eruptive condition when scrubbing by hydrothermal fluid or aquifers might mask the presence of more acid magmatic gases such as SO2.

  4. Dental fluorosis linked to degassing of Ambrym volcano, Vanuatu: a novel exposure pathway. (United States)

    Allibone, Rachel; Cronin, Shane J; Charley, Douglas T; Neall, Vince E; Stewart, Robert B; Oppenheimer, Clive


    Ambrym in Vanuatu is a persistently degassing island volcano whose inhabitants harvest rainwater for their potable water needs. The findings from this study indicate that dental fluorosis is prevalent in the population due to fluoride contamination of rainwater by the volcanic plume. A dental survey was undertaken of 835 children aged 6-18 years using the Dean's Index of Fluorosis. Prevalence of dental fluorosis was found to be 96% in the target area of West Ambrym, 71% in North Ambrym, and 61% in Southeast Ambrym. This spatial distribution appears to reflect the prevailing winds and rainfall patterns on the island. Severe cases were predominantly in West Ambrym, the most arid part of the island, and the most commonly affected by the volcanic plume. Over 50 km downwind, on a portion of Malakula Island, the dental fluorosis prevalence was 85%, with 36% prevalence on Tongoa Island, an area rarely affected by volcanic emissions. Drinking water samples from West Ambrym contained fluoride levels from 0.7 to 9.5 ppm F (average 4.2 ppm F, n = 158) with 99% exceeding the recommended concentration of 1.0 ppm F. The pathway of fluoride-enriched rainwater impacting upon human health as identified in this study has not previously been recognised in the aetiology of fluorosis. This is an important consideration for populations in the vicinity of degassing volcanoes, particularly where rainwater comprises the primary potable water supply for humans or animals.

  5. Cationic Nitrogen Doped Helical Nanographenes. (United States)

    Xu, Kun; Feng, Xinliang; Berger, Reinhard; Popov, Alexey A; Weigand, Jan J; Vincon, Ilka; Machata, Peter; Hennersdorf, Felix; Zhou, Youjia; Fu, Yubin


    Herein, we report on the synthesis of a series of novel cationic nitrogen doped nanographenes (CNDN) by rhodium catalyzed annulation reactions. This powerful method allows for the synthesis of cationic nanographenes with non-planar, axial chiral geometries. Single-crystal X-ray analysis reveals helical and cove-edged structures. Compared to their all-carbon analogues, the CNDN exhibit energetically lower lying frontier orbitals with a reduced optical energy gap and an electron accepting behavior. All derivatives show quasi reversible reductions in cyclic voltammetry. Depending on the number of nitrogen dopant, in situ spectroelectrochemistry proves the formation of neutral radicals (one nitrogen dopant) or radical cations (two nitrogen dopants) upon reduction. The developed synthetic protocol paves the way for the design and synthesis of expanded nanographenes or even graphene nanoribbons containing cationic nitrogen doping. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong


    and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...

  7. 不同黏度钻井液脱气效率实验%Experiment of Degassing Efficiency for Different Viscosity Drilling Fluids

    Institute of Scientific and Technical Information of China (English)



    Accurate detection of gaseous hydrocarbon content of drilling fluid is one of means for discovering and evaluating the shows of oil and gas.However,the viscosity of drilling fluid greatly affects the detection result.With the help of high-temperature and high-pressure rotary simulator for drilling fluid,the degassing experiments of different viscosity drilling fluid are conducted,regressing the degassing efficiency chart and equations of the different viscosity drilling fluid,including establishing the coefficient-corrected chart and equations.By them,the real-time calibration of the volume fraction of the gaseous hydrocarbon in drilling fluid can be made at the well site,being good for timely discovery and exact evaluation of the shows of oil and gas.%准确检测钻井液内烃类气体含量是发现和评价油气显示的重要方式之一,然而钻井液黏度对检测结果存在很大影响。借助钻井液高温高压旋转模拟装置,进行了不同黏度钻井液的脱气实验,回归了不同黏度钻井液脱气效率图版及方程,建立了不同黏度钻井液校正系数图版及方程,可对现场测取的钻井液内烃类气体体积分数进行实时校正,有利于油气显示的及时发现和准确评价。

  8. Fault-Related CO2 Degassing, Geothermics, and Fluid Flow in Southern California Basins--Physiochemical Evidence and Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Garven, Grant [Tufts University


    Our studies have had an important impact on societal issues. Experimental and field observations show that CO2 degassing, such as might occur from stored CO2 reservoir gas, can result in significant stable isotopic disequilibrium. In the offshore South Ellwood field of the Santa Barbara channel, we show how oil production has reduced natural seep rates in the area, thereby reducing greenhouse gases. Permeability is calculated to be ~20-30 millidarcys for km-scale fault-focused fluid flow, using changes in natural gas seepage rates from well production, and poroelastic changes in formation pore-water pressure. In the Los Angeles (LA) basin, our characterization of formation water chemistry, including stable isotopic studies, allows the distinction between deep and shallow formations waters. Our multiphase computational-based modeling of petroleum migration demonstrates the important role of major faults on geological-scale fluid migration in the LA basin, and show how petroleum was dammed up against the Newport-Inglewood fault zone in a “geologically fast” interval of time (less than 0.5 million years). Furthermore, these fluid studies also will allow evaluation of potential cross-formational mixing of formation fluids. Lastly, our new study of helium isotopes in the LA basin shows a significant leakage of mantle helium along the Newport Inglewood fault zone (NIFZ), at flow rates up to 2 cm/yr. Crustal-scale fault permeability (~60 microdarcys) and advective versus conductive heat transport rates have been estimated using the observed helium isotopic data. The NIFZ is an important deep-seated fault that may crosscut a proposed basin decollement fault in this heavily populated area, and appears to allow seepage of helium from the mantle sources about 30 km beneath Los Angeles. The helium study has been widely cited in recent weeks by the news media, both in radio and on numerous web sites.

  9. Continuous monitoring of diffuse CO2 degassing at Taal volcano, Philippines (United States)

    Padron, E.; Hernandez Perez, P. A.; Arcilla, C. A.; Lagmay, A. M. A.; Perez, N. M.; Quina, G.; Padilla, G.; Barrancos, J.; Cótchico, M. A.; Melián, G.


    Observing changes in the composition and discharge rates of volcanic gases is an important part of volcanic monitoring programs, because some gases released by progressive depressurization of magma during ascent are highly mobile and reach the surface well before their parental magma. Among volcanic gases, CO2 is widely used in volcano studies and monitoring because it is one of the earliest released gas species from ascending magma, and it is considered conservative. Taal Volcano in Southwest Luzon, Philippines, lies between a volcanic arc front (facing the subduction zone along the Manila Trench) and a volcanic field formed from extension beyond the arc front. Taal Volcano Island is formed by a main tuff cone surrounded by several smaller tuff cones, tuff rings and scoria cones. This island is located in the center of the 30 km wide Taal Caldera, now filled by Taal Lake. To monitor the volcanic activity of Taal volcano is a priority task in the Philippines, because several million people live within a 20-km radius of Taal's caldera rim. In the period from 2010-2011, during a period of volcanic unrest, the main crater lake of Taal volcano released the highest diffuse CO2 emission rates reported to date by volcanic lakes worldwide. The maximum CO2 emission rate measured in the study period occurred two months before the strongest seismic activity recorded during the unrest period (Arpa et al., 2013, Bull Volcanol 75:747). In the light of the excellent results obtained through diffuse degassing studies, an automatic geochemical station to monitor in a continuous mode the diffuse CO2 degassing in a selected location of Taal, was installed in January 2016 to improve the early warning system at the volcano. The station is located at Daang Kastila, at the northern portion of the main crater rim. It measures hourly the diffuse CO2 efflux, atmospheric CO2 concentration, soil water content and temperature, wind speed and direction, air temperature and humidity, rainfall

  10. The Dynamic Role of Melt-Vapor Surface Tension in Magmatic Degassing (United States)

    Mangan, M.; Sisson, T.


    It is well known from classical nucleation theory that melt-vapor surface tension (σ ) critically influences both the supersaturation pressure needed to initiate eruptive degassing (Δ Pcritical) and the rate of gas bubble nucleation (J ). Here we highlight an important aspect of melt-vapor surface tension that is generally ignored, namely, that σ is dynamic quantity responsive to the changes in melt composition, water content, and temperature that occur during magma storage and ascent. Crystallization, degassing, and cooling impart a time-dependency to σ that must be considered in any effort to accurately model eruption processes. In this study, we document changes to σ in natural, water-saturated dacitic melt at 200 MPa and 950-1055° C and 5.7-4.8 wt% H2O. Rather than traditional macroscopic measurements (sessile drop, capillarity, detachment techniques), we experimentally determine the Δ Pcritical of bubble nucleation during depressurization from 200 MPa as a function of T and wt% H2O (techniques as in Mangan and Sisson, E&PSL, 2000), and then solve for σ at those conditions using classical nucleation theory (Blander and Katz, AIChE Jour., 1975). Meshing experiment and theory gives σ = 42 (±3), 60 (±7), 73 (±3) mN/m at T= 950, 1000, 1055° C, and H2O = 5.7 (±0.1), 5.3 (±0.2), 4.8 (±0.1) wt%, respectively. Our data show a negative dependence of σ on dissolved water content of -33 mN/m/wt% H2O and a positive dependence of σ on temperature of +0.30 mN/m/° C. Comparable relationships between σ and changing water content and temperature were obtained in sessile-drop style experiments using hydrous haplogranite melts (Bagdassarov et al., Amer. Mineral., 2000). To illustrate how the observed σ -H2O-T dependencies might impact degassing models we consider two idealized regimes. The first is a storage regime in which isobaric cooling and crystallization in the magma chamber gradually increases the H2O content of the residual melt. Surface tension is

  11. Observation of Catastrophic Degassing from Mantle-Crust in Yinggehai Basin, South China Sea

    Institute of Scientific and Technical Information of China (English)

    Chen Honghan; John Parnell; Gong Zaisheng; Li Sitian


    To lower the CO2 risk for hydrocarbon exploration in the west continental shelf of Yinggehai basin, South China Sea, we do attempt not only to know the CO2 origins, but also to make an understanding of the degassing processes from the mantle and crust. Based on the stable carbon isotope ratios of CO2 alone, the organic and inorganic CO2 can be successively distinguished, but the formation conditions and mixing processes for inorganic CO2 are still not clear. The relationships between lg[R(=3He/4He)/Ra(=1.386×10-6)] and CO2 content (%), CO2/3He and δ13CCO2 have been employed, respectively, to obtain that the CO2 gases in the reservoirs can be classified into three categories: (1) organic CO2 with very low contents but contaminated by mantle-derived helium; (2) inorganic CO2 gases with lower to higher contents being mixtures of crustal CO2 with mantle-derived CO2, the mantle-contributed percentage being in the range of 0 %-27 %, and (3) mainly crust-derived inorganic CO2 gases being characterized by high contents (more than 50 %) and indicating the crustal addition by metamorphism of rich-in carbon rocks in basement. Nevertheless, some CO2/3He ratios of organic CO2 fall into the range 108-1010, which made us inquire whether the CO2/3He=(1-10)×109 can be the unique signature of magmatic CO2 or not. All the observation of plutonic activities, fluid inclusion measurements in gas reservoirs, pre-stack depth/time seismic sections and the satellite infrared remote photography taken from Yinggehai basin, South China Sea, during Chichi earthquake in Taiwan on September 21, 1999, supports that the degassing processes are in a discontinuous mode, which may be triggered by igneous intrusion or extrusion, or earthquakes. In the central diapir zone of the basin, at least 3 to 4 orders of discharge of across-formational thermal fluid flows through fractures can be determined in different scales. The mantle degassing process may have a strong effect on overpressured system

  12. Halogens behaviours in Magma Degassing: Insights into Eruptive Dynamics, Hydrothermal Systems and Atmospheric Impact of Andesitic Volcanism (United States)

    Villemant, B.; Balcone, H.; Mouatt, J.; Michel, A.; Komorowski, J.; Boudon, G.


    Shallow degassing of H2O in andesitic magmas determines the eruptive styles of volcanic eruptions and contributes to the hydrothermal systems developed around active volcanoes. Halogens behaviour during magma degassing primarily depends on their incompatible behaviour in the melts and on water solubility. Thus, residual contents of halogens in volcanic juvenile vitric clasts may be used as tracers of H2O degassing processes during explosive and effusive eruptions. Because of the large range of water-melt partition coefficients of halogens and their relatively low diffusion coefficients, a comparison of F, Cl, Br and I contents in volcanic clasts in function of their vesicularity and micro-cristallinity allows to precisely model the main degassing processes and to establish constraints on pre-eruptive conditions. Halogens acids (HCl, HBr and HI) extracted in the vapour phase have much more complex behaviours because of their high solubility in low temperature thermal waters, their variable condensation temperatures and their very high reactivity when mixed with low temperature and oxidizing atmospheric gases. A comparison of model compositions of high temperature gases with the composition of thermal waters, and gases from fumaroles or plumes of active volcanoes allows to characterise the shallow volcanic system and its evolutionary states. Variable halogen behaviours are discussed for a variety of eruption types (plinian, vulcanian and dome-forming) and active volcanic systems from the Lesser Antilles (Montagne Pelee, Soufrière of Guadeloupe, Soufriere Hills of Montserrat).

  13. Degassing effect of ultrasonic vibration in molten melt and semi-solid slurry of Al-Si alloys

    Directory of Open Access Journals (Sweden)

    Wu Shusen


    Full Text Available In the process of semi-solid slurry preparation with direct ultrasonic vibration (UV by dipping the horn into the melt, one of the questions is whether the gas content in the melt would be increased or not by the cavitation effect of ultrasonic vibration. By application of quantitative gas content measurement technique, this paper investigated the effect of the ultrasonic vibration on the gas content of both the melt and the semi-solid slurry of Al-Si alloys, and the variations of the gas contents in two kinds of aluminum alloys, i.e., A356 alloy and Al-20Si-2Cu-1Ni-0.6RE alloy (Al-20Si for short. The results show that ultrasonic vibration has an obvious degassing effect on the molten melt, especially on the semi-solid slurry of Al-Si alloy which is below the liquidus temperature by less than 20 ℃. The ultrasonic degassing efficiency of the A356 alloy decreases with the reduction of the initial gas content in the melt, and it is nearly unchanged for the Al-20Si alloy. The gas content of both alloys decreases when the ultrasonic vibration time is increased. The best vibration time for Al-20Si alloy at the liquid temperature of 710 ℃ and semi-solid temperature of 680 ℃ is 60 s and 90 s, respectively; and the degassing efficiency is 48% and 35%, respectively. The mechanism of ultrasonic degassing effect is discussed.

  14. Open system degassing, bubble rise and flow dynamics within volcanic conduits- an experimental approach (United States)

    Pioli, L.; Azzopardi, B. J.; Bonadonna, C.; Marchetti, E.; Ripepe, M.


    Open conduit basaltic volcanoes are characterized by frequent eruptions, usually consisting in mild Strombolian and Hawaiian explosions, alternating years to months of quiescence periods, with degassing activity from the central conduit. Recent improvements of thermal, video, radar and acoustic monitoring techniques have provided new powerful tools for the study of degassing processes and made available geophysical and geochemical datasets for many central volcanoes, such as Stromboli, Etna (Italy), Kilauea (Hawaii), Villarrica (Chile). These studies revealed that degassing is an unsteady, often pulsatory process, characterized by fluctuations in both intensity and composition of the emitted gases. Unambiguous interpretation of monitoring data of surface activity in terms of conduit dynamics and flow processes is, however, not possible, due to partial knowledge of the physical processes controlling the dynamics of two-phase flows in magmas. We performed a series of experiments to gain further insights on the dynamics of the gas-bubble rise in magmas within a cylindrical conduit, their ability to segregate and coalesce and the effect of these processes on the degassing dynamics. The experiments consisted in generating fluxes at variable intensities of air through stagnant water or glucose syrup in a bubble column apparatus 6.5 m high and with a diameter of 24 cm diameter. Glucose syrup and water are Newtonian liquids with viscosity ranging from 2.4 to 204.0 Pa*s and from 1.7 to 0.2 10 -3 Pa*s respectively, depending on temperature. Air was inserted at the base of the column through a variable number (1 to 25) of 5mm-diameter nozzles reaching surficial gas velocities of up to 0.5 m/s. The activity of the bubble column was monitored through temperature, pressure, void fraction and acoustic measurements and filmed by a high-speed camera with maximum resolution of 800x600 pixels. Pressure fluctuations, vesicularity and acoustic signal were then analyzed and correlated

  15. Conduit dynamics and post explosion degassing on Stromboli: A combined UV camera and numerical modeling treatment (United States)

    McGonigle, A. J. S.; James, M. R.; Tamburello, G.; Aiuppa, A.; Delle Donne, D.; Ripepe, M.


    Abstract Recent gas flux measurements have shown that Strombolian explosions are often followed by periods of elevated flux, or “gas codas,” with durations of order a minute. Here we present UV camera data from 200 events recorded at Stromboli volcano to constrain the nature of these codas for the first time, providing estimates for combined explosion plus coda SO2 masses of ≈18–225 kg. Numerical simulations of gas slug ascent show that substantial proportions of the initial gas mass can be distributed into a train of “daughter bubbles” released from the base of the slug, which we suggest, generate the codas, on bursting at the surface. This process could also cause transitioning of slugs into cap bubbles, significantly reducing explosivity. This study is the first attempt to combine high temporal resolution gas flux data with numerical simulations of conduit gas flow to investigate volcanic degassing dynamics. PMID:27478285

  16. Cell volume-regulated cation channels. (United States)

    Wehner, Frank


    Considering the enormous turnover rates of ion channels when compared to carriers it is quite obvious that channel-mediated ion transport may serve as a rapid and efficient mechanism of cell volume regulation. Whenever studied in a quantitative fashion the hypertonic activation of non-selective cation channels is found to be the main mechanism of regulatory volume increase (RVI). Some channels are inhibited by amiloride (and may be related to the ENaC), others are blocked by Gd(3) and flufenamate (and possibly linked to the group of transient receptor potential (TRP) channels). Nevertheless, the actual architecture of hypertonicity-induced cation channels remains to be defined. In some preparations, hypertonic stress decreases K(+) channel activity so reducing the continuous K(+) leak out of the cell; this is equivalent to a net gain of cell osmolytes facilitating RVI. The hypotonic activation of K(+) selective channels appears to be one of the most common principles of regulatory volume decrease (RVD) and, in most instances, the actual channels involved could be identified on the molecular level. These are BKCa (or maxi K(+)) channels, IK(Ca) and SK(Ca) channels (of intermediate and small conductance, respectively), the group of voltage-gated (Kv) channels including their Beta (or Kv ancilliary) subunits, two-pore K(2P) channels, as well as inwardly rectifying K(+) (Kir) channels (also contributing to K(ATP) channels). In some cells, hypotonicity activates non-selective cation channels. This is surprising, at first sight, because of the inside negative membrane voltage and the sum of driving forces for Na(+) and K(+) diffusion across the cell membrane rather favouring net cation uptake. Some of these channels, however, exhibit a P(K)/P(Na) significantly higher than 1, whereas others are Ca(++) permeable linking hypotonic stress to the activation of Ca(++) dependent ion channels. In particular, the latter holds for the group of TRPs which are specialised in the

  17. The Effect of Degassing Efficiency on the Fragmentation Behavior of Volcanic Rocks (United States)

    Mueller, S.; Scheu, B.; Spieler, O.; Dingwell, D. B.


    The degassing efficiency of volcanic rocks is a decisive measure for the eruptive style and thus the explosivity of a volcano, since it directly affects magma fragmentation behaviour. Vesicles in ascending magma may bear overpressure if the relevant magma viscosity entails a relaxation time scale which is significantly larger than the time scale of ambient pressure reduction due to magma ascent. As long as this overpressure does not overcome the tensile strength of the magma, the system is in a structurally stable state, eventually degassing quiescently via an interconnected pore network. However, if a decompressive event (e.g. sector collapse) disturbs this stable pressure situation, two possible scenarios are conceivable: (1) An interconnected pore network has been established whose permeability is sufficiently high, so vesicle overpressure can be reduced efficiently by gas filtration. (2) The permeability of the network (or cluster of isolated pores, respectively) is low and gas overpressure can not be reduced within the required time scale. In this case the expansion of the pressurized gas may cause bubble wall failure and magma fragmentation into pyroclasts. This study compares experimentally derived fragmentation threshold values of volcanic rock samples, determined with a shock-tube based setup, to unsteady-state permeability values of the same sample sets. In order to cover a wide range in rock properties, we analysed samples from a broad variety of volcanic deposits. Among the treated volcanoes were Colima (Mexico), Bezymianny (Russia), Krakatoa and Merapi, (both Indonesia), Unzen (Japan), Lipari and Campi Flegrei (both Italy), Pinatubo (Philippines), and Santorini (Greece). The correlation of extensive databases of both investigated parameters revealed that permeabilities above a transition zone between 10-13 and 10-12 m2 shift the fragmentation threshold towards higher values. By means of this dataset the influence of the permeability on fragmentation

  18. Magma fracturing and degassing associated with obsidian formation: The explosive–effusive transition (United States)

    Cabrera, Agustin; Weinberg, Roberto; Wright, Heather M.


    This paper explores the role of melt fracturing in degassing rhyolitic volcanic systems. The Monte Pilato-Rocche Rosse eruptions in Italy evolved from explosive to effusive in style, and H2O content in quenched glasses changed over time from relatively H2O-rich (~ 0.90 wt.%) to H2O-poor dense obsidian (~ 0.10–0.20 wt.%). In addition, healed fractures have been recorded in all different eruptive materials, from the glass of early-erupted tube pumice and rinds of breadcrusted obsidian pyroclasts, to the glass of late-erupted dense obsidian pyroclasts, and throughout the final effusive Rocche Rosse lava flow. These rocks show multiple fault sets, some with crenulated fault planes indicating resumption of viscous flow after faulting, complex obsidian breccias with evidence for post-brecciation folding and stretching, and centimetre- to metre-thick tuffisite preserved in pyroclasts and lava, representing collapsed foam due to fracturing of vesicle walls. These microstructural observations indicate that multiple fracturing and healing events occurred during both explosive and effusive eruptions. H2O content in glass decreases by as much as 0.14 wt.% towards healed fractures/faults and decreases in stretched obsidian breccias towards regions of intense brecciation. A drop in pressure and/or increase in temperature along fractures caused diffusive H2O migration through melt towards fracture surfaces. Repetitive and pervasive fracturing and healing thereby create conditions for diffusive H2O loss into fractures and subsequent escape through permeable paths. This type of progressive magma degassing provides a potential mechanism to explain the formation of dense obsidian and the evolution from explosive to effusive eruption style.

  19. Magma fracturing and degassing associated with obsidian formation: The explosive-effusive transition (United States)

    Cabrera, Agustín; Weinberg, Roberto F.; Wright, Heather M. N.


    This paper explores the role of melt fracturing in degassing rhyolitic volcanic systems. The Monte Pilato-Rocche Rosse eruptions in Italy evolved from explosive to effusive in style, and H2O content in quenched glasses changed over time from relatively H2O-rich (~ 0.90 wt.%) to H2O-poor dense obsidian (~ 0.10-0.20 wt.%). In addition, healed fractures have been recorded in all different eruptive materials, from the glass of early-erupted tube pumice and rinds of breadcrusted obsidian pyroclasts, to the glass of late-erupted dense obsidian pyroclasts, and throughout the final effusive Rocche Rosse lava flow. These rocks show multiple fault sets, some with crenulated fault planes indicating resumption of viscous flow after faulting, complex obsidian breccias with evidence for post-brecciation folding and stretching, and centimetre- to metre-thick tuffisite preserved in pyroclasts and lava, representing collapsed foam due to fracturing of vesicle walls. These microstructural observations indicate that multiple fracturing and healing events occurred during both explosive and effusive eruptions. H2O content in glass decreases by as much as 0.14 wt.% towards healed fractures/faults and decreases in stretched obsidian breccias towards regions of intense brecciation. A drop in pressure and/or increase in temperature along fractures caused diffusive H2O migration through melt towards fracture surfaces. Repetitive and pervasive fracturing and healing thereby create conditions for diffusive H2O loss into fractures and subsequent escape through permeable paths. This type of progressive magma degassing provides a potential mechanism to explain the formation of dense obsidian and the evolution from explosive to effusive eruption style.

  20. River sequesters atmospheric carbon and limits the CO2 degassing in karst area, southwest China. (United States)

    Zhang, Tao; Li, Jianhong; Pu, Junbing; Martin, Jonathan B; Khadka, Mitra B; Wu, Feihong; Li, Li; Jiang, Feng; Huang, Siyu; Yuan, Daoxian


    CO2 fluxes across water-air interfaces of river systems play important roles in regulating the regional and global carbon cycle. However, great uncertainty remains as to the contribution of these inland water bodies to the global carbon budget. Part of the uncertainty stems from limited understanding of the CO2 fluxes at diurnal and seasonal frequencies caused by aquatic metabolism. Here, we measured surface water characteristics (temperature, pH, and DO, DIC, Ca(2+) concentrations) and CO2 fluxes across the air-water interface at two transects of Guijiang River, southwest China to assess the seasonal and diurnal dynamics of fluvial carbon cycling and its potential role in regional and global carbon budgets. The two transects had differing bedrock; DM transect is underlain by carbonate and detrital rock and PY is underlain by pure carbonate. Our results show that the river water both degasses CO2 to and absorbs CO2 from the atmosphere in both summer and winter, but the degassing and absorption varied between the two transects. Further, CO2 fluxes evolve through diurnal cycles. At DM, the river evaded CO2 from early morning through noon and absorbed CO2 from afternoon through early morning. At PY in summer, the CO2 evasion decreased during the daytime and increased at night while in winter at night, CO2 uptake increased in the morning and decreased in the afternoon but remained relatively stable at night. Although the river is a net source of carbon to the atmosphere (~15mMm(-2)day(-1)), the evasion rate is the smallest of all reported world's inland water bodies reflecting sequestration of atmospheric carbon through the carbonate dissolution and high primary productivity. These results emphasize the need of seasonal and diurnal monitoring of CO2 fluxes across water-air interface, particularly in highly productive rivers, to reduce uncertainty in current estimates of global riverine CO2 emission. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Open-path FTIR spectroscopy of magma degassing processes during eight lava fountains on Mount Etna (United States)

    La Spina, Alessandro; Burton, Mike; Allard, Patrick; Alparone, Salvatore; Murè, Filippo


    In June-July 2001 a series of 16 discrete lava fountain paroxysms occurred at the Southeast summit crater (SEC) of Mount Etna, preceding a 28-day long violent flank eruption. Each paroxysm was preceded by lava effusion, growing seismic tremor and a crescendo of Strombolian explosive activity culminating into powerful lava fountaining up to 500m in height. During 8 of these 16 events we could measure the chemical composition of the magmatic gas phase (H2O, CO2, SO2, HCl, HF and CO), using open-path Fourier transform infrared (OP-FTIR) spectrometry at ˜1-2km distance from SEC and absorption spectra of the radiation emitted by hot lava fragments. We show that each fountaining episode was characterized by increasingly CO2-rich gas release, with CO2/SO2and CO2/HCl ratios peaking in coincidence with maxima in seismic tremor and fountain height, whilst the SO2/HCl ratio showed a weak inverse relationship with respect to eruption intensity. Moreover, peak values in both CO2/SO2ratio and seismic tremor amplitude for each paroxysm were found to increase linearly in proportion with the repose interval (2-6 days) between lava fountains. These observations, together with a model of volatile degassing at Etna, support the following driving process. Prior to and during the June-July 2001 lava fountain sequence, the shallow (˜2km) magma reservoir feeding SEC received an increasing influx of deeply derived carbon dioxide, likely promoted by the deep ascent of volatile-rich primitive basalt that produced the subsequent flank eruption. This CO2-rich gas supply led to gas accumulation and overpressure in SEC reservoir, generating a bubble foam layer whose periodical collapse powered the successive fountaining events. The anti-correlation between SO2/HCl and eruption intensity is best explained by enhanced syn-eruptive degassing of chlorine from finer particles produced during more intense magma fragmentation.

  2. Long period seismicity and very long period infrasound driven by shallow magmatic degassing at Mount Pagan, Mariana Islands (United States)

    Lyons, John; Haney, Matt; Werner, Cynthia A.; Kelly, Peter; Patrick, Matthew R.; Kern, Christoph; Trusdell, Frank A.


    Long period (LP) seismicity and very long period infrasound (iVLP) were recorded during continuous degassing from Mount Pagan, Mariana Islands, in July 2013 to January 2014. The frequency content of the LP and iVLP events and delay times between the two arrivals were remarkably stable and indicate nearly co-located sources. Using phase-weighted stacking over similar events to dampen noise, we find that the LP source centroid is located 60 m below and 180 m west of the summit vent. The moment tensor reveals a volumetric source modeled as resonance of a subhorizontal sill intersecting a dike. We model the seismoacoustic wavefields with a coupled earth-air 3-D finite difference code. The ratios of pressure to velocity measured at the infrasound arrays are an order of magnitude larger than the synthetic ratios, so the iVLP is not the result of LP energy transmitting into the atmosphere at its epicenter. Based on crater shape and dimensions determined by structure from motion, we model the iVLP as acoustic resonance of an exponential horn. The source of the continuous plume from gas analysis is shallow magmatic degassing, which repeatedly pressurized the dike-sill portion of the conduit over the 7 months of observation. Periodic gas release caused the geologically controlled sill to partially collapse and resonate, while venting of gas at the surface triggered resonance in the crater. LP degassing only accounts for ~12% of total degassing, indicating that most degassing is relatively aseismic and that multiple active pathways exist beneath the vent.

  3. Geochemical evidence for a magmatic CO2 degassing event at Mammoth Mountain, California, September-December 1997 (United States)

    McGee, K.A.; Gerlach, T.M.; Kessler, R.; Doukas, M.P.


    Recent time series soil CO2 concentration data from monitoring stations in the vicinity of Mammoth Mountain, California, reveal strong evidence for a magmatic degassing event during the fall of 1997 lasting more than 2 months. Two sensors at Horseshoe Lake first recorded the episode on September 23, 1997, followed 10 days later by a sensor on the north flank of Mammoth Mountain. Direct degassing from shallow intruding magma seems an implausible cause of the degassing event, since the gas released at Horseshoe Lake continued to be cold and barren of other magmatic gases, except for He. We suggest that an increase in compressional strain on the area south of Mammoth Mountain driven by movement of major fault blocks in Long Valley caldera may have triggered an episode of increased degassing by squeezing additional accumulated CO2 from a shallow gas reservoir to the surface along faults and other structures where it could be detected by the CO2 monitoring network. Recharge of the gas reservoir by CO2 emanating from the deep intrusions that probably triggered deep long-period earthquakes may also have contributed to the degassing event. The nature of CO2 discharge at the soil-air interface is influenced by the porous character of High Sierra soils and by meteorological processes. Solar insolation is the primary source of energy for the Earth atmosphere and plays a significant role in most diurnal processes at the Earth surface. Data from this study suggest that external forcing due largely to local orographic winds influences the fine structure of the recorded CO2 signals.

  4. The impact of degassing on the oxidation state of basaltic magmas: A case study of Kīlauea volcano (United States)

    Moussallam, Yves; Edmonds, Marie; Scaillet, Bruno; Peters, Nial; Gennaro, Emanuela; Sides, Issy; Oppenheimer, Clive


    Volcanic emissions link the oxidation state of the Earth's mantle to the composition of the atmosphere. Whether the oxidation state of an ascending magma follows a redox buffer - hence preserving mantle conditions - or deviates as a consequence of degassing remains under debate. Thus, further progress is required before erupted basalts can be used to infer the redox state of the upper mantle or the composition of their co-emitted gases to the atmosphere. Here we present the results of X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge carried out for a series of melt inclusions and matrix glasses from ejecta associated with three eruptions of Kīlauea volcano (Hawai'i). We show that the oxidation state of these melts is strongly correlated with their volatile content, particularly in respect of water and sulfur contents. We argue that sulfur degassing has played a major role in the observed reduction of iron in the melt, while the degassing of H2O and CO2 appears to have had a negligible effect on the melt oxidation state under the conditions investigated. Using gas-melt equilibrium degassing models, we relate the oxidation state of the melt to the composition of the gases emitted at Kīlauea. Our measurements and modelling yield a lower constraint on the oxygen fugacity of the mantle source beneath Kīlauea volcano, which we infer to be near the nickel nickel-oxide (NNO) buffer. Our findings should be widely applicable to other basaltic systems and we predict that the oxidation state of the mantle underneath most hotspot volcanoes is more oxidised than that of the associated lavas. We also suggest that whether the oxidation states of a basalt (in particular MORB) reflects that of its source, is primarily determined by the extent of sulfur degassing.

  5. Enabling two-phase microfluidic thermal transport systems using a novel thermal-flux degassing and fluid charging approach (United States)

    Singh Dhillon, Navdeep; Pisano, Albert P.


    A novel two-port thermal-flux method has been proposed and demonstrated for degassing and charging two-phase microfluidic thermal transport systems with a degassed working fluid. In microscale heat pipes and loop heat pipes (mLHPs), small device volumes and large capillary forces associated with smaller feature sizes render conventional vacuum pump-based degassing methods quite impractical. Instead, we employ a thermally generated pressure differential to purge non-condensable gases from these devices before charging them with a degassed working fluid in a two-step process. Based on the results of preliminary experiments studying the effectiveness and reliability of three different high temperature-compatible device packaging approaches, an optimized compression packaging technique was developed to degas and charge a mLHP device using the thermal-flux method. An induction heating-based noninvasive hermetic sealing approach for permanently sealing the degassed and charged mLHP devices has also been proposed. To demonstrate the efficacy of this approach, induction heating experiments were performed to noninvasively seal 1 mm square silicon fill-hole samples with donut-shaped solder preforms. The results show that the minimum hole sealing induction heating time is heat flux limited and can be estimated using a lumped capacitance thermal model. However, further continued heating of the solder uncovers the hole due to surface tension-induced contact line dynamics of the molten solder. It was found that an optimum mass of the solder preform is required to ensure a wide enough induction-heating time window for successful sealing of a fill-hole.

  6. Cation Uptake and Allocation by Red Pine Seedlings under Cation-Nutrient Stress in a Column Growth Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Zhenqing; Balogh-Brunstad, Zsuzsanna; Grant, Michael R.; Harsh, James B.; Gill, Richard; Thomashow, Linda; Dohnalkova, Alice; Stacks, Daryl; Letourneau, Melissa; Keller, Chester K.


    Background and Aims Plant nutrient uptake is affected by environmental stress, but how plants respond to cation-nutrient stress is poorly understood. We assessed the impact of varying degrees of cation-nutrient limitation on cation uptake in an experimental plant-mineral system. Methods Column experiments, with red pine (Pinus resinosa Ait.) seedlings growing in sand/mineral mixtures, were conducted for up to nine months under a range of Ca- and K-limited conditions. The Ca and K were supplied from both minerals and nutrient solutions with varying Ca and K concentrations. Results Cation nutrient stress had little impact on carbon allocation after nine months of plant growth and K was the limiting nutrient for biomass production. The Ca/Sr and K/Rb ratio results allowed independent estimation of dissolution incongruency and discrimination against Sr and Rb during cation uptake processes. The fraction of K in biomass from biotite increased with decreasing K supply from nutrient solutions. The mineral anorthite was consistently the major source of Ca, regardless of nutrient treatment. Conclusions Red pine seedlings exploited more mineral K in response to more severe K deficiency. This did not occur for Ca. Plant discrimination factors must be carefully considered to accurately identify nutrient sources using cation tracers.

  7. Sorption of the organic cation metoprolol on silica gel from its aqueous solution considering the competition of inorganic cations. (United States)

    Kutzner, Susann; Schaffer, Mario; Börnick, Hilmar; Licha, Tobias; Worch, Eckhard


    Systematic batch experiments with the organic monovalent cation metoprolol as sorbate and the synthetic material silica gel as sorbent were conducted with the aim of characterizing the sorption of organic cations onto charged surfaces. Sorption isotherms for metoprolol (>99% protonated in the tested pH of around 6) in competition with mono- and divalent inorganic cations (Na(+), NH4(+), Ca(2+), and Mg(2+)) were determined in order to assess their influence on cation exchange processes and to identify the role of further sorptive interactions. The obtained sorption isotherms could be described well by an exponential function (Freundlich isotherm model) with consistent exponents (about 0.8). In general, a decreasing sorption of metoprolol with increasing concentrations in inorganic cations was observed. Competing ions of the same valence showed similar effects. A significant sorption affinity of metoprolol with ion type dependent Freundlich coefficients KF,0.77 between 234.42 and 426.58 (L/kg)(0.77) could still be observed even at very high concentrations of competing inorganic cations. Additional column experiments confirm this behavior, which suggests the existence of further relevant interactions beside cation exchange. In subsequent batch experiments, the influence of mixtures with more than one competing ion and the effect of a reduced negative surface charge at a pH below the point of zero charge (pHPZC ≈ 2.5) were also investigated. Finally, the study demonstrates that cation exchange is the most relevant but not the sole mechanism for the sorption of metoprolol on silica gel.

  8. An experimental insight into the evolution of permeability at high temperatures and applications for shallow conduit and lava dome degassing (United States)

    Chadderton, Amy; Sammonds, Peter; Meredith, Philip; Smith, Rosanna; Tuffen, Hugh; Gaunt, Elizabeth


    Two recent eruptions in Chile, at Chaitén Volcano in 2008-10 and Cordón Caulle in 2011-12, allowed the first detailed observations of rhyolitic activity and provided insights into the evolution of highly silicic eruptions. Both events exhibited simultaneous explosive and effusive activity, with both lava and ash plumes emitted from the same vent [1]. The permeability of fracture networks that act as fluid flow pathways is key to understanding such eruptive behaviour. Here, we report results from a systematic experimental investigation of permeability in volcanic rocks at magmatic temperatures and pressures, in the presence of pore fluids using our newly-developed high-temperature permeability facility. Enhancements to the High Temperature Triaxial Deformation Cell at UCL [2] have enabled us to make permeability measurements on 25mm x 50mm cores at both elevated temperature and elevated hydrostatic pressure [3]. We present results from several suites of permeability measurements on samples of dome dacite from the 2004-08 eruption of Mount St Helens, and rhyolite collected from the lava dome formed during the 2008-10 eruption of Chaitén, Chile. Tests were conducted at temperatures up to 900oC and under an effective pressure of 5 MPa, using the steady-state flow technique. Samples were cooled to room temperature between each high temperature test, and the permeability of each sample was re-measured before heating to the next temperature increment in the series. Additional longer duration high temperature tests were also conducted to investigate the development of a permeable network at high temperatures over time. The results show a complex permeability evolution that includes a reduction in permeability by approximately 3 orders of magnitude up to 600oC. Together with thermal cracking tests, AE data and SEM/thin section analysis these new experimental permeability results are applied to enhance our understanding of the complex issue of shallow conduit and lava

  9. Electrical conductivities and chemical stabilities of mixed conducting pyrochlores for SOFC applications

    DEFF Research Database (Denmark)

    Holtappels, P.; Poulsen, F.W.; Mogensen, Mogens Bjerg


    Pyrochlores with praseodymium as the A-site cation and zirconium, tin, cerium and manganese cations on the B-site were prepared in air and their electrical conductivities were investigated as a function of oxygen partial pressure and temperature. Pure Pr2Zr2O7+/-delta as well as samples modified...

  10. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)

    CHENG JiaGao; LUO XiaoMin; YAN XiuHua; LI Zhong; TANG Yun; JIANG HuaLiang; ZHU WeiLiang


    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system, which has been viewed as a new kind of binding force, as being compared with the classical interac-tions (e.g. hydrogen bonding, electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper, we present an overview of the typi-cal cation-π interactions in biological systems, the experimental and theoretical investigations on cation-π interactions, as well as the research results on cation-π interactions in our group.

  11. Research progress in cation-π interactions

    Institute of Scientific and Technical Information of China (English)


    Cation-π interaction is a potent intermolecular interaction between a cation and an aromatic system,which has been viewed as a new kind of binding force,as being compared with the classical interactions(e.g. hydrogen bonding,electrostatic and hydrophobic interactions). Cation-π interactions have been observed in a wide range of biological contexts. In this paper,we present an overview of the typical cation-π interactions in biological systems,the experimental and theoretical investigations on cation-π interactions,as well as the research results on cation-π interactions in our group.

  12. The influence of large cations on the electrochemical properties of tunnel-structured metal oxides (United States)

    Yuan, Yifei; Zhan, Chun; He, Kun; Chen, Hungru; Yao, Wentao; Sharifi-Asl, Soroosh; Song, Boao; Yang, Zhenzhen; Nie, Anmin; Luo, Xiangyi; Wang, Hao; Wood, Stephen M.; Amine, Khalil; Islam, M. Saiful; Lu, Jun; Shahbazian-Yassar, Reza


    Metal oxides with a tunnelled structure are attractive as charge storage materials for rechargeable batteries and supercapacitors, since the tunnels enable fast reversible insertion/extraction of charge carriers (for example, lithium ions). Common synthesis methods can introduce large cations such as potassium, barium and ammonium ions into the tunnels, but how these cations affect charge storage performance is not fully understood. Here, we report the role of tunnel cations in governing the electrochemical properties of electrode materials by focusing on potassium ions in α-MnO2. We show that the presence of cations inside 2 × 2 tunnels of manganese dioxide increases the electronic conductivity, and improves lithium ion diffusivity. In addition, transmission electron microscopy analysis indicates that the tunnels remain intact whether cations are present in the tunnels or not. Our systematic study shows that cation addition to α-MnO2 has a strong beneficial effect on the electrochemical performance of this material.

  13. Electrical Conductivity in Transition Metals (United States)

    Talbot, Christopher; Vickneson, Kishanda


    The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

  14. DECADE Web Portal: Integrating MaGa, EarthChem and GVP Will Further Our Knowledge on Earth Degassing (United States)

    Cardellini, C.; Frigeri, A.; Lehnert, K. A.; Ash, J.; McCormick, B.; Chiodini, G.; Fischer, T. P.; Cottrell, E.


    The release of gases from the Earth's interior to the exosphere takes place in both volcanic and non-volcanic areas of the planet. Fully understanding this complex process requires the integration of geochemical, petrological and volcanological data. At present, major online data repositories relevant to studies of degassing are not linked and interoperable. We are developing interoperability between three of those, which will support more powerful synoptic studies of degassing. The three data systems that will make their data accessible via the DECADE portal are: (1) the Smithsonian Institution's Global Volcanism Program database (GVP) of volcanic activity data, (2) EarthChem databases for geochemical and geochronological data of rocks and melt inclusions, and (3) the MaGa database (Mapping Gas emissions) which contains compositional and flux data of gases released at volcanic and non-volcanic degassing sites. These databases are developed and maintained by institutions or groups of experts in a specific field, and data are archived in formats specific to these databases. In the framework of the Deep Earth Carbon Degassing (DECADE) initiative of the Deep Carbon Observatory (DCO), we are developing a web portal that will create a powerful search engine of these databases from a single entry point. The portal will return comprehensive multi-component datasets, based on the search criteria selected by the user. For example, a single geographic or temporal search will return data relating to compositions of emitted gases and erupted products, the age of the erupted products, and coincident activity at the volcano. The development of this level of capability for the DECADE Portal requires complete synergy between these databases, including availability of standard-based web services (WMS, WFS) at all data systems. Data and metadata can thus be extracted from each system without interfering with each database's local schema or being replicated to achieve integration at

  15. Special astronomical configurations, solar activity and deep degassing as a trigger of natural hazards (United States)

    Natyaganov, Vladimir; Syvorotkin, Vladimir; Fedorov, Valeriy; Shopin, Sergey


    Extraordinary cases of tectonic events (strong earthquakes, volcano eruptions), mine explosions, typhoons, hurricanes, tornado outbreak sequences, ball lightnings, transient luminous events are analyzed in relation with special astronomical configurations, which are specific relative positions of the Sun, Earth, Moon and the closest planets of the Solar System (Venus, Mars and Jupiter) [1]. Usage of special astronomical coordinate systems give evidence not only of correlations but also of hidden causes-and-effect relations between the analyzed phenomena. The geocentric ecliptic latitude system is an example of such astronomical coordinate systems. It gives clear evidence of coherence between strong earthquakes and the maximal Moon declination from the plane of the ecliptic. Extraordinary cases of planet activity from the beginning of XX century till the present time are shown in the years of special astronomical configurations and abrupt increasing of solar activity. According to the empirical scheme of short-term earthquake prediction [3], geomagnetic disturbances are the triggers of earthquakes. Geomagnetic disturbances perform electromagnetic pumping (electromagnetic excitation) of the Earth's interior in the regions of intersections of seismomagnetic meridians with the plate boundaries as a result of electrothermal breakdowns in the heterogeneous medium of tectonic faults. This results in the local intensification of deep degassing [4], decreasing of shear strength of the medium that triggers earthquakes usually after 2 or 3 weeks (±2 days) after the geomagnetic disturbance. Examples of officially registered predictions of Kamchatka earthquakes with M7+ without missing events, including deep-focus earthquakes in the Okhotsk Sea since the year of 2002, are shown. It is discussed correlations and possible cause-and-effect relations between a different phenomena such as - dangerous natural hazardous events such as the record tornado outbreak sequences in the USA

  16. Tripodal Receptors for Cation and Anion Sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman,; Verboom, Willem; Reinhoudt, David N.


    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  17. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.


    Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or

  18. Diffusive Soil Degassing of Radon and Carbon Dioxide at San Miguel Volcano, El Salvador, Central America (United States)

    Lopez, D. L.; Olmos, R.; Cartagena, R.; Soriano, T.; Barahona, F.


    San Miguel volcano is located 15 km to the Southwest of San Miguel City (population ~300,000) and lies on the southern fault of the Central American graben at an intersection with NW-SE faults. The composition of San Miguel lavas varies from olivine-pyroxene basalts for the older lava flows to more andesitic compositions for the more recent products. This volcano have been degassing and having small ash emission since the late nineteen eighties. During December 1999 and January 2000, radon gas concentrations (pCi/l) in soils were measured using a Pylon AB5 radon monitor, and flux of CO2 (g/m2/day) was determined using the accumulation chamber method at 205 sampling stations. High gas emission inside the crater did not allow measurements to be taken in that region. CO2 fluxes throughout the soils of the volcanic edifice show low values compared to other active volcanoes of the world, suggesting that San Miguel is degassing preferentially throughout the summit region. CO2 fluxes range from less than 1 to 14 g/m2/day, with an average value of 5.6 g/m2/day. Radon concentrations range from 2 to 833 pCi/l with an average value of 110 pCi/l. Thoron concentrations range from 20 to 2178 pCi/l with an average value of 362 pCi/l. These values are comparable to radon concentrations found in other active volcanoes (e.g. Cerro Negro, Connor et al., 1996). CO2 flux, radon and thoron concentrations show higher values to the northwest and northeast faulted regions. Some anomalies seem to be related to the contact region between the older and more recent lava flows. Thoron/radon ratios show high anomalies aligning in the NW-SE direction where faulting also occurs. These results suggests that low permeability rocks forming the volcanic edifice of San Miguel volcano do not allow large fluxes of magmatic CO2 to be discharged throughout the soils. Higher permeability at faults and contacts allow slightly larger fluxes of CO2 and radon and thoron concentrations.

  19. Role of the Earth degassing (the core emission) for the global tectonics (United States)

    Pavlenkova, Ninel


    source of the deep fluids advection and the resulting Earth degassing is the Earth's core with the high content of hydrogen and helium. The regular system of rifts and of the global rings of the earthquake epicenters may be a result of the Earth expansion generated by strong core emission. This system is traced now as zones of the higher hydrogen degassing. The data on the movement of paleomagnetic poles was explained in the fluids-rotation model by rotation of the whole mantle around the liquid core. Such interpretation, however, is too problematic. It is more reliable to propose that there were no any large movements of the continents or of the whole mantle and the mobile magnetic fields were created by the irregular convection in the core.

  20. Heavy metal cations permeate the TRPV6 epithelial cation channel. (United States)

    Kovacs, Gergely; Danko, Tamas; Bergeron, Marc J; Balazs, Bernadett; Suzuki, Yoshiro; Zsembery, Akos; Hediger, Matthias A


    TRPV6 belongs to the vanilloid family of the transient receptor potential channel (TRP) superfamily. This calcium-selective channel is highly expressed in the duodenum and the placenta, being responsible for calcium absorption in the body and fetus. Previous observations have suggested that TRPV6 is not only permeable to calcium but also to other divalent cations in epithelial tissues. In this study, we tested whether TRPV6 is indeed also permeable to cations such as zinc and cadmium. We found that the basal intracellular calcium concentration was higher in HEK293 cells transfected with hTRPV6 than in non-transfected cells, and that this difference almost disappeared in nominally calcium-free solution. Live cell imaging experiments with Fura-2 and NewPort Green DCF showed that overexpression of human TRPV6 increased the permeability for Ca(2+), Ba(2+), Sr(2+), Mn(2+), Zn(2+), Cd(2+), and interestingly also for La(3+) and Gd(3+). These results were confirmed using the patch clamp technique. (45)Ca uptake experiments showed that cadmium, lanthanum and gadolinium were also highly efficient inhibitors of TRPV6-mediated calcium influx at higher micromolar concentrations. Our results suggest that TRPV6 is not only involved in calcium transport but also in the transport of other divalent cations, including heavy metal ions, which may have toxicological implications.

  1. A new degassing membrane coupled upflow anaerobic sludge blanket (UASB) reactor to achieve in-situ biogas upgrading and recovery of dissolved CH4 from the anaerobic effluent

    DEFF Research Database (Denmark)

    Luo, Gang; Wang, Wen; Angelidaki, Irini


    A new technology for in-situ biogas upgrading and recovery of CH4 from the effluent of biogas reactors was proposed and demonstrated in this study. A vacuum degassing membrane module was used to desorb CO2 from the liquid phase of a biogas reactor. The degassing membrane was submerged into a dega......A new technology for in-situ biogas upgrading and recovery of CH4 from the effluent of biogas reactors was proposed and demonstrated in this study. A vacuum degassing membrane module was used to desorb CO2 from the liquid phase of a biogas reactor. The degassing membrane was submerged......, the COD removal efficiency and CH4 yield were not obviously affected by the gas desorption....

  2. Ionic conduction of lithium hydride single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Pilipenko, G.I.; Oparin, D.V.; Zhuravlev, N.A.; Gavrilov, F.F.


    Using the electrical-conductivity- and NMR-measurement- methods, the ionic-conduction mechanism is established in stoichiometric lithium hydride single crystals. The activation energies of migration of anion- and cation-vacancies and the formation of Schottky-pair defects are determined. They assume that the mechanisms of self-diffusion and conductivity are different in lithium hydride.

  3. Degassing and microlite crystallization during pre-climactic events of the 1991 eruption of Mt. Pinatubo, Philippines (United States)

    Hammer, J.E.; Cashman, K.V.; Hoblitt, R.P.; Newman, S.


    Dacite tephras produced by the 1991 pre-climactic eruptive sequence at Mt. Pinatubo display extreme heterogeneity in vesicularity, ranging in clast density from 700 to 2580 kg m-3. Observations of the 13 surge-producing blasts that preceded the climactic plinian event include radar-defined estimates of column heights and seismically defined eruptive and intra-eruptive durations. A comparison of the characteristics of erupted material, including microlite textures, chemical compositions, and H2O contents, with eruptive parameters suggests that devolatilization-induced crystallization of the magma occurred to a varying extent prior to at least nine of the explosive events. Although volatile loss progressed to the same approximate level in all of the clasts analyzed (weight percent H2O=1.26-1.73), microlite crystallization was extremely variable (0-22%). We infer that syn-eruptive volatile exsolution from magma in the conduit and intra-eruptive separation of the gas phase was facilitated by the development of permeability within magma residing in the conduit. Correlation of maximum microlite crystallinity with repose interval duration (28-262 min) suggests that crystallization occurred primarily intra-eruptively, in response to the reduction in dissolved H2O content that occurred during the preceding event. Detailed textural characterization, including determination of three-dimensional shapes and crystal size distributions (CSD), was conducted on a subset of clasts in order to determine rates of crystal nucleation and growth using repose interval as the time available for crystallization. Shape and size analysis suggests that crystallization proceeded in response to lessening degrees of feldspar supersaturation as repose interval durations increased. We thus propose that during repose intervals, a plug of highly viscous magma formed due to the collapse of vesicular magma that had exsolved volatiles during the previous explosive event. If plug thickness grew

  4. Evaluation of the Effects of Rotary Degassing Process Variables on the Quality of A357 Aluminum Alloy Castings (United States)

    Mostafaei, M.; Ghobadi, M.; Eisaabadi B., Ghasem; Uludağ, Muhammet; Tiryakioğlu, Murat


    The effects of rotary degassing process variables on the melt and casting quality have been investigated using reduced pressure test results and quality index calculations from tensile data. The results showed that the effectiveness of the rotary degassing process of Al alloys is highly dependent on the combination of rotational speed and the gas flow rate, and that the wrong combination of these factors may result in no improvement or even degradation in quality of castings. For the first time, it has been found that the effectiveness of the pouring and filling system to produce high-quality castings can be characterized numerically. This new method of quantifying the casting system is introduced as a new quality improvement tool for materials and process engineers.

  5. Integrated geochemical modelling of magmatic degassing and hydrothermal interaction: a case study from Kawah Ijen volcano, Indonesia (United States)

    Vigouroux-Caillibot, N.; Williams-Jones, G.; Berlo, K.; van Hinsberg, V.; Palmer, S.; Scher, S.; Williams-Jones, W.; Wallace, P. J.


    Monitoring active volcanoes requires an understanding of magmatic degassing in relation to magma depth, temperature, composition, style of degassing (open vs closed) and interactions with hydrothermal systems. This study combines results of subsurface degassing (interpreted from melt inclusions) with measurements of fumarole gases and acid spring waters from Kawah Ijen volcano, Indonesia. Kawah Ijen is a stratovolcano with a growing rhyolite dome on the shore of a hyperacidic crater lake. The dome is emitting sulfur-rich gases from high temperature fumaroles (350-450°C). Matrix glass and melt inclusion compositions (including H2O, CO2, S, Cl and F) were measured for basaltic, dacitic and rhyolitic magmas. The behavior of the volatile species (Dvap-melt) during ascent, degassing and crystallization were modeled for an open system (including vapor fluxing) assuming Rayleigh fractionation, and for closed system processes assuming batch degassing and crystallization. The variable H2O-CO2 contents of the melt inclusions suggest that open system vapor fluxing (XH2Ovapor = 0.25-0.95 for basalt; 0.9-0.95 for dacite) is the dominant degassing style. The modeled S Dvap-melt values for basalt remain low (2-10) as the melt ascends (P= 400 to 100 MPa), then increase sharply to 200 at pressures independent of pressure. Evolution from dacite to rhyolite is characterized by a constant Dvap-melt value of 35. Chlorine behavior is strongly affected by crystallization of Cl-rich apatite in the basaltic magma. In dacite and rhyolite, Cl is mostly dissolved in the melt. The Dvap-melt values range from 7-9 as basalt evolves to dacite and reach 5 for dacite to rhyolite (low pressure degassing). Fluorine contents are highly variable due to crystallization of F-apatite, especially in the more evolved rocks. This precludes meaningful modeling of F-release to the vapor. The best-fit modeled gas compositions (mass ratio) are: CO2/H2O = 0.13-0.27, CO2/S(total) = 2.9-5.7, H2O/S(total) = 21

  6. Using 81Kr-age of groundwater in the Guarani Aquifer, Brazil, to constrain estimates of continental degassing flux of 4He (United States)

    Aggarwal, P. K.; Matsumoto, T.; Sturchio, N. C.; Chang, H. K.; Gastmans, D.; Lu, Z.; Jiang, W.; Müller, P.; Yokochi, R.; Han, L.; Klaus, P.; Torgersen, T.


    Continental degassing flux of helium is the dominant component of dissolved helium in deep groundwater together with that produced in-situ in the aquifer. A reliable estimate of the degassing flux is critical to the use of 4He as a dating tool in groundwater studies. The degassing flux is also important for understanding fluid and heat transport in the mantle and the rust. An independent tracer of groundwater age is required in order to deconvolute the two signals of the external, degassing flux and in situ production. Estimates of degassing flux mostly have relied upon shorter-lived radionuclides such as 14C and tritium and the resulting flux estimates have a significant variability (Torgersen, 2010). In the Guarani Aquifer in Brazil, an effective crustal 4He degassing flux into the aquifer was estimated from 81Kr ages ranging from about 70 Ka to 570 Ka. We then used the model framework of Toregesen and Ivey (1985), modified to include a diffusive reduction of originally uniform crustal helium flux from basement rocks through a thick sedimentary layer beneath the aquifer, to calculate a distribution of radiogenic 4He within the aquifer. With this framework, we obtain 4He ages that are consistent with ages based on 81Kr and 14C, and with a crustal degassing flux equivalent to that estimated from U and Th contents in the crust. The model framework for the Guarani Aquifer is also applied to data from other deep aquifers in Africa and Australia and our results suggest that the continental flux of 4He may be uniform, at least in stable continental areas. Additionally, a reliable estimate of the 4He degassing flux also helps to constrain the surficial discharge of deep groundwater.

  7. Quantifying melt production and degassing rate at mid-ocean ridges from global mantle convection models with plate motion history (United States)

    Li, Mingming; Black, Benjamin; Zhong, Shijie; Manga, Michael; Rudolph, Maxwell L.; Olson, Peter


    The Earth's surface volcanism exerts first-order controls on the composition of the atmosphere and the climate. On Earth, the majority of surface volcanism occurs at mid-ocean ridges. In this study, based on the dependence of melt fraction on temperature, pressure, and composition, we compute melt production and degassing rate at mid-ocean ridges from three-dimensional global mantle convection models with plate motion history as the surface velocity boundary condition. By incorporating melting in global mantle convection models, we connect deep mantle convection to surface volcanism, with deep and shallow mantle processes internally consistent. We compare two methods to compute melt production: a tracer method and an Eulerian method. Our results show that melt production at mid-ocean ridges is mainly controlled by surface plate motion history, and that changes in plate tectonic motion, including plate reorganizations, may lead to significant deviation of melt production from the expected scaling with seafloor production rate. We also find a good correlation between melt production and degassing rate beneath mid-ocean ridges. The calculated global melt production and CO2 degassing rate at mid-ocean ridges varies by as much as a factor of 3 over the past 200 Myr. We show that mid-ocean ridge melt production and degassing rate would be much larger in the Cretaceous, and reached maximum values at ˜150-120 Ma. Our results raise the possibility that warmer climate in the Cretaceous could be due in part to high magmatic productivity and correspondingly high outgassing rates at mid-ocean ridges during that time.

  8. Turmoil at Turrialba Volcano (Costa Rica): Degassing and eruptive processes inferred from high-frequency gas monitoring. (United States)

    de Moor, J Maarten; Aiuppa, A; Avard, G; Wehrmann, H; Dunbar, N; Muller, C; Tamburello, G; Giudice, G; Liuzzo, M; Moretti, R; Conde, V; Galle, B


    Eruptive activity at Turrialba Volcano (Costa Rica) has escalated significantly since 2014, causing airport and school closures in the capital city of San José. Whether or not new magma is involved in the current unrest seems probable but remains a matter of debate as ash deposits are dominated by hydrothermal material. Here we use high-frequency gas monitoring to track the behavior of the volcano between 2014 and 2015 and to decipher magmatic versus hydrothermal contributions to the eruptions. Pulses of deeply derived CO2-rich gas (CO2/Stotal > 4.5) precede explosive activity, providing a clear precursor to eruptive periods that occurs up to 2 weeks before eruptions, which are accompanied by shallowly derived sulfur-rich magmatic gas emissions. Degassing modeling suggests that the deep magmatic reservoir is ~8-10 km deep, whereas the shallow magmatic gas source is at ~3-5 km. Two cycles of degassing and eruption are observed, each attributed to pulses of magma ascending through the deep reservoir to shallow crustal levels. The magmatic degassing signals were overprinted by a fluid contribution from the shallow hydrothermal system, modifying the gas compositions, contributing volatiles to the emissions, and reflecting complex processes of scrubbing, displacement, and volatilization. H2S/SO2 varies over 2 orders of magnitude through the monitoring period and demonstrates that the first eruptive episode involved hydrothermal gases, whereas the second did not. Massive degassing (>3000 T/d SO2 and H2S/SO2 > 1) followed, suggesting boiling off of the hydrothermal system. The gas emissions show a remarkable shift to purely magmatic composition (H2S/SO2 < 0.05) during the second eruptive period, reflecting the depletion of the hydrothermal system or the establishment of high-temperature conduits bypassing remnant hydrothermal reservoirs, and the transition from phreatic to phreatomagmatic eruptive activity.

  9. Effect of compacting pressure, powder degassing and thermobaric treatment on densification and properties of nanocrystalline titanium nitride

    Directory of Open Access Journals (Sweden)

    Andrei V. Kapylou


    Full Text Available The effects of compacting pressure, powder degassing and high pressure sintering temperature and time on the densification and properties of nanocrystalline titanium nitride have been investigated. For this reason, TiN powder with a mean particle size of 55 nm was pressed in the range of compacting pressure from 0.2 to 1.0 GPa and sintered under static pressure of 3.5 GPa in the temperature range of 900–1600°C for 45–120 s. Some of green bodies were degassed in vacuum before sintering. It was shown that samples compacted in the pressure range of 0.2–0.6 GPa have the highest density after the thermobaric treatment. The maximum density (about 97.3 %TD was obtained with degassed samples. Microhardness and microstructure investigations have shown that recrystallization of the TiN nanopowder begins at the sintering temperatures of 1100–1200°C and sintering time less than one minute. The maximum microhardness obtained was 23.2±1.0 GPa and themaximum Young modulus was 370 GPa.

  10. Sea level fall during glaciation stabilized atmospheric CO2 by enhanced volcanic degassing (United States)

    Hasenclever, Jörg; Knorr, Gregor; Rüpke, Lars H.; Köhler, Peter; Morgan, Jason; Garofalo, Kristin; Barker, Stephen; Lohmann, Gerrit; Hall, Ian R.


    Paleo-climate records and geodynamic modelling indicate the existence of complex interactions between glacial sea level changes, volcanic degassing and atmospheric CO2, which may have modulated the climate system's descent into the last ice age. Between ~85 and 70 kyr ago, during an interval of decreasing axial tilt, the orbital component in global temperature records gradually declined, while atmospheric CO2, instead of continuing its long-term correlation with Antarctic temperature, remained relatively stable. Here, based on novel global geodynamic models and the joint interpretation of paleo-proxy data as well as biogeochemical simulations, we show that a sea level fall in this interval caused enhanced pressure-release melting in the uppermost mantle, which may have induced a surge in magma and CO2 fluxes from mid-ocean ridges and oceanic hotspot volcanoes. Our results reveal a hitherto unrecognized negative feedback between glaciation and atmospheric CO2 predominantly controlled by marine volcanism on multi-millennial timescales of ~5,000-15,000 years.

  11. Bubble dynamics during the non-isothermal degassing of liquids. Exploiting microgravity conditions. (United States)

    Kostoglou, Margaritis; Karapantsios, Thodoris D


    This work reviews the up to date state of understanding of dynamic phenomena occurring when gas bubbles grow over submerged heated surfaces. Gas bubbles are produced on hot surfaces because the adjacent liquid layers become superheated causing local desorption of dissolved gases while the liquid far afield remains at low temperatures. Non-isothermal degassing is a very complex process combining heat and mass transport coupled with momentum exchange between the two phases. Difficulties due to buoyancy effects on gas bubbles as well as natural convection of hot liquid layers hindered its thorough investigation in terrestrial conditions and only recent microgravity data allowed serious progress to be made. To reduce the complexity, gas bubble growth on a heated wall was studied here separately from bubble lateral motion and coalescence. A complete mathematical formulation was provided but given the inability to solve the problem numerically with the present resources, a series of approximate solutions were attempted. The comparison between experimental observations and theoretical predictions revealed useful information regarding the governing mechanisms of bubble growth.

  12. Toughness enhancement of powder metallurgy zirconium containing aluminum-lithium alloys through degassing

    Energy Technology Data Exchange (ETDEWEB)

    LaSalle, J.C.; Raybould, D.; Das, S.K.; Limoncelli, E.V.


    In a method for producing a consolidated article from a rapidly solidified, zirconium containing aluminum lithium alloy powder, the improvement is described comprising the step of: degassing said powder in a vacuum at a temperature of at least about 450 C, said powder consisting essentially of the formula Al[sub bal]Li[sub a]Cu[sub b]Mg[sub c]Zr[sub d], where a' ranges from about 2.4 to 2.8 wt%, b' ranges from about 0.5 to 2.0 wt%, c' ranges from 0.2 to 2.0 wt% and d' ranges from greater than about 0.8 to 1.0 wt%, the balance being aluminum and said article having an ultimate tensile strength ranging from 75 to 80 ksi, a tensile elongation ranging from about 5 to 8% and a T-L notched impact toughness ranging from about 100 to 150 in-lb/in[sup 2].

  13. The slender bubble model for very slow degassing in porous media and cold production

    Energy Technology Data Exchange (ETDEWEB)

    Chraibi, M. [Total, Paris (France); Zaleski, S. [Society of Petroleum Engineers, London (United Kingdom)]|[Paris Univ., Paris (France); Franco, F. [Society of Petroleum Engineers, London (United Kingdom)]|[Total, Paris (France)


    Cold oil production leads to degassing of the light species and the formation of a bubbly phase. This is often referred to as the foamy oil effect and is particularly observed with heavy oils, combining high viscosity and asphaltenes. The presence and behaviour of a foamy-oil effect is critical to the cold production process. However, because a wide range of different petrophysical parameters and experimental factors interact in a complex manner, this process is not a well-understood production mechanism. This study focused on improving the understanding of the solution gas drive mechanism in primary heavy oil recovery. A Darcy-scale model was developed that took into account the basic physical phenomena of bubble nucleation, bubble growth by solute diffusion and expansion, and bubble mobilization. The relative permeability of the gas phase was replaced by an expression for the gas mobility with new physical effects related to capillarity, viscosity, gravity, and bubble geometry. The purpose was to fit the productions with a limited number of parameters, having physical meaning, independently from the depletion rate. The paper also presented several simplifications of the basic Darcy-scale equations, that enabled the production prediction in a much simpler manner than through full simulations. The full set of Darcy-scale equations were solved using a numerical solution. The formation of strong gradients of the gas phase saturation were shown to depend on gravity and viscosity. 12 refs., 4 figs.

  14. Prodigious degassing of a billion years of accumulated radiogenic helium at Yellowstone. (United States)

    Lowenstern, J B; Evans, W C; Bergfeld, D; Hunt, A G


    Helium is used as a critical tracer throughout the Earth sciences, where its relatively simple isotopic systematics is used to trace degassing from the mantle, to date groundwater and to time the rise of continents. The hydrothermal system at Yellowstone National Park is famous for its high helium-3/helium-4 isotope ratio, commonly cited as evidence for a deep mantle source for the Yellowstone hotspot. However, much of the helium emitted from this region is actually radiogenic helium-4 produced within the crust by α-decay of uranium and thorium. Here we show, by combining gas emission rates with chemistry and isotopic analyses, that crustal helium-4 emission rates from Yellowstone exceed (by orders of magnitude) any conceivable rate of generation within the crust. It seems that helium has accumulated for (at least) many hundreds of millions of years in Archaean (more than 2.5 billion years old) cratonic rocks beneath Yellowstone, only to be liberated over the past two million years by intense crustal metamorphism induced by the Yellowstone hotspot. Our results demonstrate the extremes in variability of crustal helium efflux on geologic timescales and imply crustal-scale open-system behaviour of helium in tectonically and magmatically active regions.

  15. Seismic detection of increased degassing before Kīlauea's 2008 summit explosion (United States)

    Johnson, Jessica H.; Poland, Michael P.


    The 2008 explosion that started a new eruption at the summit of Kīlauea Volcano, Hawai‘i, was not preceded by a dramatic increase in earthquakes nor inflation, but was associated with increases in SO2 emissions and seismic tremor. Here we perform shear wave splitting analysis on local earthquakes spanning the onset of the eruption. Shear wave splitting measures seismic anisotropy and is traditionally used to infer changes in crustal stress over time. We show that shear wave splitting may also vary due to changes in volcanic degassing. The orientation of fast shear waves at Kīlauea is usually controlled by structure, but in 2008 showed changes with increased SO2 emissions preceding the start of the summit eruption. This interpretation for changing anisotropy is supported by corresponding decreases in Vp/Vs ratio. Our result demonstrates a novel method for detecting changes in gas flux using seismic observations and provides a new tool for monitoring under-instrumented volcanoes.

  16. Synthesis and Ionic Conduction of Cation-deficient Apatite La9.33-2x/3 MxSi6O26 Doped with Mg, Ca, Sr%掺杂的阳离子缺陷型磷灰石La9.33-2x/3MxSi6O26(M=Mg,Sr,Ca)的合成及离子导电特性

    Institute of Scientific and Technical Information of China (English)

    袁文辉; 顾亚萍; 李莉


    Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33-2x/3 MxSi6O26 (M=Mg, Ca, Sr) is prepared by the sol-gel method with sintering at 1000℃. The powder is characterized by X-ray diffraction (XRD) and scanning electron micrograph (SEM). The apatite can be obtained at relatively low temperature as compared to the conventional solid-state reaction method. The measurements of conductivity of a series of doped samples La9.33-2x/3 MxSi6O26 (M=Ca, Mg, Sr) indicate that the type of dopant and the amount have a significant effect on the conductivity. The greatest decrease in conductivity is observed for Mg doping, following the Ca and the Sr doped apatites. The effect is ultimately attributed to the amount of oxygen interstitials, which is affected by the crystal lattice distortion arising from cation vacancies.

  17. The effect of external divalent cations on spontaneous non-selective cation channel currents in rabbit portal vein myocytes. (United States)

    Albert, A P; Large, W A


    1. The effects of external divalent cations on spontaneous single non-selective cation channel currents were studied in outside-out patches from rabbit portal vein smooth muscle cells in K+-free conditions. 2. In an external medium containing 1.5 mM Ca2+ (Ca2+o) the majority of spontaneous channel currents had a unitary conductance of 23 pS, reversal potential (Vr) of +10 mV and a low open probability (Po) at negative patch potentials. Some channels opened to a lower conductance state of about 13 pS suggesting that the cation channels have two conductance states. Open time and burst duration distributions could both be described by two exponentials with time constants of about of 1 ms and 7 ms for open times and 3 ms and 16 ms for burst durations. 3. In 0 Ca2+o the majority of spontaneous cation channels had a unitary conductance of 13 pS and Vr was shifted to +4 mV. Moreover the longer open time and longer burst duration time constants were both reduced to approximately half the values in 1.5 mM Ca2+o. 4. Compared to 0 Ca2+o the single channel currents in 3 microM and 100 microM Ca2+o had a 5- to 6-fold increase in Po which was accompanied by increases in both open times and burst durations. In 3 microM and 100 microM Ca2+o the unitary conductance of the single channel currents was between 22 and 26 pS. 5. At positive membrane potentials the single channel currents had an increased Po compared to negative potentials which was associated with increased open times and burst durations but these values were similar in 3 microM, 100 microM and 1.5 mM Ca2+o. 6. In 1.5 mM Sr2+o and 1.5 mM Ba2+o channels opened to the higher conductance state of about 22-25 pS and had a 3- to 7-fold greater Po than in 0 Ca2+o. 7. In conclusion, external divalent cations have marked effects on the unitary conductance and kinetic behaviour of non-selective cation channels in rabbit portal vein smooth muscle cells.

  18. Are Avellino (4365 cal BP) and Pompeii twin plinian eruptions? Pre-eruptive constraints and degassing history (United States)

    Boudon, Georges; Balcone-Boissard, Hélène; Villemant, Benoît.; Ucciani, Guillaume; Cioni, Raffaello


    Somma-Vesuvius activity started 35 ky ago and is characterized by numerous eruptions of variable composition and eruptive style, sometimes interrupted by long periods of unrest. The main explosive eruptions are represented by four plinian eruptions: Pomici di Base eruption (22 cal ky), Mercato (~8900 cal BP), Avellino (4365 cal BP) and Pompeii (79 AD). The 79 AD eruption embodies the most famous eruption since it's responsible of the destruction of Pompeii and Herculanum and it's the first described eruption. The Avellino eruption represents the last plinian event that preceded the Pompeii eruption. The eruptive sequence is similar to the 79 AD plinian eruption, with an opening phase preceding a main plinian fallout activity which ended by a phreatomagmatic phase. The fallout deposit displays a sharp colour contrast from white to grey pumice, corresponding to a magma composition evolution. We focus our study on the main fallout deposit that we sampled in detail in the Traianello quarry, 9 km North-North East of the crater, to investigate the degassing processes during the eruption, using volatile content and textural observations. Density and vesicularity measurements were obtained on a minimum of 100 pumice clasts sampled in 10 stratigraphic levels in the fallout deposit. On the basis of the density distribution, bulk geochemical data, point analytical measurements on glasses (melt inclusions and residual glass) and textural observations were obtained simultaneously on a minimum of 5 pumice clasts per eruptive unit. The glass composition, in particular the Na/K ratio, evolves from Na-rich phonolite for white pumices to a more K-rich phonolite for grey pumices. The pre-eruptive conditions are constrained by systematic Cl measurements in melt inclusions and matrix glass of pumice clasts. The entire magma was saturated relative to sub-critical fluids (a Cl-rich H2O vapour phase and a brine), with a Cl melt content buffered at ~6000 ppm, and a mean pre-eruptive H2O

  19. Eruption Depths, Magma Storage and Magma Degassing at Sumisu Caldera, Izu-Bonin Arc: Evidence from Glasses and Melt Inclusions (United States)

    Johnson, E. R.


    Island arc volcanoes can become submarine during cataclysmal caldera collapse. The passage of a volcanic vent from atmospheric to under water environment involves complex modifications of the eruption style and subsequent transport of the pyroclasts. Here, we use FTIR measurements of the volatile contents of glass and melt inclusions in the juvenile pumice clasts in the Sumisu basin and its surroundings (Izu-Bonin arc) to investigate changes in eruption depths, magma storage and degassing over time. This study is based on legacy cores from ODP 126, where numerous unconsolidated (250 m), massive to normally graded pumice lapilli-tuffs were recovered over four cores (788C, 790A, 790B and 791A). Glass and clast geochemistry indicate the submarine Sumisu caldera as the source of several of these pumice lapilli-tuffs. Glass chips and melt inclusions from these samples were analyzed using FTIR for H2O and CO2 contents. Glass chips record variable H2O contents; most chips contain 0.6-1.6 wt% H2O, corresponding to eruption depths of 320-2100 mbsl. Variations in glass H2O and pressure estimates suggest that edifice collapse occurred prior-to or during eruption of the oldest of these samples, and that the edifice may have subsequently grown over time. Sanidine-hosted melt inclusions from two units record variably degassed but H2O-rich melts (1.1-5.6 wt% H2O). The lowest H2O contents overlap with glass chips, consistent with degassing and crystallization of melts until eruption, and the highest H2O contents suggest that large amounts of degassing accompanied likely explosive eruptions. Most inclusions, from both units, contain 2-4 wt% H2O, which further indicates that the magmas crystallized at pressures of ~50-100 MPa, or depths ~400-2800 m below the seafloor. Further glass and melt inclusion analyses, including major element compositions, will elucidate changes in magma storage, degassing and evolution over time.

  20. Phenocryst complexity in andesites and dacites from the Tequila volcanic field, Mexico: resolving the effects of degassing vs. magma mixing (United States)

    Frey, Holli M.; Lange, Rebecca A.


    The petrology of five phenocryst-poor (2-5%) andesites and dacites, all of which were erupted from different short-lived, monogenetic vents, is compared to that of phenocryst-rich (10-25%) andesites erupted from the adjacent stratovolcano, Volcán Tequila, in the Mexican arc. Despite differences in phenocryst abundances, these magmas have comparable phase assemblages (plagioclase + orthopyroxene + titanomagnetite + ilmenite + apatite ± augite ± hornblende), and similarly wide variations in phenocryst compositions, coupled to complex zoning patterns. For the phenocryst-poor lavas, equilibrium pairs of two Fe-Ti oxides lead to a narrow range of calculated temperatures for each sample that range from 934 (±24) to 1,073 (±6)°C and oxygen fugacities that range from +0.1 to +0.7 log units relative to the Ni-NiO buffer. Application of the plagioclase-liquid hygrometer to each sample at these calculated temperatures leads to maximum melt water concentrations of 4.6-3.1 wt% during plagioclase crystallization, indicating that the magmas were fluid saturated at depths ≥6.4-4.5 km. There is a wide, continuous range in the composition of plagioclase (≤44 mol% An) and orthopyroxene (≤16% Mg#) phenocrysts in each sample, which is consistent with a loss of dissolved water (≤2.8 wt%) from the melt phase during degassing as the magmas ascended rapidly to the surface. Evidence is presented that shows the effect of dissolved water is to reduce the activity of MgO relative to FeO in the melt phase, which indicates that degassing will also affect the Mg# of pyroxene phenocrysts, with higher melt water concentrations favoring Fe-rich pyroxene. Both plagioclase and orthopyroxene commonly display diffusion-limited growth textures (e.g., skeletal and hopper crystals, large interior melt hollows, and swallow tails), which are consistent with large undercoolings produced by degassing-induced crystallization. Therefore, degassing is proposed as a possible cause for the phenocryst

  1. Conduct disorder (United States)

    ... Conduct disorder is often linked to attention-deficit disorder . Conduct disorder also can be an early sign of ... child or teen has a history of conduct disorder behaviors. A physical examination and blood tests can help ...

  2. Hydrogen Isotope Composition of Magmatic Water: Review of Variations due to Source, Igneous Environment, and Degassing Processes (United States)

    Taylor, B. E.


    The familiar "magmatic water box" frequently shown on plots of δ D vs. δ 18O both represents and misrepresents the hydrogen isotope composition of magmatic water because of the influences of different source compositions and degassing processes. On the one hand, the hydrogen isotope composition of magma source materials in arcs versus continental tectonic settings contributes to differences in the primary δ D values of magmas. On the other hand, water remaining in magmatic rocks and glass is residual, and may express large variations in δ D due either to active degassing, during depressurization associated with emplacement and/or eruption, or to passive degassing during crystallization. The magnitudes of these variations are governed by hydrogen isotope fractionations involving melts, minerals, and dissolved hydrogen (H2O + OH), by water solubility, and whether the process is dominantly a closed- or open-system one. Estimating the primary δ D value of magmatic water requires extrapolation of isotopic and water content data for a suite of co-magmatic samples to a probable undegassed composition (e.g., 5 wt.% H2O). Island arcs and continental settings comprise two principal tectonic settings in which crustal source materials can differ in their hydrogen isotope composition (and dominate over mantle sources). For example, magmas formed in island arcs derive water from subducted marine clays, metamorphosed, hydrothermally altered, and weathered oceanic crust, from pore waters, and possibly, variably metasomatized mantle. Arc magmatic water, sometimes referred to as "andesitic water", tends to have an average δ D value of ca. -30 +/- 5 ‰ , whereas the average δ D value of water from magmas in continental crust regimes can be slightly lighter (e.g. δ D of ca. -45 +/- 10 ‰ ). This difference may be ascribed largely to the fact that continental crust contains water primarily as metamorphic and igneous minerals, whose average values of δ D reflect, among others

  3. Distribution of sulfur aerosol precursors in the SPCZ released by continuous volcanic degassing at Ambrym, Vanuatu (United States)

    Lefèvre, Jérôme; Menkes, Christophe; Bani, Philipson; Marchesiello, Patrick; Curci, Gabriele; Grell, Georg A.; Frouin, Robert


    The Melanesian Volcanic Arc (MVA) emits about 12 kT d- 1 of sulfur dioxide (SO2) to the atmosphere from continuous passive (non-explosive) volcanic degassing, which contributes 20% of the global SO2 emission from volcanoes. Here we assess, from up-to-date and long-term observations, the SO2 emission of the Ambrym volcano, one of the dominant volcanoes in the MVA, and we investigate its role as sulfate precursor on the regional distribution of aerosols, using both satellite observations and model results at 1° × 1° spatial resolution from WRF-Chem/GOCART. Without considering aerosol forcing on clouds, our model parameterizations for convection, vertical mixing and cloud properties provide a reliable chemical weather representation, making possible a cross-examination of model solution and observations. This preliminary work enables the identification of biases and limitations affecting both the model (missing sources) and satellite sensors and algorithms (for aerosol detection and classification) and leads to the implementation of improved transport and aerosol processes in the modeling system. On the one hand, the model confirms a 50% underestimation of SO2 emissions due to satellite swath sampling of the Ozone Monitoring Instrument (OMI), consistent with field studies. The OMI irregular sampling also produces a level of noise that impairs its monitoring capacity during short-term volcanic events. On the other hand, the model reveals a large sensitivity on aerosol composition and Aerosol Optical Depth (AOD) due to choices of both the source function in WRF-Chem and size parameters for sea-salt in FlexAOD, the post-processor used to compute offline the simulated AOD. We then proceed to diagnosing the role of SO2 volcanic emission in the regional aerosol composition. The model shows that both dynamics and cloud properties associated with the South Pacific Convergence Zone (SPCZ) have a large influence on the oxidation of SO2 and on the transport pathways of

  4. A Model of Continental Growth and Mantle Degassing Comparing Biotic and Abiotic Worlds (United States)

    Höning, D.; Hansen-Goos, H.; Spohn, T.


    While examples for interaction of the biosphere with the atmosphere can be easily cited (e.g., production and consumption of O2), interaction between the biosphere and the solid planet and its interior is much less established. It has been argued (e.g., Rosing et al. 2006; Sleep et al, 2012) that the formation of continents could be a consequence of bioactivity harvesting solar energy through photosynthesis to help build the continents and that the mantle should carry a chemical biosignature. We present an interaction model that includes mantle convection, mantle water vapor degassing at mid-oceanic ridges and regassing through subduction zones, continental crust formation and erosion and water storage and transport in a porous oceanic crust that includes hydrous mineral phases. The mantle viscosity in this model depends on the water concentration in the mantle. We use boundary layer theory of mantle convection to parameterize the mantle convection flow rate and assume that the plate speed equals the mantle flow rate. The biosphere enters the calculation through the assumption that the continental erosion rate is enhanced by a factor of several through bioactivity and through an assumed reduction of the kinetic barrier to diagenetic and metamorphic reactions (e.g., Kim et al. 2004) in the sedimentary basins in subduction zones that would lead to increased water storage capacities. We further include a stochastic model of continent-to-continent interactions that limits the effective total length of subduction zones. We use present day parameters of the Earth and explore a phase plane spanned by the percentage of surface coverage of the Earth by continents and the total water content of the mantle. We vary the ratio of the erosion rate in a postulated abiotic Earth to the present Earth, as well as the activation barrier to diagenetic and metamorphic reactions that affect the water storage capacity of the subducting crust. We find stable and unstable fixed points in

  5. Diffuse He degassing from Cumbre Vieja volcano, La Palma, Canary Islands (United States)

    Asensio-Ramos, María; De Jongh, Marli E.; Lamfers, Kristen R.; Alonso, Mar; Amonte, Cecilia; Padrón, Eleazar; Hernández, Pedro A.; Pérez, Nemesio M.


    Helium is considered as an ideal geochemical tracer due to its geochemical properties: chemical inertness, physical stability and practical insolubility in water under normal conditions. These characteristics, together with its high mobility on the crust, make the presence of helium anomalies on the surface environment of a volcanic system to be related to deep fluid migration controlled by volcano-tectonic features, also providing valuable information about the location and characteristics of the gas source and the fracturing of the crust. The recent results reported by Padrón et al. (2013) clearly show importance of helium emission studies for the prediction of major volcanic events and the importance of continuous monitoring of this gas in active volcanic regions. La Palma Island (708.32 km2) is located at the northwestern end of the Canarian Archipelago. Subaerial volcanic activity on this island started ˜2.0 My ago and has taken place exclusively at the southern part in the last 123 ka. Cumbre Vieja volcano, the most active basaltic volcano of the Canary Islands, was built in this zone, including a main north-south rift area 20 km long and up to 1,950 m in elevation, with vents located also at the northwest and northeast. Padrón et al., (2012) showed that helium is mainly emitted along both N-S and N-W rift of Cumbre Vieja, being, therefore, zones of enhanced permeability for deep gas migration and preferential routes for degassing. This work represents a continuation of the results obtained by Padrón et al. (2012) until the year 2016. Each study covered the 220 km2 of Cumbre Vieja with an average of 570 homogenously distributed sampling points. At each sampling site, soil gas samples were collected at 40 cm depth by withdrawing the gas aliquots into 60 cc hypodermic syringes. He content in the soil gases was analyzed by means of quadrupole mass spectrometry (QMS). Atmospheric gas was used periodically to calibrate the instrument. To estimate the helium

  6. Monitoring quiescent volcanoes by diffuse He degassing: case study Teide volcano (United States)

    Pérez, Nemesio M.; Melián, Gladys; Asensio-Ramos, María; Padrón, Eleazar; Hernández, Pedro A.; Barrancos, José; Padilla, Germán; Rodríguez, Fátima; Calvo, David; Alonso, Mar


    Tenerife (2,034 km2), the largest of the Canary Islands, is the only island that has developed a central volcanic complex (Teide-Pico Viejo stratovolcanoes), characterized by the eruption of differentiated magmas. This central volcanic complex has been built in the intersection of the three major volcanic rift-zones of Tenerife, where most of the historical volcanic activity has taken place. The existence of a volcanic-hydrothermal system beneath Teide volcano is suggested by the occurrence of a weak fumarolic system, steamy ground and high rates of diffuse CO2 degassing all around the summit cone of Teide (Pérez et al., 2013). Diffuse emission studies of non-reactive and/or highly mobile gases such as helium have recently provided promising results to detect changes in the magmatic gas component at surface related to volcanic unrest episodes (Padrón et al., 2013). The geochemical properties of He minimize the interaction of this noble gas on its movement toward the earth's surface, and its isotopic composition is not affected by subsequent chemical reactions. It is highly mobile, chemically inert, physically stable, non-biogenic, sparingly soluble in water under ambient conditions, almost non-adsorbable, and highly diffusive with a diffusion coefficient ˜10 times that of CO2. As part of the geochemical monitoring program for the volcanic surveillance of Teide volcano, yearly surveys of diffuse He emission through the surface of the summit cone of Teide volcano have been performed since 2006. Soil He emission rate was measured yearly at ˜130 sampling sites selected in the surface environment of the summit cone of Teide volcano (Tenerife, Canary Islands), covering an area of ˜0.5 km2, assuming that He emission is governed by convection and diffusion. The distribution of the sampling sites was carefully chosen to homogeneously cover the target area, allowing the computation of the total He emission by sequential Gaussian simulation (sGs). Nine surveys have been

  7. Volcanic degassing and secondary hydration of volcanic ash and scoria: Implications for paleoaltimetry and paleoclimate studies (United States)

    Seligman, A. N.; Bindeman, I. N.


    The use of δD of ash as a reliable recorder of δD (and δ18O) values of paleoprecipitation in paleoclimate and paleoaltimetry research still requires experimental verification and testing. It is currently assumed that ash is deposited with a water content of no significance, and that within a few thousand years it becomes sufficiently (up to 4 wt.% H2O) hydrated, although the rate of hydration and whether or not the initial isotopic signature is held, are not well understood. We report analyses of δD and H2O of distal ash from recent eruptions (1980 Mount St. Helens, 1992 Mt. Spurr, and 1974 Volcán de Fuego) that were collected syneruption, in addition to scoria ranging in age from ~50 to 7300 years old from Klyuchevskoy volcano (Kamchatka, Russia), using the TC/EA - MAT 253 continuous flow system. Natural variability of studied samples in wt.% H2O (δD in ‰), with errors represented as 1 s.d. for the average, for recent ash eruptions, range from 0.1 × 0.07 (-102 × 4.7) for Volcán de Fuego up to 0.7 × 0.10 (-104 × 3.5) for Mount St. Helens. Ash from the Mt. Spurr eruption averaged 0.4 × 0.04 (-109 × 4.0), and we plan to also analyze ash from Mt. Pinatubo. The δD values are consistent with a magmatic degassing trend, where the last remaining water is depleted in deuterium, suggesting ash may be deposited with up to 0.7 wt.% H2O as primary magmatic water. Klyuchevskoy scoria (basaltic andesite) shows a general trend of increasing wt.% H2O with increasing age: the youngest samples (<2.0 ka) have ~0.2 wt.% water (-99 to -109 ‰), which is likely primary magmatic, while the older samples (4.7-7.3 ka) generally have a higher water concentration (~0.3-0.5 wt.%); likely local meteoric water based on δD values that are lower than degassed magmatic δD values and higher water content. The samples between ~2.3 and 3.6 ka (0.1 to 0.4 wt.% water) have variable water concentrations due to variations in porosity and therefore surface area between the different

  8. Reconstructing Magma Degassing and Fragmentation: The 1060 CE Plinian Eruption of Medicine Lake Volcano, California (United States)

    Giachetti, T.; Gonnermann, H. M.; Crozier, J.


    Magma fragmentation during explosive volcanic eruptions occurs when the bubble overpressure exceeds some threshold. Because bubble coalescence and ensuing permeable outgassing allow partial release of bubble overpressure, high magma permeabil
ity is thought to adversely affect magma fragmentation and the ability of magma to erupt explosively. We used the Plinian phase of the 1060 CE Glass Mountain eruption of Medicine Lake Volcano, California, to show that this is not necessarily the case. We performed numerical modeling of eruptive magma ascent and bubble growth to predict the development of magma porosity, permeability, and the built-up of gas pressure inside bubbles. We explicitly took into account permeable outgassing in the model. We used the measured porosity and permeability of the Plinian pyroclasts, together with percolation modeling, to reconstruct the conditions for magma degassing and fragmentation. Our results show that the porosity and permeability of pyroclasts coincide with the conditions required for fragmentation of the erupting magma. The onset of fragmentation occurs when the decompression rate reaches about 2 MPa.s-1, corresponding to a constant melt viscosity of ˜107 Pa.s and a magma porosity of approximately 0.75, conditions met for a mass discharge rate of about 107 kg.s-1, a cross sectional area of about 2,000 m2, and at a depth of approximately 1 km. Pyroclasts formed from magma that fragmented over a depth range of several tens of meters, probably reflecting some degree of lateral variability in magma porosity in the conduit. The model also indicates that, even if the magma was highly permeable at the onset of fragmentation, permeable outgassing did not affect fragmentation. The transition to an effusive activity and the emission of obsidian after the Plinian phase of the Glass Mountain eruption is most probably due to a decrease in decompression rate.

  9. Statistical tools applied for the reduction of the defect rate of coffee degassing valves

    Directory of Open Access Journals (Sweden)

    Giorgio Olmi


    Full Text Available Coffee is a very common beverage exported all over the world: just after roasting, coffee beans are packed in plastic or paper bags, which then experience long transfers with long storage times. Fresh roasted coffee emits large amounts of CO2 for several weeks. This gas must be gradually released, to prevent package over-inflation and to preserve aroma, moreover beans must be protected from oxygen coming from outside. Therefore, one-way degassing valves are applied to each package: their correct functionality is strictly related to the interference coupling between their bodies and covers and to the correct assembly of the other involved parts. This work takes inspiration from an industrial problem: a company that assembles valve components, supplied by different manufacturers, observed a high level of defect rate, affecting its valve production. An integrated approach, consisting in the adoption of quality charts, in an experimental campaign for the dimensional analysis of the mating parts and in the statistical processing of the data, was necessary to tackle the question. In particular, a simple statistical tool was made available to predict the defect rate and to individuate the best strategy for its reduction. The outcome was that requiring a strict protocol, regarding the combinations of parts from different manufacturers for assembly, would have been almost ineffective. Conversely, this study led to the individuation of the weak point in the manufacturing process of the mating components and to the suggestion of a slight improvement to be performed, with the final result of a significant (one order of magnitude decrease of the defect rate.

  10. Volcano-tectonic structures and CO2-degassing patterns in the Laacher See basin, Germany (United States)

    Goepel, Andreas; Lonschinski, Martin; Viereck, Lothar; Büchel, Georg; Kukowski, Nina


    The Laacher See Volcano is the youngest (12,900 year BP) eruption center of the Quarternary East-Eifel Volcanic Field in Germany and has formed Laacher See, the largest volcanic lake in the Eifel area. New bathymetric data of Laacher See were acquired by an echo sounder system and merged with topographic light detection and ranging (LiDAR) data of the Laacher See Volcano area to form an integrated digital elevation model. This model provides detailed morphological information about the volcano basin and results of sediment transport therein. Morphological analysis of Laacher See Volcano indicates a steep inner crater wall (slope up to 30°) which opens to the south. The Laacher See basin is divided into a deep northern and a shallower southern part. The broader lower slopes inclined with up to 25° change to the almost flat central part (maximum water depth of 51 m) with a narrow transition zone. Erosion processes of the crater wall result in deposition of volcaniclastics as large deltas in the lake basin. A large subaqueous slide was identified at the northeastern part of the lake. CO2-degassing vents (wet mofettes) of Laacher See were identified by a single-beam echo sounder system through gas bubbles in the water column. These are more frequent in the northern part of the lake, where wet mofettes spread in a nearly circular-shaped pattern, tracing the crater rim of the northern eruption center of the Laacher See Volcano. Additionally, preferential paths for gas efflux distributed concentrically inside the crater rim are possibly related to volcano-tectonic faults. In the southern part of Laacher See, CO2 vents occur in a high spatial density only within the center of the arc-shaped structure Barschbuckel possibly tracing the conduit of a tuff ring.

  11. Early degassing of lunar urKREEP by crust-breaching impact(s) (United States)

    Barnes, Jessica J.; Tartèse, Romain; Anand, Mahesh; McCubbin, Francis M.; Neal, Clive R.; Franchi, Ian A.


    Current models for the Moon's formation have yet to fully account for the thermal evolution of the Moon in the presence of H2O and other volatiles. Of particular importance is chlorine, since most lunar samples are characterised by unique heavy δ37Cl values, significantly deviating from those of other planetary materials, including Earth, for which δ37Cl values cluster around ∼0‰. In order to unravel the cause(s) of the Moon's unique chlorine isotope signature, we performed a comprehensive study of high-precision in situ Cl isotope measurements of apatite from a suite of Apollo samples with a range of geochemical characteristics and petrologic types. The Cl-isotopic compositions measured in lunar apatite in the studied samples display a wide range of δ37Cl values (reaching a maximum value of +36‰), which are positively correlated with the amount of potassium (K), Rare Earth Element (REE) and phosphorous (P) (KREEP) component in each sample. Using these new data, integrated with existing H-isotope data obtained for the same samples, we are able to place these findings in the context of the canonical lunar magma ocean (LMO) model. The results are consistent with the urKREEP reservoir being characterised by a δ37Cl ∼+30‰. Such a heavy Cl isotope signature requires metal-chloride degassing from a Cl-enriched urKREEP LMO residue, a process likely to have been triggered by at least one large crust-breaching impact event that facilitated the transport and exposure of urKREEP liquid to the lunar surface.

  12. In-well degassing issues for measurements of dissolved gases in groundwater. (United States)

    Roy, J W; Ryan, M C


    Measurement of dissolved gases in groundwater is becoming increasingly common and important. Many of these measurements involve monitoring or sampling within wells or from water pumped from wells. We used total dissolved gas pressure (TDGP) sensors placed in the screened section of various wells (4 to 72 m deep) to assess the dissolved gas conditions for open wells compared to the conditions when sealed (i.e., isolated from the atmosphere) with a hydraulic packer (one well) or when pumped. When the packer was installed (non-pumping conditions), TDGP rose from 3.1 atm (314 kPa), with declines noted when the packer was removed or deflated. While pumping, TDGP measured in many of the wells rose to substantially higher levels, up to 4.0 atm (408 kPa) in one case. Thus, when groundwater is gas charged, the background aquifer TDGP, and likewise the dissolved gas concentrations, may be substantially higher than initially measured in open wells, indicating significant in-well degassing. This raises concerns about past and current methods of measuring the dissolved gases in groundwater. Additional procedures that may be required to obtain representative measurements from wells include (1) installing in-well hydraulic packers to seal the well, or (2) pumping to bring in fresh groundwater. However, observed transient decreased TDGPs during pumping, believed to result from gas bubble formation induced by drawdown in the well below a critical pressure (relative to TDGP), may disrupt the measurements made during or after pumping. Thus, monitoring TDGP while pumping gas-charged wells is recommended. Copyright © 2010 The Author(s). Journal compilation © 2010 National Ground Water Association.

  13. Human impact on the historical change of CO2 degassing flux in River Changjiang

    Directory of Open Access Journals (Sweden)

    Zhang Jing


    Full Text Available Abstract The impact of water quality changes in River Changjiang (formally known as the Yangtze River on dissolved CO2 and silicate concentrations and seasonal carbon flux in the past several decades (1960s–2000 was evaluated, based on monitoring data from hydrographic gauge. It was found that dissolved CO2 and silicate in Changjiang decreased dramatically during this decades, as opposed to a marked increase in nutrient (e.g. NO3- concentrations. Our analyses revealed that dissolved CO2 in Changjiang was over-saturated with the atmosphere CO2, and its concentration had showed a declining trend since the 1960s, despite that fluvial DIC flux had maintained stable. Analysis results also suggested that the decrease in dissolved CO2 concentration was attributed to changes on the riverine trophic level and river damming activities in the Changjiang drainage basin. Due to the economic innovation (e.g. agriculture and industry development across the Changjiang watershed, fertilizers application and river regulations have significantly altered the original state of the river. Its ecosystem and hydrological condition have been evolving toward the "lacustrine/reservoir" autotrophic type prevailing with plankton. Accordingly, average CO2 diffusing flux to the atmosphere from the river had been reduced by three-fourth from the 1960s to 1990s, with the flux value being down to 14.2 mol.m-2.yr-1 in the 1990s. For a rough estimate, approximately 15.3 Mt of carbon was degassed annually into the atmosphere from the entire Changjiang drainage basin in the 1990s.

  14. The Free Tricoordinated Silyl Cation Problem

    Directory of Open Access Journals (Sweden)

    Čičak, H.


    Full Text Available As the importance and abundance of silicon in our environment is large, it has been thought that silicon might take the place of carbon in forming a host of similar compounds and silicon-based life. However, until today there is no experimental evidence for such a hypothesis and carbon is still unique among the elements in the vast number and variety of compounds it can form. Also, the corresponding derivatives of the two elements show considerable differences in their chemical properties.The essential debate concerning organosilicon chemistry relates to the existence of the free planar tricoordinated silyl cations in condensed phase (R3Si+, in analogy to carbocations (R3C+ which have been known and characterized as free species. Although silyl cations are thermodynamically more stable than their carbon analogs, they are very reactive due to their high inherent electrophilicity and the ability of hypervalent coordination. On the other hand, stabilization by inductive and hyperconjugative effects and larger steric effects of carbocations make them less sensitive to solvation or other environmental effects than silyl cations. Hence, observation of free silyl cations in the condensed phase proved extremely difficult and the actual problem is the question of the degree of the (remaining silyl cation character.The first free silyl cation, trimesitylsilyl cation, and in analogy with it tridurylsilyl cation, were synthesized by Lambert et al. Free silyl cations based on analogy to aromatic ions (homocyclopropenylium and tropylium have also been prepared. However, in these silyl cations the cationic character is reduced by internal π -conjugation. Čičak et al. prepared some silyl-cationic intermediates (Me3Si--CH≡CR+in solid state. With the help of quantum-mechanical calculations it was concluded that these adducts have much more silyl cation than carbocation character.

  15. Strong S-wave attenuation and actively degassing magma beneath Taal volcano, Philippines, inferred from source location analysis using high-frequency seismic amplitudes (United States)

    Kumagai, H.; Lacson, R. _Jr., Jr.; Maeda, Y.; Figueroa, M. S., II; Yamashina, T.


    Taal volcano, Philippines, is one of the world's most dangerous volcanoes given its history of explosive eruptions and its close proximity to populated areas. A key feature of these eruptions is that the eruption vents were not limited to Main Crater but occurred on the flanks of Volcano Island. This complex eruption history and the fact that thousands of people inhabit the island, which has been declared a permanent danger zone, together imply an enormous potential for disasters. The Philippine Institute of Volcanology and Seismology (PHIVOLCS) constantly monitors Taal, and international collaborations have conducted seismic, geodetic, electromagnetic, and geochemical studies to investigate the volcano's magma system. Realtime broadband seismic, GPS, and magnetic networks were deployed in 2010 to improve monitoring capabilities and to better understand the volcano. The seismic network has recorded volcano-tectonic (VT) events beneath Volcano Island. We located these VT events based on high-frequency seismic amplitudes, and found that some events showed considerable discrepancies between the amplitude source locations and hypocenters determined by using onset arrival times. Our analysis of the source location discrepancies points to the existence of a region of strong S-wave attenuation near the ground surface beneath the east flank of Volcano Island. This region is beneath the active fumarolic area and above sources of pressure contributing inflation and deflation, and it coincides with a region of high electrical conductivity. The high-attenuation region matches that inferred from an active-seismic survey conducted at Taal in 1993. Our results, synthesized with previous results, suggest that this region represents actively degassing magma near the surface, and imply a high risk of future eruptions on the east flank of Volcano Island.

  16. Probing optical band gaps at nanoscale from tetrahedral cation vacancy defects and variation of cation ordering in NiCo2O4 epitaxial thin films (United States)

    Dileep, K.; Loukya, B.; Silwal, P.; Gupta, A.; Datta, R.


    High resolution electron energy loss spectroscopy (HREELS) is utilized to probe the optical band gaps at the nanoscale in epitaxial NiCo2O4 (NCO) thin films with different structural order (cation/charge). The structure of NCO deviates from the ideal inverse spinel (non-magnetic and insulating) for films grown at higher temperatures (>500 °C) towards a mixed cation structure (magnetic with metallic conductivity) at lower deposition temperatures (<450 °C). This significantly modifies the electronic structure as well as the nature of the band gap of the material. Nanoscale regions with unoccupied tetrahedral A site cations are additionally observed in all the samples and direct measurement from such areas reveals considerably lower band gap values as compared to the ideal inverse spinel and mixed cation configurations. Experimental values of band gaps have been found to be in good agreement with the theoretical mBJLDA exchange potential based calculated band gaps for various cation ordering and consideration of A site cation vacancy defects. The origin of rich variation in cation ordering observed in this system is discussed.

  17. Temporal evolution of magma flow and degassing conditions during dome growth, insights from 2D numerical modeling (United States)

    Chevalier, Laure; Collombet, Marielle; Pinel, Virginie


    Understanding magma degassing evolution during an eruption is essential to improving forecasting of effusive/explosive regime transitions at andesitic volcanoes. Lava domes frequently form during effusive phases, inducing a pressure increase both within the conduit and within the surrounding rocks. To quantify the influence of dome height on magma flow and degassing, we couple magma and gas flow in a 2D numerical model. The deformation induced by magma flow evolution is also quantified. From realistic initial magma flow conditions in effusive regime (Collombet, 2009), we apply increasing pressure at the conduit top as the dome grows. Since volatile solubility increases with pressure, dome growth is then associated with an increase in magma dissolved water content at a given depth, which corresponds with a decrease in magma porosity and permeability. Magma flow evolution is associated with ground deflation of a few μrad in the near field. However this signal is not detectable as it is hidden by dome subsidence (a few mrad). A Darcy flow model is used to study the impact of pressure and permeability conditions on gas flow in the conduit and surrounding rock. We show that dome permeability has almost no influence on magma degassing. However, increasing pressure in the surrounding rock, due to dome loading, as well as decreasing magma permeability in the conduit limit permeable gas loss at the conduit walls, thus causing gas pressurization in the upper conduit by a few tens of MPa. Decreasing magma permeability and increasing gas pressure increase the likelihood of magma explosivity and hazard in the case of a rapid decompression due to dome collapse.

  18. Immiscibility of high salinity fluids in volcanic rocks and the mechanism of magma degassing in the Dongying sag, eastern China

    Institute of Scientific and Technical Information of China (English)

    CHEN Yong; ZHOU Yaoqi; XIAO Huanqin; REN Yongjun; SUN Xinian; WANG Qiang; YAN Shiyong; LIU Chaoying


    Fluid inclusions that bear halite daughter min- erals were discovered in volcanic rocks at Pingnan area in the Dongying sag. The samples of the fluid inclusions collected from the BGX-15 well drill cores are hosted in quartz of diorite-porphyrite. The daughter minerals are identified as NaCl crystals after being observed under a microscope and analyzed by in situ Raman spectroscopy at -185℃. The results of micro-thermal analysis show that the homogeniza- tion temperatures of primary fluid inclusions are between 359 and 496℃, and the salinities of fluid inclusions are from 43.26 to 54.51 wt-%. All fluid inclusions in the studied sam- ples can be divided into five types including primary fluid inclusions and secondary fluid inclusions. The fact that five types of fluid inclusions were symbiotic in the same quartz grain implies that immiscibility happened in magma. Due to the decrease in temperature and pressure during the ascent of magma, the fluids became intensively immiscible. This pro- cess accelerates the degassing of CO2 from magma, but the remnant fluids with high salinity are preserved in fluid inclu- sions. Thus, the primary fluid inclusions are mainly in NaCl- H2O fluids and poor in CO2. The results of our study indicate that the degassing of magma and accumulation of CO2 gas at the Pingnan area are relative to the immiscibility of high salinity fluids. This discovery is important because it can help us have a further understanding of the mechanism of magma degassing and accumulation of the inorganic CO2 in eastern China.

  19. CO2 and CH4 degassing from vents and soil in the Salton Sea Geothermal System (California, USA) (United States)

    Mazzini, A.; Etiope, G.; Svensen, H.; Polteau, S.; Planke, S.


    Surface expulsion of mud, water, oil and gas from vents is abundant in the Davis-Schrimpf hydrothermal field (Salton Sea, California). These vents consist of gryphons and pools that commonly cluster in 10-20 m diameter calderas. Additionally, soil degassing occurs all over the field through microfractures or mm-sized conduits. Large temperature variations measured in pools and gryphons are ascribed to different mud/water content and to the influence from hot and cold fluid pulses. We have carried out extensive studies of the Davis-Schrimpf field to determine the flux and the origin of the expelled gases. Gas composition has been analysed over several years (2003, 2006, 2007, 2008), whereas gas flux were measured in December 2008. Compositionally, CO2 is the dominant gas (~98%), with an average CH4 concentration around 1.5%. The CO2 carbon isotopes suggest a mixed mantle-metasediment source, whereas the CH4 is derived from thermal maturation of organic matter. Helium isotope analyses suggest a strong input from the mantle, consistent with CO2 stable carbon isotopic ratio. Gas flux was measured both from vents (i.e., pools and gryphons) by volumetric flux-meter techniques and from diffuse soil degassing by a closed-chamber system equipped with portable CO2 and CH4 sensors, over an area of 20 000 m2, following a 20x20m grid. A conservative estimate from 86 measured focussed vents shows that at least 2 046 kg of CO2 and 11 kg of CH4 vented daily to the atmosphere. Our results also show that at least 15 535 kg/day of CO2 and 61.84 kg/day of CH4 were pervasively released due to soil degassing. These data emphasise that soil degassing can be the dominant component of gas released from hydrothermal fields, even in systems with large and vigorous focussed vents. These results are thus important when calculating global budgets of CO2 emissions of hydrothermal fields.

  20. Experimental fractionation of stable carbon isotopes during degassing of carbon dioxide and precipitation of calcite from aqueous solutions (United States)

    Müller, K.; Winde, V.; Escher, P.; von Geldern, R.; Böttcher, M. E.


    Processes in the carbonate system of surface waters are in particular sensitive to variations of boundary conditions as, for instance, the partial pressure of carbon dioxide in the atmosphere and the aqueous solution. Examples range from streams, rivers, to coastal marine waters. The flux of carbon dioxide from continental flowing waters was recently included into calculations of the global carbon budget (Butman & Raymond, 2011, Nature Geo.). These solutions, are often supersaturated in carbon dioxide with respect to the atmosphere. The degassing of carbon dioxide is associated with a kinetically controlled fractionation of the stable carbon isotopes, which has to be considered in balancing water-air carbon dioxide fluxes. The degassing process additionally leads to the super-saturation of the aqueous solution with respect to calcium carbonate. Stable isotope fractionation is of particular value to identify and quantify processes at the water-gas phase interface and link these non-equilibrium processes to the formation mechanisms of calcite and the hydrodynamics of surface waters. Experiments were carried out with or without inert N2 gas flow to degas carbon dioxide from initially supersaturated solutions. Natural solutions used are from different stations of the Elbe estuary, the Jade Bay, the backbarrier tidal area of Spiekeroog Island, carbonate springs of Rügen Island, and the Baltic Sea coastline. Results are compared experiments using bottled mineral waters. By following the (physico) chemical changes in the solutions (pH, TA, Ca PHREEQC modeling) it was found, that two evolutionary stages can be differentiated. Reaction progress led to the preferential liberation of carbon dioxide containing the light carbon isotope, following a Rayleigh-type process. After an induction period, where only degassing of carbon dioxide took place, a second stage was observed where calcite began to form from the highly supersaturated solutions. In this stage the carbonate

  1. Turmoil at Turrialba Volcano (Costa Rica): Degassing and eruptive processes inferred from high‐frequency gas monitoring (United States)

    Aiuppa, A.; Avard, G.; Wehrmann, H.; Dunbar, N.; Muller, C.; Tamburello, G.; Giudice, G.; Liuzzo, M.; Moretti, R.; Conde, V.; Galle, B.


    Abstract Eruptive activity at Turrialba Volcano (Costa Rica) has escalated significantly since 2014, causing airport and school closures in the capital city of San José. Whether or not new magma is involved in the current unrest seems probable but remains a matter of debate as ash deposits are dominated by hydrothermal material. Here we use high‐frequency gas monitoring to track the behavior of the volcano between 2014 and 2015 and to decipher magmatic versus hydrothermal contributions to the eruptions. Pulses of deeply derived CO2‐rich gas (CO2/Stotal > 4.5) precede explosive activity, providing a clear precursor to eruptive periods that occurs up to 2 weeks before eruptions, which are accompanied by shallowly derived sulfur‐rich magmatic gas emissions. Degassing modeling suggests that the deep magmatic reservoir is ~8–10 km deep, whereas the shallow magmatic gas source is at ~3–5 km. Two cycles of degassing and eruption are observed, each attributed to pulses of magma ascending through the deep reservoir to shallow crustal levels. The magmatic degassing signals were overprinted by a fluid contribution from the shallow hydrothermal system, modifying the gas compositions, contributing volatiles to the emissions, and reflecting complex processes of scrubbing, displacement, and volatilization. H2S/SO2 varies over 2 orders of magnitude through the monitoring period and demonstrates that the first eruptive episode involved hydrothermal gases, whereas the second did not. Massive degassing (>3000 T/d SO2 and H2S/SO2 > 1) followed, suggesting boiling off of the hydrothermal system. The gas emissions show a remarkable shift to purely magmatic composition (H2S/SO2 < 0.05) during the second eruptive period, reflecting the depletion of the hydrothermal system or the establishment of high‐temperature conduits bypassing remnant hydrothermal reservoirs, and the transition from phreatic to phreatomagmatic eruptive activity. PMID:27774371

  2. Shallow-ocean methane leakage and degassing to the atmosphere: triggered by offshore oil-gas and methane hydrate explorations


    Yong eZHANG; Weidong eZhai


    Both offshore oil-gas exploration and marine methane hydrate recovery can trigger massive CH4 release from seafloor. During upward transportation of CH4 plume through water column, CH4 is subjected to dissolution and microbial consumption despite the protection of hydrate and oil coating on bubbles surface. The ultimate CH4 degassing to the atmosphere appears to be water-depth dependent. In shallow oceans with water depth less than 100 m, the natural or human-induced leakages or both lead to ...

  3. Degassing dynamics of basaltic lava lake at a top-ranking volatile emitter: Ambrym volcano, Vanuatu arc (United States)

    Allard, Patrick; Burton, Mike; Sawyer, Georgina; Bani, Philipson


    Persistent lava lakes are rare on Earth and provide volcanologists with a remarkable opportunity to directly investigate magma dynamics and degassing at the open air. Ambrym volcano, in Vanuatu, is one of the very few basaltic arc volcanoes displaying such an activity and voluminous gas emission, but whose study has long remained hampered by challenging accessibility. Here we report the first high temporal resolution (every 5 s) measurements of vigorous lava lake degassing inside its 300 m deep Benbow crater using OP-FTIR spectroscopy. Our results reveal a highly dynamic degassing pattern involving (i) recurrent (100-200 s) short-period oscillations of the volcanic gas composition and temperature, correlating with pulsated gas emission and sourced in the upper part of the lava lake, (ii) a continuous long period (∼8 min) modulation probably due to the influx of fresh magma at the bottom of the lake, and (iii) discrete CO2 spike events occurring in coincidence with the sequential bursting of meter-sized bubbles, which indicates the separate ascent of large gas bubbles or slugs in a feeder conduit with estimated diameter of 6 ± 1 m. This complex degassing pattern, measured with unprecedented detail and involving both coupled and decoupled magma-gas ascent over short time scales, markedly differs from that of quieter lava lakes at Erebus and Kilauea. It can be accounted for by a modest size of Benbow lava lake and its very high basalt supply rate (∼20 m3 s-1), favouring its rapid overturn and renewal. We verify a typical basaltic arc signature for Ambrym volcanic gas and, based on contemporaneous SO2 flux measurements, we evaluate huge emission rates of 160 Gg d-1 of H2O, ∼10 Gg d-1 of CO2 and ∼8 Gg d-1 of total acid gas (SO2, HCl and HF) during medium activity of the volcano in 2008. Such rates make Ambrym one of the three most powerful volcanic gas emitters at global scale, whose atmospheric impact at local and regional scale may be considerable.

  4. Afrikaans Syllabification Patterns

    Directory of Open Access Journals (Sweden)

    Tilla Fick


    Full Text Available In contrast to English, automatic hyphenation by computer of Afrikaans words is a problem that still needs to be addressed, since errors are still often encountered in printed text. An initial step in this task is the ability to automatically syllabify words. Since new words are created continuously by joining words, it is necessary to develop an “intelligent” technique for syllabification. As a first phase of the research, we consider only the orthographic information of words, and disregard both syntactic and morphological information. This approach allows us to use machine-learning techniques such as artificial neural networks and decision trees that are known for their pattern recognition abilities. Both these techniques are trained with isolated patterns consisting of input patterns and corresponding outputs (or targets that indicate whether the input pattern should be split at a certain position, or not. In the process of compiling a list of syllabified words from which to generate training data for the  syllabification problem, irregular patterns were identified. The same letter patterns are split differently in different words and complete words that are spelled identically are split differently due to meaning. We also identified irregularities in and between  the different dictionaries that we used. We examined the influence range of letters that are involved in irregularities. For example, for their in agter-ente and vaste-rente we have to consider three letters to the left of r to be certain where the hyphen should be inserted. The influence range of the k in verstek-waarde and kleinste-kwadrate is four to the left and three to the right. In an analysis of letter patterns in Afrikaans words we found that the letter e has the highest frequency overall (16,2% of all letters in the word list. The frequency of words starting with s is the highest, while the frequency of words ending with e is the highest. It is important to

  5. Mantle CO2 degassing through the Icelandic crust: Evidence from carbon isotopes in groundwater (United States)

    Stefánsson, Andri; Sveinbjörnsdóttir, Árný E.; Heinemeier, Jan; Arnórsson, Stefán; Kjartansdóttir, Ríkey; Kristmannsdóttir, Hrefna


    Carbon isotopes of groundwater in Iceland were studied in order to determine the source and reactions of carbon at divergent plate boundaries not associated with active volcanic systems. All the waters were of meteoric origin, with temperatures of 1-130 °C, pH of ∼4.5-10.5 and dissolved inorganic carbon (∑CO2) between 1.8 and 4100 ppm. The measured range of δ13CO2 and 14CO2 in these waters was large, -27.4 to +2.0‰ and 0.6-118 pMC, respectively. The sources and reactions of dissolved inorganic carbon were studied by comparing the measured chemical and isotope composition with those simulated using isotope geochemical models. Three major sources of CO2 were identified: (1) dissolution of partially degassed basaltic rocks formed at the surface or shallow depths, (2) atmospheric CO2 through air-water exchange at surface, and (3) input of gas at depth into the groundwater systems that has similar carbon and isotope composition as the pre-erupted melt of the upper mantle and lower crust beneath Iceland. In the groundwater systems the CO2 chemistry and isotope content are modified due to carbonate mineral precipitation and changes in aqueous species distribution upon progressive water-rock interaction; these changes needed to be quantified in order to reveal the various CO2 sources. The CO2 flux of the Icelandic crust was estimated to be ∼5-10 · 1010 mol/yr with as high as 50% of the flux not associated with active volcanic centers but placed off-axis where a significant proportion of the CO2 may originate from the mantle. The mantle input of the groundwater off-axis corresponds to CO2 partial pressures of ∼10-6-1 bar and to a mantle CO2 flux of <5 · 105 mol/km2/yr for most areas and up to 125 · 105 and 1600 · 105 for the Southern Lowlands and Snæfellsnes Peninsula, respectively. The CO2 flux from active volcanic geothermal systems in Iceland was estimated to be ∼500-3000 · 105 mol CO2/km2/yr, considerably greater than the highest values observed off-axis.

  6. Mineralogical evidence for H 2 degassing during serpentinization at 300 °C/300 bar (United States)

    Marcaillou, C.; Muñoz, M.; Vidal, O.; Parra, T.; Harfouche, M.


    Hydrogen is produced in large amounts during hydrothermal alteration of peridotite in low-spreading-rate mid-ocean ridges. This production is directly linked to reducing conditions in hydrothermal fluids induced by the oxidation of Fe2+ in primary minerals (olivine and pyroxene) to Fe3+ in secondary minerals (magnetite and serpentine). A better knowledge of iron speciation in serpentine is therefore crucial to the quantification of hydrogen production during the serpentinization process. For the first time, we have determined the amount of ferric iron in altered peridotite as a function of alteration time. We investigated experimentally the alteration of powdered lherzolite in pure water at 300 °C/300 bar. For each experimental run (0, 7, 18, 34 and 70 days), H2 degassing was measured using in-situ gas chromatography and the experimental products were analyzed using XRD, Raman and X-ray absorption spectroscopy at the iron K-edge. In parallel, aqueous solutions were analyzed by ICP-AES. Our results show quasi-complete serpentinization at 70 days with replacement of primary olivine and pyroxene by secondary lizardite and magnetite. The Fe3+/Fetotal ratio is linearly dependent on the hydrogen production and ranges from 0 to 0.66 at the end of the experiment. Our results reveal strong variations in Fe3+ in serpentine for different alteration times, from 0 to 100% of ferric iron, including up to 12% of tetrahedral iron. Hydrogen was produced in three main stages: (1) a first stage during which the H2 production rate reaches a maximum at 18 days and is controlled by the crystallization of magnetite, (2) an intermediate stage during which serpentine incorporates ferric iron and thus plays a major role (up to 50%) in the hydrogen formation, and (3) a final stage during which magnetite amount increases from ~ 2 to ~ 5% of the mineral assemblage. The last alteration stage is accompanied by a slight increase of the Fe3+/Fetotal ratio, while the rate of hydrogen production

  7. Monitoring diffuse He degassing from the summit crater of Pico do Fogo volcano, Cape Verde (United States)

    Alonso, Mar; Dionis, Samara; Fernandes, Paulo; Melián, Gladys; Asensio-Ramos, María; Padilla, Germán D.; Hernández, Pedro A.; Pérez, Nemesio M.; Silva, Sonia


    released the highest value (up to 8 kg d-1), followed by a decrease after the eruption. The last emission value was measured in October 2016 and represents the lowest value of the series (1 kg d-1). This data suggest that monitoring of He degassing rate in volcanic areas is an excellent warning geochemical precursory signal for volcanic unrest. This work demonstrates and reinforces the importance of performing helium emission studies as an important promising volcano monitoring technique that might help to detect early warning signals of volcanic unrest in oceanic volcanic islands.

  8. Geochemical monitoring of Taal volcano (Philippines) by means of diffuse CO2 degassing studies (United States)

    Padrón, Eleazar; Hernández, Pedro A.; Arcilla, Carlo; Pérez, Nemesio M.; Lagmay, Alfredo M.; Rodríguez, Fátima; Quina, Gerald; Alonso, Mar; Padilla, Germán D.; Aurelio, Mario A.


    Observing changes in the discharge rate of CO2 is an important part of volcanic monitoring programs, because it is released by progressive depressurization of magma during ascent and reach the surface well before their parental magma. Taal Volcano in Southwest Luzon, Philippines, lies between a volcanic arc front facing the subduction zone along the Manila Trench and a volcanic field formed from extension beyond the arc front. Taal Volcano Island is formed by a main tuff cone surrounded by several smaller tuff cones, tuff rings and scoria cones. This island is located in the center of the 30 km wide Taal Caldera, now filled by Taal Lake. To monitor the volcanic activity of Taal volcano is a priority task in the Philippines, because several million people live within a 20-km radius of Taal's caldera rim. During the last period of volcanic unrest from 2010 to 2011, the main crater lake of Taal volcano released the highest diffuse CO2 emission rates through the water surface reported to date by volcanic lakes worldwide. The maximum CO2 emission rate measured in the study period occurred two months before the strongest seismic activity recorded during the unrest period (Arpa et al., 2013, Bull Volcanol 75:747). After the unrest period, diffuse CO2 emission has remained in the range 532-860 t/d in the period 2013-2016. In January 2016, an automatic geochemical station to monitor in a continuous mode the diffuse CO2 degassing in a selected location of Taal, was installed in January 2016 to improve the early warning system at the volcano. The station is located at Daang Kastila, at the northern portion of the main crater rim. It measures hourly the diffuse CO2 efflux, atmospheric CO2 concentration, soil water content and temperature, wind speed and direction, air temperature and humidity, rainfall, and barometric pressure. The 2016 time series show CO2 efflux values in the range 20-690 g m-2 d-1.Soil temperature, heavily influenced by rainfall, ranged between 74 and 96o

  9. Tracking Magma Degassing and Changes in Magma Rheology Between Major Dome Collapse Events (United States)

    Genareau, K.; Cronin, S. J.; Lube, G.


    -induced crystallization of plagioclase in addition to late-stage rapid crystallization of pyroxene and Fe-oxides due to oxidation in the extruded dome prior to collapse. Geochemical analyses of the microlites and the groundmass glass will also be presented to examine the behavior of volatiles during the two phases of dome extrusion and quantify how progressive stages of degassing, resulting decompression-induced crystallization, and consequent changes in magma rheology contributed to lava dome collapse at this persistently active stratovolcano.

  10. The Evidence from Inclusions in Pumices for the Direct Degassing of Volatiles from the Magma to the Hydrothermal Fluids in the Okinawa Trough

    Institute of Scientific and Technical Information of China (English)

    YU Zenghui; ZHAI Shikui; ZHAO Guangtao


    This article presents the evidence in support of the direct magma degassing as the principal mechanism of volatilesreleasing into the hydrothermal fluids in the Okinawa Trough, as contrasted to the argument for the hydrothermal strippingof volatiles from the volcanic rocks.Laser Raman microprobe and stepped-heating techniques are employed to determine the compositions and contents of thevolatiles in pumices in the middle Okinawa Trough. The results show that the volatiles are similar to the gases in the hy-drothermal fluids and hydrothermal minerals in composition, the mean percent content of each component and variationtrend. This indicates the direct influence of magma degassing on the hydrothermal fluids. In addition, the contents ofvolatiles in pumices are rather low and do not support the hydrothermal stripping as the main mechanism to enrich the fluidswith gases. The results are consistent with the idea that the direct magma degassing is more important than hydrothermalstripping in supplying gases to the hydrothermal fluids in the Okinawa Trough.

  11. The generation and spectral characterization of oligothiophenes radical cations. A pulse radiolysis investigation

    Energy Technology Data Exchange (ETDEWEB)

    Emmi, S.S. [Istituto FRAE of CNR, Via P. Gobetti 101, 40129 Bologna (Italy); D' Angelantonio, M. [Istituto FRAE of CNR, Via P. Gobetti 101, 40129 Bologna (Italy); Beggiato, G. [Istituto FRAE of CNR, Via P. Gobetti 101, 40129 Bologna (Italy); Poggi, G. [Dipartimento ' G. Ciamician' , Universita di Bologna, Via Selmi 2, 40126 Bologna (Italy); Geri, A. [Istituto FRAE of CNR, Via P. Gobetti 101, 40129 Bologna (Italy); Pietropaolo, D. [Istituto ICOCEA of CNR, Via P. Gobetti 101, 40129 Bologna (Italy); Zotti, G. [Istituto IPELP of CNR, Stati Uniti 4, 35020 Padova (Italy)


    Conjugated polymers and oligomers of thiophene have been employed in a number of electronic devices due to the change in their conductivity by several orders of magnitude when oxidized to their cationic states. The radical cations of oligothiophenes (nT), with number of rings n=1-6, have been produced by pulse radiolysis for the first time and their spectra have been characterized. Electronic structure and transition energies are briefly discussed in the light of semiempirical theoretical calculations.

  12. Advancements in Anion Exchange Membrane Cations

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, Matthew R. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Long, Hai [National Renewable Energy Lab. (NREL), Golden, CO (United States); Park, Andrew M. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Pivovar, Bryan S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)


    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  13. Shallow degassing events as a trigger for very-long-period seismicity at Kīlauea Volcano, Hawai‘i (United States)

    Patrick, Matthew; Wilson, David; Fee, David; Orr, Tim R.; Swanson, Donald A.


    The first eruptive activity at Kīlauea Volcano’s summit in 25 years began in March 2008 with the opening of a 35-m-wide vent in Halema‘uma‘u crater. The new activity has produced prominent very-long-period (VLP) signals corresponding with two new behaviors: episodic tremor bursts and small explosive events, both of which represent degassing events from the top of the lava column. Previous work has shown that VLP seismicity has long been present at Kīlauea’s summit, and is sourced approximately 1 km below Halema‘uma‘u. By integrating video observations, infrasound and seismic data, we show that the onset of the large VLP signals occurs within several seconds of the onset of the degassing events. This timing indicates that the VLP is caused by forces—sourced at or very near the lava free surface due to degassing—transmitted down the magma column and coupling to the surrounding rock at 1 km depth.

  14. Role of degassing of the Noril'sk nickel deposits in the Permian-Triassic mass extinction event. (United States)

    Le Vaillant, Margaux; Barnes, Stephen J; Mungall, James E; Mungall, Emma L


    The largest mass extinction event in Earth's history marks the boundary between the Permian and Triassic Periods at circa 252 Ma and has been linked with the eruption of the basaltic Siberian Traps large igneous province (SLIP). One of the kill mechanisms that has been suggested is a biogenic methane burst triggered by the release of vast amounts of nickel into the atmosphere. A proposed Ni source lies within the huge Noril'sk nickel ore deposits, which formed in magmatic conduits widely believed to have fed the eruption of the SLIP basalts. However, nickel is a nonvolatile element, assumed to be largely sequestered at depth in dense sulfide liquids that formed the orebodies, preventing its release into the atmosphere and oceans. Flotation of sulfide liquid droplets by surface attachment to gas bubbles has been suggested as a mechanism to overcome this problem and allow introduction of Ni into the atmosphere during eruption of the SLIP lavas. Here we use 2D and 3D X-ray imagery on Noril'sk nickel sulfide, combined with simple thermodynamic models, to show that the Noril'sk ores were degassing while they were forming. Consequent "bubble riding" by sulfide droplets, followed by degassing of the shallow, sulfide-saturated, and exceptionally volatile and Cl-rich SLIP lavas, permitted a massive release of nickel-rich volcanic gas and subsequent global dispersal of nickel released from this gas as aerosol particles.

  15. Recent mantle degassing recorded by carbonic spring deposits along sinistral strike-slip faults, south-central Australia (United States)

    Ring, Uwe; Tonguç Uysal, I.; Yüce, Galip; Ünal-İmer, Ezgi; Italiano, Francesco; İmer, Ali; Zhao, Jian-xin


    The interior of the Australian continent shows evidence for late Quaternary to Recent fault-controlled mantle 3He and CO2 degassing. A series of interconnected NW-striking sinistral faults, the Norwest fault zone (NFZ), in south-central Australia are associated with travertine mounds, the latter show a regular spacing of 50-70 km. U-series ages on 26 samples range from 354 ± 7 to 1.19 ± 0.02ka (2σ errors) and suggest a clustering every ∼3-4 ka since ∼26 ka. Geochemical data demonstrate a remarkable mantle-to-groundwater connection. Isotopic data indicate that the groundwater is circulating to depths >3 km and interacting with Neoproterozoic/Cambrian basement and mantle volatiles. 3He/4He isotope ratios show that the He comes in part from the mantle. This demonstrates that the NFZ cuts through the entire crust and provides pathways for mantle degassing. Scaling relationships suggest that the series of sinistral faults that make up the NFZ are interconnected at depths and have a significant strike length of 60-70 km or more. The NFZ occurs where a major compositional boundary and a significant heat flow anomaly occurs, and a major step in lithospheric thickness has been mapped. We discuss a tectonic model in which recent stress field, heat flow and lithospheric structure in central Australia reactivated a set of steeply dipping Neoproterozoic faults, which may now be growing into a crustal/lithospheric-scale structure.

  16. Cation diffusion in the natural zeolite clinoptilolite

    Energy Technology Data Exchange (ETDEWEB)

    Dyer, A.; White, K.J. [Science Research Institute, Chemistry Division, Cockcroft Building, University of Salford, Salford (United Kingdom)


    The natural zeolite clinoptilolite is mined commercially in many parts of the world. It is a selective exchanger for the ammonium cation and this has prompted its use in waste water treatment, swimming pools and in fish farming. It is also used to scavenge radioisotopes in nuclear waste clean-up. Further potential uses for clinoptilolite are in soil amendment and remediation. The work described herein provides thermodynamic data on cation exchange processes in clinoptilolite involving the NH{sub 4}, Na, K, Ca, and Mg cations. The data includes estimates of interdiffusion coefficients together with free energies, entropies and energies of activation for the cation exchanges studied. Suggestions are made as to the mechanisms of cation-exchanges involved.

  17. Soil CO2 degassing path along volcano-tectonic structures in the Pico-Faial-São Jorge islands (Azores archipelago, Portugal) (United States)

    Viveiros, Fátima; Marcos, Márcio; Faria, Carlos; Gaspar, João L.; Ferreira, Teresa; Silva, Catarina


    The Azores archipelago is composed of nine volcanic islands located at the triple junction between the North American, Eurasian and Nubian plates. Nowadays the volcanic activity in the archipelago is characterized by the presence of secondary manifestations of volcanism, such as hydrothermal fumaroles, thermal and cold CO2-rich springs as well as soil diffuse degassing areas, and low magnitude seismicity. Soil CO2 degassing (concentration and flux) surveys have been performed at Pico, Faial and São Jorge islands to identify possible diffuse degassing structures. Since the settlement of the Azores in the 15th Century these three islands were affected by seven onshore volcanic eruptions and at least six destructive earthquakes. These islands are crossed by numerous active tectonic structures with dominant WNW-ESE direction, and less abundant conjugate NNW-SSE trending faults. A total of 2855 soil CO2 concentration measurements have been carried out with values varying from 0 to 20.7 vol.%. Soil CO2 flux measurements, using the accumulation chamber method, have also been performed at Pico and Faial islands in the summer of 2011 and values varied from absence of CO2 to 339 g m-2 d-1. The highest CO2 emissions were recorded at Faial Island and were associated with the Pedro Miguel graben faults, which seem to control the CO2 diffuse degassing and were interpreted as the pathways for the CO2 ascending from deep reservoirs to the surface. At São Jorge Island, four main degassing zones have been identified at the intersection of faults or associated to WNW-ESE tectonic structures. Four diffuse degassing structures were identified at Pico Island essentially where different faults intersect. Pico geomorphology is dominated by a 2351 m high central volcano that presents several steam emissions at its summit. These emissions are located along a NW-SE fault and the highest measured soil CO2 concentration reached 7.6 vol.% with a maximum temperature of 77 ºC. The diffuse

  18. Soil CO2 Degassing Path along Volcano-Tectonic Structures in the Pico-Faial-São Jorge Islands (Azores Archipelago, Portugal

    Directory of Open Access Journals (Sweden)

    Fátima Viveiros


    Full Text Available The Azores archipelago is composed of nine volcanic islands located at the triple junction between the North American, Eurasian, and Nubian plates. Nowadays the volcanic activity in the archipelago is characterized by the presence of secondary manifestations of volcanism, such as hydrothermal fumaroles, thermal and cold CO2-rich springs as well as soil diffuse degassing areas, and low magnitude seismicity. Soil CO2 degassing (concentration and flux surveys have been performed at Pico, Faial, and São Jorge islands to identify possible diffuse degassing structures. Since the settlement of the Azores in the fifteenth Century these three islands were affected by seven onshore volcanic eruptions and at least six destructive earthquakes. These islands are crossed by numerous active tectonic structures with dominant WNW-ESE direction, and less abundant conjugate NNW-SSE trending faults. A total of 2,855 soil CO2 concentration measurements have been carried out with values varying from 0 to 20.7 vol.%. Soil CO2 flux measurements, using the accumulation chamber method, have also been performed at Pico and Faial islands in the summer of 2011 and values varied from absence of CO2 to 339 g m−2 d−1. The highest CO2 emissions were recorded at Faial Island and were associated with the Pedro Miguel graben faults, which seem to control the CO2 diffuse degassing and were interpreted as the pathways for the CO2 ascending from deep reservoirs to the surface. At São Jorge Island, four main degassing zones have been identified at the intersection of faults or associated to WNW-ESE tectonic structures. Four diffuse degassing structures were identified at Pico Island essentially where different faults intersect. Pico geomorphology is dominated by a 2,351 m high central volcano that presents several steam emissions at its summit. These emissions are located along a NW-SE fault and the highest measured soil CO2 concentration reached 7.6 vol.% with a maximum

  19. 210Pb- 226Ra and 228Ra- 232Th systematics in young arc lavas: implications for magma degassing and ascent rates (United States)

    Turner, Simon; Black, Stuart; Berlo, Kim


    New data show that island arc rocks have ( 210Pb/ 226Ra) o ratios which range from as low as 0.24 up to 2.88. In contrast, ( 228Ra/ 232Th) appears always within error of 1 suggesting that the large 226Ra-excesses observed in arc rocks were generated more than 30 years ago. This places a maximum estimate on melt ascent velocities of around 4000 m/year and provides further confidence that the 226Ra excesses reflect deep (source) processes rather than shallow level alteration or seawater contamination. Conversely, partial melting must have occurred more than 30 years prior to eruption. The 210Pb deficits are most readily explained by protracted magma degassing. Using published numerical models, the data suggest that degassing occurred continuously for periods up to several decades just prior to eruption but no link with eruption periodicity was found. Longer periods are required if degassing is discontinuous, less than 100% efficient or if magma is recharged or stored after degassing. The long durations suggest much of this degassing occurs at depth with implications for the formation of hydrothermal and copper-porphyry systems. A suite of lavas erupted in 1985-1986 from Sangeang Api volcano in the Sunda arc are characterised by deficits of 210Pb relative to 226Ra from which 6-8 years of continuous 222Rn degassing would be inferred from recent numerical models. These data also form a linear ( 210Pb)/Pb-( 226Ra)/Pb array which might be interpreted as a 71-year isochron. However, the array passes through the origin suggesting displacement downwards from the equiline in response to degassing and so the slope of the array is inferred not to have any age significance. Simple modelling shows that the range of ( 226Ra)/Pb ratios requires thousands of years to develop consistent with differentiation occurring in response to cooling at the base of the crust. Thus, degassing post-dated, and was not responsible for magma differentiation. The formation, migration and extraction

  20. Electrical conductivity, ionic conductivity, optical absorption, and gas separation properties of ionically conductive polymer membranes embedded with Si microwire arrays


    Spurgeon, Joshua M.; Walter, Michael G.; Zhou, Junfeng; Kohl, Paul A.; Lewis, Nathan S.


    The optical absorption, ionic conductivity, electronic conductivity, and gas separation properties have been evaluated for flexible composite films of ionically conductive polymers that contain partially embedded arrays of ordered, crystalline, p-type Si microwires. The cation exchange ionomer Nafion, and a recently developed anion exchange ionomer, poly(arylene ether sulfone) that contains quaternary ammonium groups (QAPSF), produced composite microwire array/ionomer membrane films that were...

  1. Mobility of alkali cations in polypyrrole-dodecyl sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Kupila, E.L. [Department of Chemistry, University of Turku, 20500 Turku (Finland); Kankare, J. [Department of Chemistry, University of Turku, 20500 Turku (Finland)


    Due to the immobility of the large dodecyl sulfate anion, the mobile ions in polypyrrole-dodecyl sulfate are small ions from the solution. Virgin PP-dodecyl sulfate does not contain other ionic species, but already the first reduction causes the incorporation of cations into the membrane. Using in situ AC conductimetry on a double-band platinum electrode, we show that the insertion of cations from the solution into the PP membrane proceeds as a non-conducting zone advancing from the solution interface toward the substrate. The model allows to estimate ion mobilities in the membrane giving 8.6x10{sup -7}cm{sup 2}s{sup -1}V{sup -1} for K{sup +}. (orig.)

  2. Radical Cations and Acid Protection during Radiolysis

    Energy Technology Data Exchange (ETDEWEB)

    Bruce J. Mincher; Christopher A. Zarzana; Stephen P. Mezyk


    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO3. It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  3. Cationic Bolaamphiphiles for Gene Delivery (United States)

    Tan, Amelia Li Min; Lim, Alisa Xue Ling; Zhu, Yiting; Yang, Yi Yan; Khan, Majad


    Advances in medical research have shed light on the genetic cause of many human diseases. Gene therapy is a promising approach which can be used to deliver therapeutic genes to treat genetic diseases at its most fundamental level. In general, nonviral vectors are preferred due to reduced risk of immune response, but they are also commonly associated with low transfection efficiency and high cytotoxicity. In contrast to viral vectors, nonviral vectors do not have a natural mechanism to overcome extra- and intracellular barriers when delivering the therapeutic gene into cell. Hence, its design has been increasingly complex to meet challenges faced in targeting of, penetration of and expression in a specific host cell in achieving more satisfactory transfection efficiency. Flexibility in design of the vector is desirable, to enable a careful and controlled manipulation of its properties and functions. This can be met by the use of bolaamphiphile, a special class of lipid. Unlike conventional lipids, bolaamphiphiles can form asymmetric complexes with the therapeutic gene. The advantage of having an asymmetric complex lies in the different purposes served by the interior and exterior of the complex. More effective gene encapsulation within the interior of the complex can be achieved without triggering greater aggregation of serum proteins with the exterior, potentially overcoming one of the great hurdles faced by conventional single-head cationic lipids. In this review, we will look into the physiochemical considerations as well as the biological aspects of a bolaamphiphile-based gene delivery system.

  4. Fault-related CO2 degassing, geothermics, and fluid flow in southern California basins---Physiochemical evidence and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Boles, James R. [Univ. of California, Santa Barbara, CA (United States); Garven, Grant [Tufts Univ., Medford, MA (United States)


    Our studies have had an important impact on societal issues. Experimental and field observations show that CO2 degassing, such as might occur from stored CO2 reservoir gas, can result in significant stable isotopic disequilibrium. In the offshore South Ellwood field of the Santa Barbara channel, we show how oil production has reduced natural seep rates in the area, thereby reducing greenhouse gases. Permeability is calculated to be ~20-30 millidarcys for km-scale fault-focused fluid flow, using changes in natural gas seepage rates from well production, and poroelastic changes in formation pore-water pressure. In the Los Angeles (LA) basin, our characterization of formation water chemistry, including stable isotopic studies, allows the distinction between deep and shallow formations waters. Our multiphase computational-based modeling of petroleum migration demonstrates the important role of major faults on geological-scale fluid migration in the LA basin, and show how petroleum was dammed up against the Newport-Inglewood fault zone in a “geologically fast” interval of time (less than 0.5 million years). Furthermore, these fluid studies also will allow evaluation of potential cross-formational mixing of formation fluids. Lastly, our new study of helium isotopes in the LA basin shows a significant leakage of mantle helium along the Newport Inglewood fault zone (NIFZ), at flow rates up to 2 cm/yr. Crustal-scale fault permeability (~60 microdarcys) and advective versus conductive heat transport rates have been estimated using the observed helium isotopic data. The NIFZ is an important deep-seated fault that may crosscut a proposed basin decollement fault in this heavily populated area, and appears to allow seepage of helium from the mantle sources about 30 km beneath Los Angeles. The helium study has been widely cited in recent weeks by the news media, both in radio and on numerous web sites.

  5. Electrical Conductivity. (United States)

    Hershey, David R.; Sand, Susan


    Explains how electrical conductivity (EC) can be used to measure ion concentration in solutions. Describes instrumentation for the measurement, temperature dependence and EC, and the EC of common substances. (PR)

  6. Cation distributions on rapidly solidified cobalt ferrite (United States)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.


    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  7. Cation distributions on rapidly solidified cobalt ferrite (United States)

    De Guire, Mark R.; Kalonji, Gretchen; O'Handley, Robert C.


    The cation distributions in two rapidly solidified cobalt ferrites have been determined using Moessbauer spectroscopy at 4.2 K in an 8-T magnetic field. The samples were obtained by gas atomization of a Co0-Fe2O3-P2O5 melt. The degree of cation disorder in both cases was greater than is obtainable by cooling unmelted cobalt ferrite. The more rapidly cooled sample exhibited a smaller departure from the equilibrium cation distribution than did the more slowly cooled sample. This result is explained on the basis of two competing effects of rapid solidification: high cooling rate of the solid, and large undercooling.

  8. Hydraulic conductivity of GCLs in MSW landfills

    Institute of Scientific and Technical Information of China (English)

    LI Guo-cheng; YANG Wu-chao; DAN Tang-hui


    The state of the art of the study on the hydraulic conductivity of GCLs is presented in terms of the in-fluence of the effective stress, chemical interactions, freeze - thaw cycles and temperature gradients. The chan-ges of void ratio caused by changes of effective stress have a direct linear effect on the hydraulic conductivity, regardless of the cation concentration or the thickness of the adsorbed layer. The hydraulic conductivity is relat-ed to the relative abundance of monovalent and divalent cation(RMD), and RMD has a great effect on the hy-draulic conductivity in weak solution. The long-term susceptibility of GCLs to increased hydraulic conductivity as a response to repeated freeze-thaw cycling is minimal, which has been proved after 150 freeze-thaw cycles. The potential of desiccation cracking increases with the increasing temperature gradient and is related to the ini-tial subsoil water content, the applied overburden stress, etc.

  9. Solution behaviour of new cationic surfactants derived from Guerbet alcohols and their use in hair conditioners. (United States)

    Yahagi, K; Hoshino, N; Hirota, H


    Summary The solution behaviour of new cationic surfactants, synthesized by using long-chain Guerbet alcohols, in water was investigated by a polarizing microscopic technique, differential scanning calorimetry, and electric conductivity measurements. These surfactants show the gel-liquid crystalline phase transition to be lower than 0 degrees C and form lamellar liquid crystals even in cold water and at low concentrations of surfactants. The sorption of cationic surfactants from aqueous solutions onto hair was determined as a function of temperature. The effect of adsorbed cationic surfactants on the critical surface tension and kinetic frictional coefficients of hair surface have been investigated. These surface characteristics of hair treated with quaternary ammonium compounds derived from Guerbet alcohols were found to be significantly improved. These results can be explained by the high ability of sorption onto hair. Hair rinses and conditioners having excellent ease of combing or brushing for wet and dry hair can be formulated by the application of these cationic surfactants.

  10. Ammonia vapor sensing properties of polyaniline-titanium(IV)phosphate cation exchange nanocomposite. (United States)

    Khan, Asif Ali; Baig, Umair; Khalid, Mohd


    In this study, the electrically conducting polyaniline-titanium(IV)phosphate (PANI-TiP) cation exchange nanocomposite was synthesized by sol-gel method. The cation exchange nanocomposite based sensor for detection of ammonia vapors was developed at room temperature. It was revealed that the sensor showed good reversible response towards ammonia vapors ranging from 3 to 6%. It was found that the sensor with p-toluene sulphonic acid (p-TSA) doped exhibited higher sensing response than hydrochloric acid doped. This sensor has detection limit ≤1% ammonia. The response of resistivity changes of the cation exchange nanocomposite on exposure to different concentrations of ammonia vapors shows its utility as a sensing material. These studies suggest that the cation exchange nanocomposite could be a good material for ammonia sensor at room temperature.

  11. Enhance performance of micro direct methanol fuel cell by in situ CO2 removal using novel anode flow field with superhydrophobic degassing channels (United States)

    Liang, Junsheng; Luo, Ying; Zheng, Sheng; Wang, Dazhi


    Capillary blocking caused by CO2 bubbles in anode flow field (AFF) is one of the bottlenecks for performance improvement of a micro direct methanol fuel cell (μDMFC). In this work, we present a novel AFF structure with nested layout of hydrophilic fuel channels and superhydrophobic degassing channels which can remove most of CO2 from AFF before it is released to the fuel channels. The new AFFs are fabricated on Ti substrates by using micro photochemical etching combined with anodization and fluorination treatments. Performance of the μDMFCs with and without superhydrophobic degassing channels in their AFF is comparatively studied. Results show that the superhydrophobic degassing channels can significantly speed up the exhaust of CO2 from the AFF. CO2 clogging is not observed in the new AFFs even when their comparison AFFs have been seriously blocked by CO2 slugs under the same operating conditions. 55% and 60% of total CO2 produced in μDMFCs with N-serpentine and N-spiral AFF can be respectively removed by the superhydrophobic degassing channels. The power densities of the μDMFCs equipped with new serpentine and spiral AFFs are respectively improved by 30% and 90% compared with those using conventional AFFs. This means that the new AFFs developed in this work can effectively prevent CO2-induced capillary blocking in the fuel channels, and finally significantly improve the performance of the μDMFCs.

  12. Cationic ruthenium alkylidene catalysts bearing phosphine ligands. (United States)

    Endo, Koji; Grubbs, Robert H


    The discovery of highly active catalysts and the success of ionic liquid immobilized systems have accelerated attention to a new class of cationic metathesis catalysts. We herein report the facile syntheses of cationic ruthenium catalysts bearing bulky phosphine ligands. Simple ligand exchange using silver(i) salts of non-coordinating or weakly coordinating anions provided either PPh3 or chelating Ph2P(CH2)nPPh2 (n = 2 or 3) ligated cationic catalysts. The structures of these newly reported catalysts feature unique geometries caused by ligation of the bulky phosphine ligands. Their activities and selectivities in standard metathesis reactions were also investigated. These cationic ruthenium alkylidene catalysts reported here showed moderate activity and very similar stereoselectivity when compared to the second generation ruthenium dichloride catalyst in ring-closing metathesis, cross metathesis, and ring-opening metathesis polymerization assays.

  13. Stable isotope and petrologic evidence for open-system degassing during the climactic and pre-climactic eruptions of Mt. Mazama, Crater Lake, Oregon (United States)

    Mandeville, C.W.; Webster, J.D.; Tappen, C.; Taylor, B.E.; Timbal, A.; Sasaki, A.; Hauri, E.; Bacon, C.R.


    Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km3 of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43??N, long. 122??W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H2O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing. Sulfur isotope analyses of climactic rhyodacitic whole rocks yield ??34S values of 2.8-14.8??? with corresponding matrix glass values of 2.4-13.2???. ??34S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H2O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in ??34S from -0.4??? to 5.8??? and from -0.1??? to 3.5???, respectively. Initial ??34S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0???. Hydrogen isotope (??D) and total H2O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values ??f -103 to -53??? and 0.23-1.74 wt%, respectively. Values of

  14. MaGa, a web-based collaborative database for gas emissions: a tool to improve the knowledge on Earth degassing (United States)

    Frigeri, A.; Cardellini, C.; Chiodini, G.; Frondini, F.; Bagnato, E.; Aiuppa, A.; Fischer, T. P.; Lehnert, K. A.


    The study of the main pathways of carbon flux from the deep Earth requires the analysis of a large quantity and variety of data on volcanic and non-volcanic gas emissions. Hence, there is need for common frameworks to aggregate available data and insert new observations. Since 2010 we have been developing the Mapping Gas emissions (MaGa) web-based database to collect data on carbon degassing form volcanic and non-volcanic environments. MaGa uses an Object-relational model, translating the experience of field surveyors into the database schema. The current web interface of MaGa allows users to browse the data in tabular format or by browsing an interactive web-map. Enabled users can insert information as measurement methods, instrument details as well as the actual values collected in the field. Measurements found in the literature can be inserted as well as direct field observations made by human-operated instruments. Currently the database includes fluxes and gas compositions from active craters degassing, diffuse soil degassing and fumaroles both from dormant volcanoes and open-vent volcanoes from literature survey and data about non-volcanic emission of the Italian territory. Currently, MaGa holds more than 1000 volcanic plume degassing fluxes, data from 30 sites of diffuse soil degassing from italian volcanoes, and about 60 measurements from fumarolic and non volcanic emission sites. For each gas emission site, the MaGa holds data, pictures, descriptions on gas sampling, analysis and measurement methods, together with bibliographic references and contacts to researchers having experience on each site. From 2012, MaGa developments started to be focused towards the framework of the Deep Earth Carbon Degassing research initiative of the Deep Carbon Observatory. Whithin the DECADE initiative, there are others data systems, as EarthChem and the Smithsonian Institution's Global Volcanism Program. An interoperable interaction between the DECADE data systems is being

  15. Review on cation exchange selectivity coefficients for MX-80 bentonite

    Energy Technology Data Exchange (ETDEWEB)

    Domenech, C.; Arcos, D.; Duro, L. [ENVIROS, Passeig de Rubi, 29-31, 08197 Valldoreix (Spain); Sellin, P. [SKB, Brahegatan 47, SE-102 40 Stockholm (Sweden)


    Full text of publication follows: Bentonite is considered as engineered barrier in the near field of a nuclear waste repository due to its low permeability, what impedes groundwater flow to the nuclear waste, and its high retention capacity (sorption) of radionuclides in the eventuality of groundwater intrusion. One of the main retention processes occurring at the bentonite surface is ion exchange. This process may exert a strong control on the mobility of major pore water cations. Changes in major cation concentration, especially calcium, can affect the dissolution-precipitation of calcite, which in turn controls one of the key parameters in the system: pH. The cation exchange process is usually described according to the Gaines-Thomas convention: Ca{sup 2+} + 2 NaX = CaX{sub 2} + 2 Na{sup +}, K{sub Ca} = (N{sub Ca} x a{sup 2}{sub Na{sup +}})/(N{sup 2}{sub Na} x a{sub Ca{sup 2+}}) where K{sub Ca} is the selectivity coefficient for the Ca by Na exchange, ai is the activity of cation 'i' in solution and NJ the equivalent fractional occupancy of cation 'J' in bentonite. Parameters such as solid to liquid (S:L) ratio and dry density of the solid have an important influence on the value of selectivity coefficients (K{sub ex}). Although in most geochemical modelling works, K{sub ex} values are directly taken from experiments conducted at low S:L ratios and low dry densities, the expected conditions in a deep geological nuclear waste repository are higher S:L and higher bentonite density (1.6{sup -3} in the SKB design to obtain a fully water saturated density of around 2.0{sup -3}). Experiments focused at obtaining selectivity coefficients under the conditions of interest face the difficulty of achieving a proper extraction and analyses of pore water without disturbing the system by the sampling method itself. In this work we have conducted a complete analyses of published data on MX-80 bentonite cationic exchange in order to assess the

  16. Conduct disorders

    NARCIS (Netherlands)

    Buitelaar, J.K.; Smeets, K.C.; Herpers, P.; Scheepers, F.; Glennon, J.; Rommelse, N.N.J.


    Conduct disorder (CD) is a frequently occurring psychiatric disorder characterized by a persistent pattern of aggressive and non-aggressive rule breaking antisocial behaviours that lead to considerable burden for the patients themselves, their family and society. This review paper updates diagnostic

  17. Cationized Carbohydrate Gas-Phase Fragmentation Chemistry (United States)

    Bythell, Benjamin J.; Abutokaikah, Maha T.; Wagoner, Ashley R.; Guan, Shanshan; Rabus, Jordan M.


    We investigate the fragmentation chemistry of cationized carbohydrates using a combination of tandem mass spectrometry, regioselective labeling, and computational methods. Our model system is D-lactose. Barriers to the fundamental glyosidic bond cleavage reactions, neutral loss pathways, and structurally informative cross-ring cleavages are investigated. The most energetically favorable conformations of cationized D-lactose were found to be similar. In agreement with the literature, larger group I cations result in structures with increased cation coordination number which require greater collision energy to dissociate. In contrast with earlier proposals, the B n -Y m fragmentation pathways of both protonated and sodium-cationized analytes proceed via protonation of the glycosidic oxygen with concerted glycosidic bond cleavage. Additionally, for the sodiated congeners our calculations support sodiated 1,6-anhydrogalactose B n ion structures, unlike the preceding literature. This affects the subsequent propensity of formation and prediction of B n /Y m branching ratio. The nature of the anomeric center (α/β) affects the relative energies of these processes, but not the overall ranking. Low-energy cross-ring cleavages are observed for the metal-cationized analytes with a retro-aldol mechanism producing the 0,2 A 2 ion from the sodiated forms. Theory and experiment support the importance of consecutive fragmentation processes, particularly for the protonated congeners at higher collision energies.

  18. Cationized Carbohydrate Gas-Phase Fragmentation Chemistry (United States)

    Bythell, Benjamin J.; Abutokaikah, Maha T.; Wagoner, Ashley R.; Guan, Shanshan; Rabus, Jordan M.


    We investigate the fragmentation chemistry of cationized carbohydrates using a combination of tandem mass spectrometry, regioselective labeling, and computational methods. Our model system is D-lactose. Barriers to the fundamental glyosidic bond cleavage reactions, neutral loss pathways, and structurally informative cross-ring cleavages are investigated. The most energetically favorable conformations of cationized D-lactose were found to be similar. In agreement with the literature, larger group I cations result in structures with increased cation coordination number which require greater collision energy to dissociate. In contrast with earlier proposals, the B n -Y m fragmentation pathways of both protonated and sodium-cationized analytes proceed via protonation of the glycosidic oxygen with concerted glycosidic bond cleavage. Additionally, for the sodiated congeners our calculations support sodiated 1,6-anhydrogalactose B n ion structures, unlike the preceding literature. This affects the subsequent propensity of formation and prediction of B n /Y m branching ratio. The nature of the anomeric center (α/β) affects the relative energies of these processes, but not the overall ranking. Low-energy cross-ring cleavages are observed for the metal-cationized analytes with a retro-aldol mechanism producing the 0,2 A 2 ion from the sodiated forms . Theory and experiment support the importance of consecutive fragmentation processes, particularly for the protonated congeners at higher collision energies.

  19. The effusive-explosive transitions at Rokatenda 2012-2013: unloading by extrusion of degassed magma with lateral gas flow (United States)

    Primulyana, Sofyan; Bani, Philipson; Harris, Andrew


    Between October 2012 and August 2013, Rokatenda, one of the most poorly understood volcanoes in Indonesia, entered a phase of intense eruptive activity which involved extrusion of viscous lava, gas discharge and explosive activity. During the 10-month-long eruption, a lava volume of 2-5 × 106 m3 was extruded at mean output rate of 0.3 m3 s-1, with 2 to 3-month-long high extrusion rate phases being terminated by explosive events. Extrusion built a lava dome attaining a maximum height of ˜80 m above the crater rim, with a basal width of about 250 m. The composition of the 2012-2013 lava dome is comparable to that of the 1980 lava dome, both being andesite-trachydacite. Mineralogically, the 2012-2013 lava dome is mainly composed of plagioclase, pyroxene and an undetermined opaque mineral. Halogens released during eruption are consistent with the extrusion being fed, at least in the first eruption phase, by a degassed magma. This resulted in the formation of a dense, viscous plug in the conduit that led to a lateral gas flow, with gasses escaping around the plug to form multiple craters surrounding the dome. During the course of the eruptive activity, degassed magma was progressively forced out of the vent to unload deeper magma and force the system into an explosive phase. Such a scenario has occurred in the past at Rokatenda and is likely to be repeated in the future and creates an activity pattern that may be used to characterize such systems.

  20. Noble gas solubility in silicate melts:a review of experimentation and theory, and implications regarding magma degassing processes

    Directory of Open Access Journals (Sweden)

    A. Paonita


    Full Text Available Noble gas solubility in silicate melts and glasses has gained a crucial role in Earth Sciences investigations and in the studies of non-crystalline materials on a micro to a macro-scale. Due to their special geochemical features, noble gases are in fact ideal tracers of magma degassing. Their inert nature also allows them to be used to probe the structure of silicate melts. Owing to the development of modern high pressure and temperature technologies, a large number of experimental investigations have been performed on this subject in recent times. This paper reviews the related literature, and tries to define our present state of knowledge, the problems encountered in the experimental procedures and the theoretical questions which remain unresolved. Throughout the manuscript I will also try to show how the thermodynamic and structural interpretations of the growing experimental dataset are greatly improving our understanding of the dissolution mechanisms, although there are still several points under discussion. Our improved capability of predicting noble gas solubilities in conditions closer to those found in magma has allowed scientists to develop quantitative models of magma degassing, which provide constraints on a number of questions of geological impact. Despite these recent improvements, noble gas solubility in more complex systems involving the main volatiles in magmas, is poorly known and a lot of work must be done. Expertise from other fields would be extremely valuable to upcoming research, thus focus should be placed on the structural aspects and the practical and commercial interests of the study of noble gas solubility.

  1. DECADE web portal: toward the integration of MaGa, EarthChem and VOTW data systems to further the knowledge on Earth degassing (United States)

    Cardellini, Carlo; Frigeri, Alessandro; Lehnert, Kerstin; Ash, Jason; McCormick, Brendan; Chiodini, Giovanni; Fischer, Tobias; Cottrell, Elizabeth


    The release of volatiles from the Earth's interior takes place in both volcanic and non-volcanic areas of the planet. The comprehension of such complex process and the improvement of the current estimates of global carbon emissions, will greatly benefit from the integration of geochemical, petrological and volcanological data. At present, major online data repositories relevant to studies of degassing are not linked and interoperable. In the framework of the Deep Earth Carbon Degassing (DECADE) initiative of the Deep Carbon Observatory (DCO), we are developing interoperability between three data systems that will make their data accessible via the DECADE portal: (1) the Smithsonian Institutionian's Global Volcanism Program database (VOTW) of volcanic activity data, (2) EarthChem databases for geochemical and geochronological data of rocks and melt inclusions, and (3) the MaGa database (Mapping Gas emissions) which contains compositional and flux data of gases released at volcanic and non-volcanic degassing sites. The DECADE web portal will create a powerful search engine of these databases from a single entry point and will return comprehensive multi-component datasets. A user will be able, for example, to obtain data relating to compositions of emitted gases, compositions and age of the erupted products and coincident activity, of a specific volcano. This level of capability requires a complete synergy between the databases, including availability of standard-based web services (WMS, WFS) at all data systems. Data and metadata can thus be extracted from each system without interfering with each database's local schema or being replicated to achieve integration at the DECADE web portal. The DECADE portal will enable new synoptic perspectives on the Earth degassing process allowing to explore Earth degassing related datasets over previously unexplored spatial or temporal ranges.

  2. Stretch-activated cation channel from larval bullfrog skin. (United States)

    Hillyard, Stanley D; Willumsen, Niels J; Marrero, Mario B


    Cell-attached patches from isolated epithelial cells from larval bullfrog skin revealed a cation channel that was activated by applying suction (-1 kPa to -4.5 kPa) to the pipette. Activation was characterized by an initial large current spike that rapidly attenuated to a stable value and showed a variable pattern of opening and closing with continuing suction. Current-voltage plots demonstrated linear or inward rectification and single channel conductances of 44-56 pS with NaCl or KCl Ringer's solution as the pipette solution, and a reversal potential (-V(p)) of 20-40 mV. The conductance was markedly reduced with N-methyl-D-glucamide (NMDG)-Cl Ringer's solution in the pipette. Neither amiloride nor ATP, which are known to stimulate an apical cation channel in Ussing chamber preparations of larval frog skin, produced channel activation nor did these compounds affect the response to suction. Stretch activation was not affected by varying the pipette concentrations of Ca(2+) between 0 mmol l(-1) and 4 mmol l(-1) or by varying pH between 6.8 and 8.0. However, conductance was reduced with 4 mmol l(-1) Ca(2+). Western blot analysis of membrane homogenates from larval bullfrog and larval toad skin identified proteins that were immunoreactive with mammalian TRPC1 and TRPC5 (TRPC, canonical transient receptor potential channel) antibodies while homogenates of skin from newly metamorphosed bullfrogs were positive for TRPC1 and TRPC3/6/7 antibodies. The electrophysiological response of larval bullfrog skin resembles that of a stretch-activated cation channel characterized in Xenopus oocytes and proposed to be TRPC1. These results indicate this channel persists in all life stages of anurans and that TRP isoforms may be important for sensory functions of their skin.

  3. Divalent cation shrinks DNA but inhibits its compaction with trivalent cation (United States)

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


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

  4. Ensemble classi…cation methods for autism disordered speech

    Directory of Open Access Journals (Sweden)

    Zoubir Abdeslem Benselama


    Full Text Available In this paper, we present the results of our investigation on Autism classifi…cation by applying ensemble classi…ers to disordered speech signals. The aim is to distinguish between Autism sub-classes by comparing an ensemble combining three decision methods, the sequential minimization optimization (SMO algorithm, the random forests (RF, and the feature-subspace aggregating approach (Feating. The conducted experiments allowed a reduction of 30% of the feature space with an accuracy increase over the baseline of 8.66% in the development set and 6.62% in the test set.

  5. Conduction apraxia. (United States)

    Ochipa, C; Rothi, L J; Heilman, K M


    A left hemisphere damaged patient with ideomotor apraxia is described, whose performance on pantomime to verbal command was superior to pantomime imitation. His reception of these same gestures (gesture naming) was spared. This syndrome has been named conduction apraxia. To account for this selective impaired performance on gesture imitation, a separation of the representations for gesture production and reception is proposed and a non-lexical gesture processing route for gesture imitation is suggested. Images PMID:7931387

  6. Conduction apraxia.


    Ochipa, C; Rothi, L J; Heilman, K M


    A left hemisphere damaged patient with ideomotor apraxia is described, whose performance on pantomime to verbal command was superior to pantomime imitation. His reception of these same gestures (gesture naming) was spared. This syndrome has been named conduction apraxia. To account for this selective impaired performance on gesture imitation, a separation of the representations for gesture production and reception is proposed and a non-lexical gesture processing route for gesture imitation is...

  7. Conductivity Probe (United States)


    The Thermal and Electrical Conductivity Probe (TECP) for NASA's Phoenix Mars Lander took measurements in Martian soil and in the air. The needles on the end of the instrument were inserted into the Martian soil, allowing TECP to measure the propagation of both thermal and electrical energy. TECP also measured the humidity in the surrounding air. The needles on the probe are 15 millimeters (0.6 inch) long. The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

  8. Effect of primycin on monovalent cation transport of erythrocyte membrane and lipid bilayer. (United States)

    Blaskó, K; Györgyi, S; Horváth, I


    The effects of primycin were investigated on the alkali-cation transport of human erythrocytes and on the electric conduction of bimolecular lipid membranes. In the concentration range of 3.10(-6) approximately 10(-5) M primycin increased the permeability of erythrocytes to alkali-cations according to the sequences Cs+ greater than Rb+ approximately K+ greater than Na+, while the conductance of the negatively charged phosphatidylserine bimolecular lipid membrane increased by 2 approximately 3 orders of magnitude. The resistance-lowering effect of primycin strongly depended on the cationic species applied and a selectivity order Na+ greater than K+ greater than Rb+ greater than Cs+ was found. A possible mechanism of the primycin-membrane interaction is suggested on the basis of experimental data.

  9. A new view of the He-Ar-CO 2 degassing at mid-ocean ridges: Homogeneous composition of magmas from the upper mantle (United States)

    Paonita, Antonio; Martelli, Mauro


    Deep-sea exploration is rapidly improving our understanding of volatiles geochemistry in mid-ocean-ridge igneous products. It is also placing greater constraints on degassing processes of the Earth's mantle, with the result that degassing models based on vapour-melt equilibrium are no longer able to explain the increasing number of data. In fact, such models force to postulate an upper mantle strongly heterogeneous at any scale, and cannot account for the widespread carbon supersaturation of the recovered igneous products. Here we review the global He-Ar-CO 2 dataset of fluid inclusions in mid-ocean-ridge glasses using the framework of advanced modelling of multicomponent bubble growth in magmas. We display that non-equilibrium fractionations among He, Ar and CO 2, driven by their different diffusivities in silicate melts, are common in most of the natural conditions of magma decompression and their signature strongly depends on pressure of degassing. Due to the comparable Ar and CO 2 diffusivity, magma degassing at low pressure fractionates both the He/Ar and He/CO 2 ratio by a similar extent, while the slower CO 2 diffusion at high pressure causes early kinetic effects on Ar/CO 2 ratio and dramatically changes the degassing path. On this ground, the very different geochemical signatures among suites of data coming from different ridge segments mainly depend on the depth of the magma chamber where the melt was stored. Besides, the variations inside a single suite highlight variable ascent speed and cooling rate of the emplaced lava. The large variations in both the He/CO 2 and Ar/CO 2 ratios at almost constant He/Ar, displayed in glasses coming from the Mid-Atlantic Ridge 24-30°N segment and the Rodriguez Triple Junction, are therefore interpreted as a high-pressure signature. In contrast, the simultaneous increase in both He/CO 2 and He/Ar of the East Pacific Rise, Pito Seamount and South-East Indian Ridge data sets suggests the dominance of low

  10. Solid Electrolytes for Multivalent Cations (United States)


    Hochstrasser, "Preparation and Optical Spectroscopy of Na-Bu(ll)-Beta" Alumina," Journal of the Electrochemical Society . vol 133, Iss 8, C343-C343, 1986 G...Rohrer, G.C. Farrington, "Color Center Formation and Electronic Conductivity in the Multivalent Beta" Alumina," Journal of the Electrochemical Society . vol...of Multivalent Beta" Aluminas," Journal of the Electrochemical Society . vol 135, Iss 3, C148-C148, 1988 M.A. Zendejas and J.O. Thomas, "A Molecular

  11. Conducted Vasoreactivity

    DEFF Research Database (Denmark)

    Postnov, D. E.; Neganova, A Y; Sosnovtseva, Olga


    , the underlying mechanisms are debated. Here, we focus on dynamical aspects of the problem hypothesizing the existence of a bistability-powered mechanism for regenerative pulse transmission along the endothelium. Bistability implies that the cell can have two different stable resting potentials and can switch......Conducted vasodilation is part of the physiological response to increasing metabolic demand of the tissue. Similar responses can be elicited by focal electrical or chemical stimulation. Some evidence suggests an endothelial pathway for nondecremental transmission of hyperpolarizing pulses. However...... a theoretical analysis as well as numerical simulations of both single- and multiunit bistable systems mimicking endothelial cells to investigate the self-consistence and stability of the proposed mechanism. We find that the individual cell may switch readily between two stable potentials. An array of coupled...


    Laboratory experiments using multi-species inorganic solutions (containing calcium and sodium) were conducted on specimens of a new geosynthetic clay liner (GCL) containing sodium bentonite to determine how cation exchange and desiccation affected the hydraulic conductivity. Calc...

  13. Hydrocarbon degassing of the earth and origin of oil-gas fields (isotope-geochemical and geodynamic aspects) (United States)

    Valyaev, Boris; Dremin, Ivan


    More than half a century ago, Academician PN Kropotkin substantiated the relationship of the formation and distribution of oil and gas fields with the processes of emanation hydrocarbon degassing of the Earth. Over the years, the concept of PN Kropotkin received further development and recognition of studies based on new factual material. Of particular importance are the following factors: a) the results of studies on global and regional uneven processes of traditional oil and gas and the role of deep faults in controlling the spread of oil and gas fields; b) the results of the research on gigantic volumes and localization of the discharges of hydrocarbon fluids (mud volcanoes, seeps) on land and into the atmosphere and through the bottom of the World ocean; c) the results of the studies on grand volumes of the spread of unconventional hydrocarbon resources in their non-traditional fields, especially on near-surface interval of unconventional oil and gas accumulation with gas hydrates, heavy oil and bitumen, as well as extraordinary resources of oil and gas in the shale and tight rocks. Deep mantle-crust nature of oil and gas in traditional and nontraditional deposits thus received further substantiation of geological and geophysical data and research results. However, isotopic and geochemical data are still interpreted in favor of the concept of the genesis of oil and gas in the processes of thermal catalytic conversion of organic matter of sedimentary rocks, at temperatures up to 200°C. In this report an alternative interpretation of the isotope carbon-hydrogen system (δ13C-δD) for gas and of oil deposits, isotope carbon system for methane and carbon dioxide (δ13C1-δ13C0) will be presented. An alternative interpretation will also be presented for the data on carbon-helium isotope geochemical system for oil and gas fields, volcanoes and mud volcanoes. These constructions agree with the geological data on the nature of deep hydrocarbon fluids involved in the

  14. Preliminary assessment of the state of CO2 soil degassing on the flanks of Gede volcano (West Java, Indonesia) (United States)

    Kunrat, S. L.; Schwandner, F. M.


    Gede Volcano (West Java) is part of an andesitic stratovolcano complex consisting of Pangrango in the north-west and Gede in the south-east. The last recorded eruptive activity was a phreatic subvolcanian ash eruption in 1957. Current activity is characterized by episodic swarms at 2-4 km depth, and low-temperature (~160°C) crater degassing in two distinct summit crater fumarolic areas. Hot springs occur in the saddle between the Gede and Pangrango edifice, as well as on the NE flank base. The most recent eruptive events produced pyroclastic material, their flow deposits concentrate toward the NE. A collaborative effort between the Center for Volcanology and Geological Hazard Mitigation (CVGHM), Geological Agency and the Earth Observatory of Singapore (EOS) is since 2010 aimed at upgrading the geophysical and geochemical monitoring network at Gede Volcano. To support the monitoring instrumentation upgrades under way, surveys of soil CO2 degassing have been performed on the flanks of Gede, in circular and radial traverses.The goal was to establish a spatial distribution of flank CO2 fluxes, and to allow smart siting for continuous gas monitoring stations. Crater fluxes were not surveyed, as its low-temperature hydrothermal system is likely prone to large hydraulic changes in this tropical environment, resulting in variable permeability effects that might mask signals from deeper reservoir or conduit degassing. The high precipitation intensity in the mountains of tropical Java pose challenges to this method, since soil gas permeability is largely controlled by soil moisture content. Simultaneous soil moisture measurements were undertaken. The soil CO2 surveys were carried out using a LI-8100A campaign flux chamber instrument (LICOR Biosciences, Lincoln, Nebraska). This instrument has a very precise and highly stable sensor and an atmospheric pressure equilibrator, making it highly sensitive to low fluxes. It is the far superior choice for higher precision low

  15. Cationically polymerizable monomers derived from renewable sources

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.


    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year's research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  16. Metalated Nitriles: Cation-Controlled Cyclizations (United States)

    Fleming, Fraser F.; Wei, Yunjing; Liu, Wang; Zhang, Zhiyu


    Judicious choice of cation allows the selective cyclization of substituted γ-hydroxynitriles to trans- or cis-decalins and trans- or cis-bicyclo[5.4.0]-undecanes. The stereoselectivities are consistent with deprotonations generating two distinctly different metalated nitriles: an internally coordinated nitrile anion with BuLi, and a C-magnesiated nitrile with i-PrMgCl. Employing cations to control the geometry of metalated nitriles permits stereodivergent cyclizations with complete control over the stereochemistry of the quaternary, nitrile-bearing carbon. PMID:17579448

  17. Cation Effect on Copper Chemical Mechanical Polishing

    Institute of Scientific and Technical Information of China (English)

    WANG Liang-Yong; LIU Bo; SONG Zhi-Tang; FENG Song-Lin


    We examine the effect of cations in solutions containing benzotriazole (BTA) and H2O2 on copper chemical mechanical polishing (CMP). On the base of atomic force microscopy (AFM) and material removal rate (MRR) results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demon-strates the worst performance. These results reveal a mechanism that sma//molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential (OCP).

  18. Cation Effect on Copper Chemical Mechanical Polishing (United States)

    Wang, Liang-Yong; Liu, Bo; Song, Zhi-Tang; Feng, Song-Lin


    We examine the effect of cations in solutions containing benzotriazole (BTA) and H2O2 on copper chemical mechanical polishing (CMP). On the base of atomic force microscopy (AFM) and material removal rate (MRR) results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demonstrates the worst performance. These results reveal a mechanism that small molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential (OCP).

  19. Cationically polymerizable monomers derived from renewable sources

    Energy Technology Data Exchange (ETDEWEB)

    Crivello, J.V.


    The objectives of this project are to design and synthesize novel monomers which orginate from renewable biological sources and to carry out their rapid, efficient, pollution-free and energy efficient cationic polymerization to useful products under the influence of ultraviolet light or heat. A summary of the results of the past year's research on cationically polymerizable monomers derived from renewable sources is presented. Three major areas of investigation corresponding to the different classes of naturally occurring starting materials were investigated; epoxidized terpenes and natural rubber and vinyl ethers from alcohols and carbohydrates.

  20. [Conduct disorders]. (United States)

    Stadler, Christina


    The diagnosis conduct disorder (CD) is characterized by aggressive (e.g., physical aggression) as well as nonaggressive symptoms (e.g., violation of rules, truancy). Conclusions regarding the course and prognosis, or recommendations for effective interventions, seem not to be equally valid for the whole patient group. DSM-IV-TR included subtyping age-of-onset as a prognostic criterion, even though the evidence base for subtyping from age of onset was rather sparse. The relevant literature on CD has grown substantially since the publication of DSM-IV-TR in 1994. For the new DSM-5 edition, some important issues were discussed, for example, consideration of personality traits, female-specific or dimensional criteria, and adding a childhood-limited subtype (Moffitt et al., 2008). Nevertheless, the diagnostic protocol for CD was not changed in the most parts in the new edition of the DSM-5; the addition of a CD specifier with limited emotions is the most relevant change. On the basis of the existing evidence base, this review discusses whether the modifications in DSM-5 are helpful for fulfilling the requirements of a reliable and valid psychiatric classification.

  1. Transport of dissolved carbon and CO2 degassing from a river system in a mixed silicate and carbonate catchment (United States)

    Khadka, Mitra B.; Martin, Jonathan B.; Jin, Jin


    Assessing the origin, transformation and transport of terrestrially derived carbon in river systems is critical to regional and global carbon cycles, particularly in carbonate terrains, which represent the largest carbon reservoir on the earth’s surface. For this reason, we evaluated sources, cycling, and fluxes of dissolved organic and inorganic carbon (DOC and DIC) and riverine CO2 degassing to the atmosphere in the Santa Fe River in north-central Florida, a sub-tropical river that flows across two distinct hydrogeological settings of a region dominated by carbonate karst. One setting occurs in the upper river catchment, where the carbonate Floridan aquifer is confined by the siliciclastic Hawthorn Group, while the other setting occurs in the lower catchment where the river flows across the unconfined Floridan aquifer. The upper catchment is characterized by DOC-rich and DIC-poor water and the DIC has more variable and lower δ13C values compared to the lower catchment. The river in the upper catchment degasses more CO2 to the atmosphere (1156 g C m-2 yr-1) than in the lower catchment (402 g C m-2 yr-1) because soil respired carbon and organic matter decomposition increase dissolved CO2 concentration, much of which is consumed during carbonate dissolution reactions in the lower catchment. The CO2 flux from the water surface to the atmosphere during a flood event is three times greater than during base flow, suggesting that excess precipitation flushes soil organic carbon to the river through interflow and enhances the loss of terrestrial carbon via river water to the atmosphere. Our values of CO2 fluxes to the atmosphere lie within the range of fluxes from the world’s rivers, but fluxes from the carbonate dominated region are at the low end, while fluxes from the siliciclastic region are at the high end. These results indicate that catchment lithologies, particularly whether carbonate or siliciclastic, as well as flow, are critical to carbon budgets in rivers

  2. Diffuse volcanic degassing and thermal energy release 2015 surveys from the summit cone of Teide volcano, Tenerife (Canary Islands, Spain) (United States)

    Melián, Gladys; Asensio-Ramos, María; Padilla, Germán; Alonso, Mar; Halliwell, Simon; Sharp, Emerson; Butters, Damaris; Ingman, Dylan; Alexander, Scott; Cook, Jenny; Pérez, Nemesio M.


    The summit cone of Teide volcano (Spain) is characterized by the presence of a weak fumarolic system, steamy ground, and high rates of diffuse CO2 degassing all around this area. The temperature of the fumaroles (83° C) corresponds to the boiling point of water at discharge conditions. Water is the major component of these fumarolic emissions, followed by CO2, N2, H2, H2S, HCl, Ar, CH4, He and CO, a composition typical of hydrothermal fluids. Previous diffuse CO2 surveys have shown to be an important tool to detect early warnings of possible impending volcanic unrests at Tenerife Island (Melián et al., 2012; Pérez et al., 2013). In July 2015, a soil and fumarole gas survey was undertaken in order to estimate the diffuse volcanic degassing and thermal energy release from the summit cone of Teide volcano. A diffuse CO2 emission survey was performed selecting 170 observation sites according to the accumulation chamber method. Soil CO2 efflux values range from non-detectable (˜0.5 g m-2d-1) up to 10,672 g m-2d-1, with an average value of 601 g m-2d-1. Spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. Measurement of soil CO2 efflux allowed an estimation of 162 ± 14 t d-1 of deep seated derived CO2. To calculate the steam discharge associated with this volcanic/hydrothermal CO2 output, we used the average H2O/CO2 mass ratio equal to 1.19 (range, 0.44-3.42) as a representative value of the H2O/CO2 mass ratios for Teide fumaroles. The resulting estimate of the steam flow associated with the gas flux is equal to 193 t d-1. The condensation of this steam results in a thermal energy release of 5.0×1011J d-1 for Teide volcano or a total heat flow of 6 MWt. The diffuse gas emissions and thermal energy released from the summit of Teide volcano are comparable to those observed at other volcanoes. Sustained surveillance using these methods will be valuable for monitoring the activity of Teide volcano.

  3. Copper isotope behavior during extreme magma differentiation and degassing: a case study on Laacher See phonolite tephra (East Eifel, Germany) (United States)

    Huang, Jian; Liu, Sheng-Ao; Wörner, Gerhard; Yu, Huimin; Xiao, Yilin


    Copper (Cu) isotopic analyses were performed on a set of samples from the Laacher See tephra (LST) (Eifel, Germany) to investigate whether Cu isotopes are fractionated during extreme magma differentiation and degassing. The LST represents a continuous fractional crystallization series from parental basanite through mafic to highly differentiated phonolites. Samples analyzed here include phonolites of variable degrees of differentiation, phonolite-basanite hybrid rocks formed by mixing basanite and phonolite magmas, and basanite-derived mega-crystals (i.e., clinopyroxene, amphibole, phlogopite). In addition, we analyzed a series of mafic parental lavas from surrounding volcanic centers to constrain the Cu isotopic features of the Eifel mantle. Mafic phonolites show strong depletion in Cu compared to their parental basanites from ~50 to ~3 ppm, indicating sulfide fractionation during the basanite-to-phonolite differentiation. Mass balance calculations, based on the most Cu-rich hybrid rock (δ65Cu = -0.21 ‰, [Cu] = 46.2 ppm), show that the parental basanite magmas have δ65Cu of ca. -0.21 ‰, lighter than those of the mafic phonolites (~0.11 ‰). This suggests that sulfide fractionation preferentially removes the lighter Cu isotope (63Cu) in S-saturated magmas. By contrast, all phonolites have a limited range of Cu contents (1.1 to 4.0 ppm) with no systematic variations with S, suggesting that Cu is not controlled by sulfide fractionation during the evolution of mafic to highly differentiated phonolites. The identical δ65Cu values (0.11 ± 0.03 ‰, 2SD, n = 10) of the phonolites, irrespective of highly diverse composition and extents of differentiation, indicate that fractional crystallization of silicates (e.g., plagioclase, sanidine, amphibole, pyroxene, olivine), Fe-Ti-oxides and phosphate (e.g., apatite) generates insignificant Cu isotope fractionation. The lack of correlations between δ65Cu and volatile contents (e.g., S, Cl) in the LST sequence implies

  4. SO2 degassing at Tungurahua volcano (Ecuador) between 2007 and 2013: Transition from continuous to episodic activity (United States)

    Hidalgo, Silvana; Battaglia, Jean; Arellano, Santiago; Steele, Alexander; Bernard, Benjamin; Bourquin, Julie; Galle, Bo; Arrais, Santiago; Vásconez, Freddy


    We present continuous SO2 measurements performed at Tungurahua volcano with a permanent network of 4 scanning DOAS instruments between 2007 and 2013. The volcano has been erupting since September 1999, but on the contrary to the first years of eruption when the activity was quasi-continuous, the activity transitioned in late 2008 towards the occurrence of distinct eruptive phases separated by periods of quiescence. During our study period we distinguish 11 phases lasting from 17 to 527 days separated by quiescence periods of 26 to 184 days. We propose a new routine to quantify the SO2 emissions when data from a dense DOAS monitoring network are available. This routine consists in summing all the highest validated SO2 measurements among all stations during the 10 h of daily working-time to obtain a daily observed SO2 mass. Since measurement time is constant at Tungurahua the "observed" amounts can be expressed in tons per 10 h and can easily be converted to a daily average flux or mass per day. Our results provide time series having an improved correlation on a long time scale with the eruptive phases and with quiescence periods. A total of 1.25 Mt (1.25 × 109 kg) of SO2 has been released by Tungurahua during the study period, with 95% of these emissions occurring during phases of activity and only 5% during quiescence. This shows a contrast with previous volcanic behaviour when passive degassing dominated the total SO2 emissions. SO2 average daily mass emission rates are of 73 ± 56 t/d during quiescent periods, 735 ± 969 t/d during long-lasting phases and 1424 ± 1224 t/d during short-lasting phases. Degassing during the different eruptive phases displays variable patterns. However, two contrasting behaviours can be distinguished for the onset of eruptive phases with both sudden and progressive onsets being observed. The first is characterised by violent opening of the conduit by high energy Vulcanian explosions; and the second by a progressive, in crescendo

  5. Cationic dialkylarylphosphates: a new family of bio-inspired cationic lipids for gene delivery. (United States)

    Le Corre, Stéphanie S; Belmadi, Nawal; Berchel, Mathieu; Le Gall, Tony; Haelters, Jean-Pierre; Lehn, Pierre; Montier, Tristan; Jaffrès, Paul-Alain


    In this work that aims to synthesize and evaluate new cationic lipids as vectors for gene delivery, we report the synthesis of a series of cationic lipids in which a phosphate functional group acts as a linker to assemble on a molecular scale, two lipid chains and one cationic polar head. The mono or dicationic moiety is connected to the phosphate group by an aryl spacer. In this work, two synthesis strategies were evaluated. The first used the Atherton-Todd coupling reaction to introduce a phenolic derivative to dioleylphosphite. The second strategy used a sequential addition of lipid alcohol and a phenolic derivative on POCl3. The two methods are efficient, but the latter allows larger yields. Different polar head groups were introduced, thus producing amphiphilic compounds possessing either one permanent (N-methyl-imidazolium, pyridinium, trimethylammonium) or two permanent cationic charges. All these cationic lipids were formulated as liposomal solutions and characterized (size and zeta potential). They formed stable liposomal solutions both in water (at pH 7.0) and in a weakly acidic medium (at pH 5.5). Finally, this new generation of cationic lipids was used to deliver DNA into various human-derived epithelial cells cultured in vitro. Compared with Lipofectamine used as a reference commercial lipofection reagent, some cationic dialkylarylphosphates were able to demonstrate potent gene transfer abilities, and noteworthily, monocationic derivatives were much more efficient than dicationic analogues.

  6. Study of impurity distribution in mechanically polished, chemically treated and ultra-high vacuum degassed pure Niobium samples using TOFSIMS technique

    CERN Document Server

    Bose, A


    The performance of Superconducting radio frequency cavities (SCRF) are highly dependent on the surface treatment processes, which in turn is influenced by the chemistry within the penetration depth of Niobium (Nb). The present study analyses various impurities within the RF penetration depth (~50nm) of Nb samples treated by SCRF cavity processing techniques like colloidal silica polishing (simulating centrifugal barrel polishing), buffer chemical polishing (BCP), high pressure rinsing (HPR) and degassing under ultra high vacuum (UHV) condition at 600{\\deg}C for 10hrs. Various modes of Time of flight secondary ion mass spectrometry (TOFSIMS) technique was employed to study the effect of the above treatments on the vast spectrum of impurities that include interstitials, hydrocarbons, oxides, acidic residuals, reaction products and metallic impurities. UHV degassing treatment was the only treatment capable of reducing hydrogen contamination, but, it led to extensive oxygen, carbon and metallic impurities in the ...

  7. Cation Selectivity in Biological Cation Channels Using Experimental Structural Information and Statistical Mechanical Simulation. (United States)

    Finnerty, Justin John; Peyser, Alexander; Carloni, Paolo


    Cation selective channels constitute the gate for ion currents through the cell membrane. Here we present an improved statistical mechanical model based on atomistic structural information, cation hydration state and without tuned parameters that reproduces the selectivity of biological Na+ and Ca2+ ion channels. The importance of the inclusion of step-wise cation hydration in these results confirms the essential role partial dehydration plays in the bacterial Na+ channels. The model, proven reliable against experimental data, could be straightforwardly used for designing Na+ and Ca2+ selective nanopores.

  8. Controlled Cationic Polymerization of N-Vinylcarbazol

    NARCIS (Netherlands)

    Nuyken, O.; Rieß, G.; Loontjens, J.A.


    Cationic polymerization of N-Vinylcarbazol (NVC) was initiated with 1-iodo-1-(2-methylpropyloxy)ethane in the presence of N(n-Bu)4ClO4 and without addition of this activator. Furthermore, 1-chloro-1-(2-methylpropyloxy) ethane, with and without activator has been applied as initiator for NVC. These i

  9. Anionic/cationic complexes in hair care. (United States)

    O'Lenick, Tony


    The formulation of cosmetic products is always more complicated than studying the individual components in aqueous solution. This is because there are numerous interactions between the components, which make the formulation truly more than the sum of the parts. This article will look at interactions between anionic and cationic surfactants and offer insights into how to use these interactions advantageously in making formulations.

  10. Resonance raman studies of phenylcyclopropane radical cations

    NARCIS (Netherlands)

    Godbout, J.T.; Zuilhof, H.; Heim, G.; Gould, I.R.; Goodman, J.L.; Dinnocenzo, J.P.; Myers Kelley, A.


    Resonance Raman spectra of the radical cations of phenylcyclopropane and trans-1-phenyl-2-methylcyclopropane are reported. A near-UV pump pulse excites a photosensitizer which oxidizes the species of interest, and a visible probe pulse delayed by 35 ns obtains the spectrum of the radical ion. The tr

  11. Mixed cation effect in sodium aluminosilicate glasses

    DEFF Research Database (Denmark)

    Kjeldsen, Jonas; Smedskjær, Morten Mattrup; Mauro, John C.

    , network structure, and the resistances associated with the deformation processes in mixed cation glasses by partially substituting magnesium for calcium and calcium for lithium in sodium aluminosilicate glasses. We use Raman and 27Al NMR spectroscopies to obtain insights into the structural...

  12. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.;


    Polypyrrole (PPy) polymer films permanently doped with large, immobile anion dodecyl benzene sulfonate (DBS) have been characterized by cyclic voltammetry in order to clarify the roles of cations and anions in the aqueous electrolyte as mobile ions in the film. Aqueous solutions of 0.05-0.1 M...... alkali metal chlorides as well as BaCl2, NaBr and (CH3CH2CH2)(4)NBr were used to investigate the effects of both the ionic charge, size and shape. In 1: 1 electrolytes using small ions only three peaks are present: a sharp cathodic peak at ca. - 0.6 V vs, SCE representing both the insertion of cations...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  13. Cationic lipids and cationic ligands induce DNA helix denaturation: detection of single stranded regions by KMnO4 probing. (United States)

    Prasad, T K; Gopal, Vijaya; Rao, N Madhusudhana


    Cationic lipids and cationic polymers are widely used in gene delivery. Using 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) as a cationic lipid, we have investigated the stability of the DNA in DOTAP:DNA complexes by probing with potassium permanganate (KMnO4). Interestingly, thymidines followed by a purine showed higher susceptibility to cationic ligand-mediated melting. Similar studies performed with other water-soluble cationic ligands such as polylysine, protamine sulfate and polyethyleneimine also demonstrated melting of the DNA but with variations. Small cations such as spermine and spermidine and a cationic detergent, cetyl trimethylammonium bromide, also rendered the DNA susceptible to modification by KMnO4. The data presented here provide direct proof for melting of DNA upon interaction with cationic lipids. Structural changes subsequent to binding of cationic lipids/ligands to DNA may lead to instability and formation of DNA bubbles in double-stranded DNA.

  14. The textural record of conduit and syn-eruptive degassing preserved in ballistic bombs from cyclic Vulcanian explosions of Galeras volcano, Colombia (United States)

    Bain, A. A.


    Volcanic bombs preserve textural data that record conduit conditions as well as syn-eruptive processes that acted upon a parcel of magma following decompression. Specifically, these pyroclasts may record several episodes of crystal and bubble growth, as well as bubble coalescence and collapse. Furthermore, bombs retrieved from sequential eruptions provide valuable insight into the unobservable evolution of a volcanic conduit over time. We present results from a morphological and textural study of vesicle size distributions in ballistic bombs from six Vulcanian eruptions from the 2004-2012 period of activity of Galeras volcano, Colombia. These violent eruptions cyclically destroyed and ejected a stalled, degassed and crystal-rich plug and a limited amount of underlying magma. They were followed by resumption of the slow rise of magma in the shallow conduit, accompanied by redevelopment of a plug and the perpetuation of a hazardous cycle. We find that bombs from these eruptions fall into three morphological classes including dense bombs, breadcrusted bombs and vesicular bombs based on the existence or absence of a primary quenched rind and comparison of the interior and exterior vesicularities. We study vesicle populations using image analysis of SEM images followed by stereological conversion to reconstruct the degassing history of each pyroclast. The results of this study will be used to produce a quantitative model of the evolution of porosity, permeability and degassing in the upper conduit of Galeras volcano during the 2004-2012 eruptive episode.

  15. The memory of volcanic waters: Shallow magma degassing revealed by halogen monitoring in thermal springs of La Soufrière volcano (Guadeloupe, Lesser Antilles) (United States)

    Villemant, Benoît; Hammouya, Gilbert; Michel, Agnès; Semet, Michel P.; Komorowski, Jean-Christophe; Boudon, Georges; Cheminée, Jean-Louis


    The halogen contents of thermal waters collected since 1979 at La Soufrière volcano (Guadeloupe, Lesser Antilles) are interpreted as a retarded record of magma degassing pulses dispersed into the hydrothermal system. The further the spring is located from the source, the larger the time delay and the older the event recorded in water chemistry. Using advection-dispersion transport models in porous media, we reconstruct the time-series of degassing pulses for the period 1971-1992 and show that it correlates with the seismic records. The 1975-1977 sismo-volcanic crisis at La Soufrière is thereby interpreted as the result of a magma intrusion at shallow depth (˜3 km) which likely began in approximately 1973 and degassed in a pulsatory regime during ˜15 yr. The recent recrudescence of fumarolic and seismic activity could represent the initial stage of new magma injection. Measurement of halogen contents in hydrothermal waters collected around active volcanoes may provide a powerful tool for detection of the initial stages of magma intrusions.

  16. Diffuse Carbon Dioxide (CO2) degassing from the summit crater of Pico do Fogo during the 2014-15 eruption, Cape Verde (United States)

    Rodríguez, Fatima; Dionis, Samara; Padrón, Eleazar; Fernandes, Paulo; Melián, Gladys V.; Pérez, Nemesio M.; Hernández, Pedro A.; Silva, Sónia; Pereira, José Manuel; Cardoso, Nadir; Asensio-Ramos, María; Barrancos, José; Padilla, Germán; Calvo, David; Semedo, Helio


    On January 3, 2015, a new diffuse CO2 degassing survey at the summit crater of Pico do Fogo volcano (2,829 m above sea level) was carried out by ITER/INVOLCAN/UNICV/OVCV research team to investigate the effect of the 2014-15 Fogo eruption on the diffuse degassing through the summit crater. Before the eruption onset on November 23, 2014, these type of surveys were periodically performed by ITER/INVOLCAN/UNICV/OVCV research team since May 2007. The first published data on diffuse CO2 degassing rate from the summit crater of Pico do Fogo volcano (219 ± 36 t d-1) is related to a survey performed on February 2010 (Dionis et al., 2015). Each survey implies about 65 CO2 efflux measurements to obtain a good spatial distribution and cover homogeneously the summit crater area (0.14 km2). Because of the sudden falls of rocks of different sizes inside the summit crater during the January 3 survey, the research team aborted continues working in the summit crater without completing the survey only 32 of the 65 CO2 efflux measurements were performed covering a smaller area (0.065 km2). Observed CO2 efflux values ranged from non detectable ( 300 t d-1). This most recent survey did not cover the hydrothermal alteration zone within the crater, where the highest CO2 efflux measurements are usually recorded. Dionis et al. (2015), Bull. Volcanol., in press;

  17. Trace metal suites in Antarctic pre-industrial ice are consistent with emissions from quiescent degassing of volcanoes worldwide (United States)

    Matsumoto, A.; Hinkley, T.K.


    Trace metals are more abundant in atmospheric load and deposition material than can be due to rock and soil dusts and ocean salt. In pre-industrial ice from coastal west Antarctica, dust and salt account for only a few percent of the lead, cadmium, and indium that is present in most samples, less than half in any sample. For these trace metals, the deposition rate to the pre-industrial ice is approximately matched by the output rate to the atmosphere by quiescent (non-explosive) degassing of volcanoes worldwide, according to a new estimate. The basis of the match is the masses and proportions of the metals, and the proportions of Pb isotopes, in ice and in volcano emissions. The isotopic compositions of Pb in ice are similar to those of a suite of ocean island volcanoes, mostly in the southern hemisphere. The natural baseline values for pre-industrial atmospheric deposition fluxes of trace metal suites at Taylor Dome, and the worldwide quiescent volcano emissions fluxes to which they are linked, constitute a reasonably well-constrained baseline component for deposition fluxes of metals in modern times. ?? 2001 Elsevier Science B.V. All rights reserved.

  18. Metal emissions from Kilauea, and a suggested revision of the estimated worldwide metal output by quiescent degassing of volcanoes (United States)

    Hinkley, T.K.; Lamothe, P.J.; Wilson, S.A.; Finnegan, David L.; Gerlach, T.M.


    Measurements of a large suite of metals (Pb, Cd, Cu, Zn and several others) and sulfur at Kilauea volcano over an extended period of time has yielded a detailed record of the atmospheric injection of ordinarily-rare metals from this quiescently degassing volcano, representative of an important type. We have combined the Kilauea data with data of recent studies by others (emissions from volcanoes in the Indonesian arc; the large Laki eruption of two centuries ago; Etna: estimates of total volcanic emissions of sulfur) to form the basis for a new working estimate of the rate of worldwide injection of metals to the atmosphere by volcanoes. The new estimate is that volcanoes inject a substantially smaller mass of ordinarily-rare metals into the atmosphere than was stated in a widely cited previous estimate [J.O. Nriagu, A global assessment of natural sources of atmospheric trace metals, Nature 338 (1989) 47-49]. Our estimate, which is an upper limit, is an annual injection mass of about 10,000 tons of the metals considered, versus the earlier estimate of about 23,000 tons. Also, the proportions of the metals are substantially different in our new estimate.

  19. Dendritic Cells Stimulated by Cationic Liposomes. (United States)

    Vitor, Micaela Tamara; Bergami-Santos, Patrícia Cruz; Cruz, Karen Steponavicius Piedade; Pinho, Mariana Pereira; Barbuto, José Alexandre Marzagão; De La Torre, Lucimara Gaziola


    Immunotherapy of cancer aims to harness the immune system to detect and destroy cancer cells. To induce an immune response against cancer, activated dendritic cells (DCs) must present tumor antigens to T lymphocytes of patients. However, cancer patients' DCs are frequently defective, therefore, they are prone to induce rather tolerance than immune responses. In this context, loading tumor antigens into DCs and, at the same time, activating these cells, is a tempting goal within the field. Thus, we investigated the effects of cationic liposomes on the DCs differentiation/maturation, evaluating their surface phenotype and ability to stimulate T lymphocytes proliferation in vitro. The cationic liposomes composed by egg phosphatidylcholine, 1,2-dioleoyl-3-trimethylammonium propane and 1,2-dioleoylphosphatidylethanolamine (50/25/25% molar) were prepared by the thin film method followed by extrusion (65 nm, polydispersity of 0.13) and by the dehydration-rehydration method (95% of the population 107 nm, polydispersity of 0.52). The phenotypic analysis of dendritic cells and the analysis of T lymphocyte proliferation were performed by flow cytometry and showed that both cationic liposomes were incorporated and activated dendritic cells. Extruded liposomes were better incorporated and induced higher CD86 expression for dendritic cells than dehydrated-rehydrated vesicles. Furthermore, dendritic cells which internalized extruded liposomes also provided stronger T lymphocyte stimulation. Thus, cationic liposomes with a smaller size and polydispersity seem to be better incorporated by dendritic cells. Hence, these cationic liposomes could be used as a potential tool in further cancer immunotherapy strategies and contribute to new strategies in immunotherapy.

  20. Independent adsorption of monovalent cations and cationic polymers at PE/PG lipid membranes (United States)

    Khomich, Daria A.; Nesterenko, Alexey M.; Kostritskii, Andrei Yu; Kondinskaia, Diana A.; Ermakov, Yuri A.; Gurtovenko, Andrey A.


    Synthetic cationic polymers constitute a wide class of polymeric biocides. Commonly their antimicrobial effect is associated to their interaction with bacterial membranes. In the present study we analyze the interaction of various cationic polymers with model bacterial membranes comprised of a mixture of phosphatidylethanolamine (PE) and phosphatidylglycerol (PG). We describe a polymer-membrane interaction as a process of modification of the surface charge. It is well known that small monovalent inorganic cations (Na+, K+) cannot overcharge the surface of a bilayer containing anionic lipids. In contrast, polycations are able to overcharge anionic membranes and demonstrate a very large input to the electric field distribution at the membrane-water interface. We aimed here to study the electrostatic effects associated with the interaction of polycations of different types with a model lipid membrane whose composition closely resembles that of bacterial membranes (PE:PG = 1:4). Four different cationic polymers (polyvinylamine, polyallylamine, poly-L-lysine and polyethylenimine) were adsorbed at a model PE/PG bilayer in MD simulations. Adsorption of sodium cations was inspected separately for PE/PG bilayers of different composition and cation’s binding parameters were determined. From computational experiments and consequent theoretical analysis we concluded that sodium adsorption at anionic binding sites does not depend on the presence of polycations. Therefore, we hypothesize that antimicrobial activity of the studied cationic polymers should depend on the ionic composition of the medium.

  1. Biosorption of silver cations onto Lactococcus lactis and Lactobacillus casei isolated from dairy products (United States)

    Milanowski, Maciej; Pomastowski, Paweł; Railean-Plugaru, Viorica; Rafińska, Katarzyna; Ligor, Tomasz; Buszewski, Bogusław


    The current work deals with the phenomenon of silver cations uptake by two kinds of bacteria isolated from dairy products. The mechanism of sorption of silver cations by Lactococcus lactis and Lactobacillus casei bacteria was investigated. Inductively coupled plasma–mass spectrometry (ICP-MS) was used for determination of silver concentration sorbed by bacteria. Analysis of charge distribution was conducted by diffraction light scattering method. Changes in the ultrastructure of Lactococcus lactis and Lactobacillus casei cells after treatment with silver cations were investigated using transmission electron microscopy observation. Molecular spectroscopy methods, namely Fourier transform-infrared spectroscopy (FT-IR) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) were employed for description of the sorption mechanism. Moreover, an analysis of volatile organic compounds (VOCs) extracted from bacterial cells was performed. PMID:28362838

  2. Structural Isomerization of the Gas Phase 2-NORBORNYL Cation Revealed with Infrared Spectroscopy and Computational Chemistry (United States)

    Mauney, Daniel; Mosley, Jonathan; Duncan, Michael A.


    The non-classical structure of the 2-norborny cation (C_7H11+) which was at the center of "the most heated chemical controversy of our time" has been observed in the condensed phase and recently using X-ray crystallography. However, no gas phase vibrational spectrum has been collected. The C_7H11+ cation is produced via H_3+ protonation of norbornene by pulsed discharge in a supersonic expansion of H_2/Ar. Ions are mass-selected and probed using infrared photodissociation spectroscopy. Due to high exothermicity, protonation via H_3+ leads to a structural isomerization to the global minimum structure 1,3-dimethylcyclopentenyl (DMCP+). Experiments are currently being conducted to find softer protonation techniques that could lead to the authentic 2-norbornyl cation. Schleyer,P.v.R. et. al.; Stable Carbocation Chemistry, John Wiley & Sons,Inc.; New York, 1997, Chapter 2

  3. Crystal Structure-Ionic Conductivity Relationships in Doped Ceria Systems

    DEFF Research Database (Denmark)

    Omar, Shobit; Wachsman, Eric D.; Jones, Jacob L.;


    In the past, it has been suggested that the maximum ionic conductivity is achieved in ceria, when doped with an acceptor cation that causes minimum distortion in the cubic fluorite crystal lattice. In the present work, this hypothesis is tested by measuring both the ionic conductivity and elastic...


    Institute of Scientific and Technical Information of China (English)

    Dongmei Yu; Chuanshan Zhao; Kefu Chen


    This study investigated the effects of several different cationic additives on the viscosity 、zeta potential and printing properties of the ink-jet coating. The cationic additives have greatly improved sheet's gloss and printabilities.

  5. Bithiophene radical cation: Resonance Raman spectroscopy and molecular orbital calculations

    DEFF Research Database (Denmark)

    Grage, M.M.-L.; Keszthelyi, T.; Offersgaard, J.F.


    The resonance Raman spectrum of the photogenerated radical cation of bithiophene is reported. The bithiophene radical cation was produced via a photoinduced electron transfer reaction between excited bithiophene and the electron acceptor fumaronitrile in a room temperature acetonitrile solution a...

  6. Ion dynamics in cationic lipid bilayer systems in saline solutions

    DEFF Research Database (Denmark)

    Miettinen, Markus S; Gurtovenko, Andrey A; Vattulainen, Ilpo


    mixture of cationic dimyristoyltrimethylammoniumpropane (DMTAP) and zwitterionic (neutral) dimyristoylphosphatidylcholine (DMPC) lipids. Using atomistic molecular dynamics simulations, we address the effects of bilayer composition (cationic to zwitterionic lipid fraction) and of NaCl electrolyte...

  7. Molecular Dynamics Study of a Dual-Cation Ionomer Electrolyte. (United States)

    Chen, Xingyu; Chen, Fangfang; Jónsson, Erlendur; Forsyth, Maria


    The poly(N1222 )x Li1-x [AMPS] ionomer system (AMPS=2-acrylamido-2-methylpropane sulfonic acid) with dual cations has previously shown decoupled Li ion dynamics from polymer segmental motions, characterized by the glass-transition temperature, which can result in a conductive electrolyte material whilst retaining an appropriate modulus (i.e. stiffness) so that it can suppress dendrite formation, thereby improving safety when used in lithium-metal batteries. To understand this ion dynamics behavior, molecular dynamics techniques have been used in this work to simulate structure and dynamics in these materials. These simulations confirm that the Li ion transport is decoupled from the polymer particularly at intermediate N1222(+) concentrations. At 50 mol % N1222(+) concentration, the polymer backbone is more rigid than for higher N1222(+) concentrations, but with increasing temperature Li ion dynamics are more significant than polymer or quaternary ammonium cation motions. Herein we suggest an ion-hopping mechanism for Li(+) , arising from structural rearrangement of ionic clusters that could explain its decoupled behavior. Higher temperatures favor an aggregated ionic structure as well as enhancing these hopping motions. The simulations discussed here provide an atomic-level understanding of ion dynamics that could contribute to designing an improved ionomer with fast ion transport and mechanical robustness.

  8. Stretch-activated cation channel from larval bullfrog skin

    DEFF Research Database (Denmark)

    Hillyard, Stanley D; Willumsen, Niels J; Marrero, Mario B


    Cell-attached patches from isolated epithelial cells from larval bullfrog skin revealed a cation channel that was activated by applying suction (-1 kPa to -4.5 kPa) to the pipette. Activation was characterized by an initial large current spike that rapidly attenuated to a stable value and showed...... was markedly reduced with N-methyl-D-glucamide (NMDG)-Cl Ringer's solution in the pipette. Neither amiloride nor ATP, which are known to stimulate an apical cation channel in Ussing chamber preparations of larval frog skin, produced channel activation nor did these compounds affect the response to suction....... Stretch activation was not affected by varying the pipette concentrations of Ca(2+) between 0 mmol l(-1) and 4 mmol l(-1) or by varying pH between 6.8 and 8.0. However, conductance was reduced with 4 mmol l(-1) Ca(2+). Western blot analysis of membrane homogenates from larval bullfrog and larval toad skin...

  9. Selective organic synthesis over metal cation-exchanged clay catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Tateiwa, J.; Uemura, S. [Kyoto University, Kyoto (Japan)


    Results of recent studies conducted by the authors are reviewed on the use, as catalysts, of metal cation-exchanged montmorillonite (M{sup n+}-mont), a modified natural clay with a layer structure, and metal cation-exchanged fluor-tetrasilicic mica (M{sup n+}-TSM), a synthetic clay with a layer structure, for the following organic synthesis: (1) Friedel-Crafts alkylation of phenol with 4-hydroxybutan-2-one to produce 4-(4-hydroxyphenyl)butan-2-one (raspberry ketone), (2) rearrangement of alkyl phenyl ethers to corresponding alkylphenols, (3) aromatic alkylation of phenol with aldehydes and ketones to produce corresponding gem-bis(hydroxyphenyl)alkanes (bisphenols) and alkylphenols, respectively, (4) a facile and an almost quantitative substrate-selective acetalization, (5) alkane oxidation with aqueous tert-butyl hydroperoxide, (6) Prins reaction of styrenes with aldehydes using clay as a Bronsted acid, and (7) inter-and intra-molecular carbonyl-ene reaction using clay as a Lewis acid in condition similar to that of Prins reaction. In almost all cases, the clay catalysts could be regenerated and reused several times, after filtration, washing and drying. 42 refs., 20 figs., 3 tabs.

  10. Colloid Facilitated Transport of Radioactive Cations in the Vadose Zone: Field Experiments Oak Ridge

    Energy Technology Data Exchange (ETDEWEB)

    James E. Saiers


    The overarching goal of this study was to improve understanding of colloid-facilitated transport of radioactive cations through unsaturated soils and sediments. We conducted a suite of laboratory experiments and field experiments on the vadose-zone transport of colloids, organic matter, and associated contaminants of interest to the U.S. Department of Energy (DOE). The laboratory and field experiments, together with transport modeling, were designed to accomplish the following detailed objectives: 1. Evaluation of the relative importance of inorganic colloids and organic matter to the facilitation of radioactive cation transport in the vadose zone; 2. Assessment of the role of adsorption and desorption kinetics in the facilitated transport of radioactive cations in the vadose zone; 3. Examination of the effects of rainfall and infiltration dynamics and in the facilitated transport of radioactive cations through the vadose zone; 4. Exploration of the role of soil heterogeneity and preferential flow paths (e.g., macropores) on the facilitated transport of radioactive cations in the vadose zone; 5. Development of a mathematical model of facilitated transport of contaminants in the vadose zone that accurately incorporates pore-scale and column-scale processes with the practicality of predicting transport with readily available parameters.

  11. Determinação simultânea de cátions empregando eletroforese capilar com detecção condutométrica sem contato em equipamento construído em laboratório Simultaneous determination of cations by capillary electrophoresis with contactless conductivity detection performed in a home-made equipment

    Directory of Open Access Journals (Sweden)

    Leandro M. de Carvalho


    Full Text Available This work describes the development of a home-made capillary electrophoresis (CE system based on the capacitively coupled contactless conductivity detection (C4D for the separation of the metallic species Zn2+, Cr3+, Pb2+, Cd2+, Co2+, Cu2+, Ni2+ e Tl+. A background electrolyte composed of MES/Histidine 0,02 mol L-1 (pH 5.0 was optimized for the separation of the metallic species by using organic solvents and complexing agents as additives. The system allowed the determination of the metallic species using MES/Histidine 0,02 mol L-1 and methanol 5% (pH 5.0 as a background electrolyte, 15 kV separation voltage and hydrodynamic injection by gravity.

  12. Production of sulfonated cation-exchangers from petroleum asphaltites

    Energy Technology Data Exchange (ETDEWEB)

    Pokonova, Yu.V.; Pol' kin, G.B.; Proskuryakov, V.A.; Vinogradov, M.V.


    Continuing our studies of the preparation of products of practical value from asphaltite, a new by-product of oil refining, we obtained sulfonated cation-exchangers from a mixture of asphaltite and acid tar. It is shown that these cation-exchangers have good kinetic properties and are superior in thermal and thermohydrolytic stability to the commercial cation-exchange resin KU-2.

  13. CO 2 degassing and trapping during hydrothermal cycles related to Gondwana rifting in eastern Australia (United States)

    Uysal, I. Tonguç; Golding, Suzanne D.; Bolhar, Robert; Zhao, Jian-xin; Feng, Yue-xing; Baublys, Kim A.; Greig, Alan


    Intensive carbonate and clay mineral authigenesis took place throughout the Late Permian Bowen-Gunnedah-Sydney basin system in eastern Australia. We conducted isotopic and trace element analyses of carbonate and clay minerals from clastic sedimentary rocks of the Gunnedah Basin and the Denison Trough in the Bowen Basin. Rb-Sr isochron age data of the illitic clays are consistent with episodic hydrothermal fluid flow events that occurred in association with Gondwana rifting accompanied by alkaline magmatism at ˜85 Ma and ˜95 Ma. Stable isotope data of carbonate and clay minerals from the Gunnedah Basin are indicative of meteoric waters from a high-latitude environment as the main fluid source, whereas trace element, Sr and Nd isotope data highlight mixing of meteoric fluids with magmatic and/or crustal components, with a possible input from marine carbonates for some samples. Trace metals, oxygen and strontium isotopes of dawsonites from the Denison Trough are interpreted to have been mobilised by fluids that interacted with evolved clastic sedimentary and marine carbonate end members. According to the carbon isotope data, CO 2 for calcite and ankerite precipitation was sourced mainly from thermal degradation of organic matter and magmatism, whereas the CO 2 used for dawsonite formation is inferred to have been derived from magmatic and marine sources. In the low permeability environments (particularly in coal seams), the increasing accumulation and oversaturation of CO 2 particularly promote the precipitation of dawsonite.

  14. Ratiometric Molecular Probes Based on Dual Emission of a Blue Fluorescent Coumarin and a Red Phosphorescent Cationic Iridium(III) Complex for Intracellular Oxygen Sensing. (United States)

    Yoshihara, Toshitada; Murayama, Saori; Tobita, Seiji


    Ratiometric molecular probes RP1 and RP2 consisting of a blue fluorescent coumarin and a red phosphorescent cationic iridium complex connected by a tetra- or octaproline linker, respectively, were designed and synthesized for sensing oxygen levels in living cells. These probes exhibited dual emission with good spectral separation in acetonitrile. The photorelaxation processes, including intramolecular energy transfer, were revealed by emission quantum yield and lifetime measurements. The ratios (R(I) = (I(p)/I(f))) between the phosphorescence (I(p)) and fluorescence (I(f)) intensities showed excellent oxygen responses; the ratio of R(I) under degassed and aerated conditions ( R(I)(0) was 20.3 and 19.6 for RP1 and RP2. The introduction of the cationic Ir (III) complex improved the cellular uptake efficiency compared to that of a neutral analogue with a tetraproline linker. The emission spectra of the ratiometric probes internalized into living HeLa or MCF-7 cells could be obtained using a conventional microplate reader. The complex RP2 with an octaproline linker provided ratios comparable to the ratiometric measurements obtained using a microplate reader: the ratio of the R(I)) value of RP2 under hypoxia (2.5% O2) to that under normoxia (21% O2) was 1.5 and 1.7 for HeLa and MCF-7 cells, respectively. Thus, the intracellular oxygen levels of MCF-7 cells could be imaged by ratiometric emission measurements using the complex RP2.

  15. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk


    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope...... of the reaction. Particularly, a formation of configurationally labile aminal centers with alkyl substituents has been a formidable challenge due to the enamine/imine equilibrium of electrophilic substrates. Herein, we report enantioselective nucleophilic addition reactions of potassium phthalimides to Boc......-protected alkyl- and aryl-substituted α-amido sulfones. In-situ generated imines smoothly reacted with the nitrogen nucleophiles to corresponding aminals with good to excellent enantioselectivitiy under mild reaction conditions. In addition, transformation of aminal products gave biologically relevant...

  16. The adjuvant mechanism of cationic dimethyldioctadecylammonium liposomes

    DEFF Research Database (Denmark)

    Korsholm, Karen Smith; Agger, Else Marie; Foged, Camilla


    Cationic liposomes are being used increasingly as efficient adjuvants for subunit vaccines but their precise mechanism of action is still unknown. Here, we investigated the adjuvant mechanism of cationic liposomes based on the synthetic amphiphile dimethyldioctadecylammonium (DDA). The liposomes...... concentrations. This efficient adsorption onto the liposomes led to an enhanced uptake of OVA by BM-DCs as assessed by flow cytometry and confocal fluorescence laser-scanning microscopy. This was an active process, which was arrested at 4 degrees and by an inhibitor of actin-dependent endocytosis, cytochalasin D....... In vivo studies confirmed the observed effect because adsorption of OVA onto DDA liposomes enhanced the uptake of the antigen by peritoneal exudate cells after intraperitoneal injection. The liposomes targeted antigen preferentially to antigen-presenting cells because we only observed a minimal uptake...

  17. Cation Permeability in Soybean Aleurone Layer


    Noda, Hiroko; Fukuda, Mitsuru


    The permeation of water and ions into bean seeds is essential for processing and cooking of beans. The permeability of cations, K, Na, Ca, and Mg ions, into soybean seed tissue, especially aleurone layer, during water uptake was investigated to characterize the ion permeation into soybeans. Aleurone layers and seed coats contained relatively high concentration of endogenous K and Ca ions, and endogenous Ca ion, respectively. The amounts of Ca ion entered seed coats and aleurone layers were gr...

  18. Regulation of Cation Balance in Saccharomyces cerevisiae (United States)

    Cyert, Martha S.; Philpott, Caroline C.


    All living organisms require nutrient minerals for growth and have developed mechanisms to acquire, utilize, and store nutrient minerals effectively. In the aqueous cellular environment, these elements exist as charged ions that, together with protons and hydroxide ions, facilitate biochemical reactions and establish the electrochemical gradients across membranes that drive cellular processes such as transport and ATP synthesis. Metal ions serve as essential enzyme cofactors and perform both structural and signaling roles within cells. However, because these ions can also be toxic, cells have developed sophisticated homeostatic mechanisms to regulate their levels and avoid toxicity. Studies in Saccharomyces cerevisiae have characterized many of the gene products and processes responsible for acquiring, utilizing, storing, and regulating levels of these ions. Findings in this model organism have often allowed the corresponding machinery in humans to be identified and have provided insights into diseases that result from defects in ion homeostasis. This review summarizes our current understanding of how cation balance is achieved and modulated in baker’s yeast. Control of intracellular pH is discussed, as well as uptake, storage, and efflux mechanisms for the alkali metal cations, Na+ and K+, the divalent cations, Ca2+ and Mg2+, and the trace metal ions, Fe2+, Zn2+, Cu2+, and Mn2+. Signal transduction pathways that are regulated by pH and Ca2+ are reviewed, as well as the mechanisms that allow cells to maintain appropriate intracellular cation concentrations when challenged by extreme conditions, i.e., either limited availability or toxic levels in the environment. PMID:23463800

  19. Diffuse degassing He/CO2 ratio before and during the 2011-12 El Hierro submarine eruption, Canary Islands (United States)

    Padrón, Eleazar; Hernández, Pedro A.; Melián, Gladys V.; Barrancos, José; Padilla, Germán; Pérez, Nemesio M.; Dionis, Samara; Rodríguez, Fátima; Asensio-Ramos, María; Calvo, David


    El Hierro Island (278 km2) is the youngest and the SW-most of the Canary Islands. On July 16, 2011, a seismic-volcanic crisis started with the occurrence of more than 11,900 seismic events and significant deformation along the island, culminating with the eruption onset in October 12. Since at El Hierro Islands there are not any surface geothermal manifestation (fumaroles, etc), we have focused our studies on soil degassing surveys. Between July 2011 to March 2012, seventeen diffuse CO2 and He emissions soil gas surveys were undertaken at El Hierro volcanic system (600 observation sites) with the aim to investigate the relationship between their temporal variations and the volcanic activity (Padrón et al., 2013; Melián et al., 2014). Based on the diffuse He/CO2 emission ratio, a sharp increase before the eruption onset was observed, reaching the maximum value on September 26 (6.8×10-5), sixteen days before the occurrence of the eruption. This increase coincided with an increase in seismic energy release during the volcanic unrest and occurred together with an increase on the 3He/4He isotopic ratio in groundwaters from a well in El Hierro Island (Padrón et al., 2013; from 2-3 RA to 7.2 RA where RA = 3He/4He ratio in air), one month prior to the eruption onset. Early degassing of new gas-rich magma batch at depth could explain the observed increase on the He/CO2 ratio, causing a preferential partitioning of CO2 in the gas phase with respect to the He, due to the lower solubility of CO2 than that of He in basaltic magmas. During the eruptive period (October 2011-March 2012) the prevalence of a magmatic CO2-dominated component is evident, as indicated by the generally lower He/CO2 ratios and high 3He/4He values (Padrón et al., 2013). The onset of the submarine eruption might have produced a sudden release of volcanic gases, and consequently, a decrease in the volcanic gas pressure of the magma bodies moving beneath the island, reflected by a drastic decrease in

  20. Basalt-Limestone and Andesite-Limestone Interaction in the Arc Crust - Implications for Volcanic Degassing of CO2 (United States)

    Carter, L. B.; Dasgupta, R.


    Volcanically emitted CO2 is generally mantle-derived, but high degassing rates at some arcs (e.g. Merapi [1] and Colli Albani Volcanic District [2]) are thought to be affected by magma-carbonate interaction in the upper plate. However, the effects of depth, temperature, and composition on this process are poorly known. We experimentally simulated magma (50%)-limestone (50%) wallrock interactions at 0.5-1.0 GPa, 1100-1200 °C using pure calcite and a hydrous (~3-5 wt.% H2O) melt (basalt, andesite, or dacite). At 1.0 GPa, 1200 °C starting melts are superliquidus, whereas in the presence of calcite, Ca-rich cpx ± Ca-scapolite are produced. With increasing T, basalt-calcite interaction causes the melt, on a volatile-free basis, to become silica-poor and Ca-rich with alumina decreasing as cpx becomes more CaTs-rich. The same trend is seen with all starting melt compositions as P decreases at a constant T (1200 °C), producing melts similar to ultracalcic (CaO/Al2O3>>1) melt inclusions found in arc settings. Shifting from basalt to andesite has little effect on SiO2 and CaO of the reacted melt (e.g. 37 wt.% SiO2, 42 wt.% CaO at 0.5 GPa, 1200 °C), whereas Al2O3 of andesite-derived reacted melt is lower, likely a result of lower alumina in the starting andesite. Wall-rock calcite consumption is observed to increase with increasing T, decreasing P, and increasing melt XSiO2. At 0.5 GPa between 1100 and 1200 °C, our basalt experiments yield carbonate assimilation from 22 to 48 wt.%. This decreases to 20 wt.% at 1.0 GPa, 1200 °C, whereas an andesitic composition assimilates 59 to 52 wt.% from 0.5 to 1.0 GPa at 1200 °C. The higher assimilation in andesite-added runs at high-T is because of lower silicate liquidus as evidenced by lower modal proportion or absence of cpx ± scapolite. Using a magma flux rate estimated for Mt. Vesuvius [3], we obtain a CO2 outflux for a single such volcano experiencing arc magma-calcite reaction [4] of at least 2-4% of the present

  1. Controlling chemistry with cations: photochemistry within zeolites. (United States)

    Ramamurthy, V; Shailaja, J; Kaanumalle, Lakshmi S; Sunoj, R B; Chandrasekhar, J


    The alkali ions present in the supercages of zeolites X and Y interact with included guest molecules through quadrupolar (cation-pi), and dipolar (cation-carbonyl) interactions. The presence of such interactions can be inferred through solid-state NMR spectra of the guest molecules. Alkali ions, as illustrated in this article, can be exploited to control the photochemical and photophysical behaviors of the guest molecules. For example, molecules that rarely phosphoresce can be induced to do so within heavy cation-exchanged zeolites. The nature (electronic configuration) of the lowest triplet state of carbonyl compounds can be altered with the help of light alkali metal ions. This state switch (n pi*-pi pi*) helps to bring out reactivity that normally remains dormant. Selectivity obtained during the singlet oxygen oxidation of olefins within zeolites illustrates the remarkable control that can be exerted on photoreactions with the help of a confined medium that also has active sites. The reaction cavities of zeolites, like enzymes, are not only well-defined and confined, but also have active sites that closely guide the reactant molecule from start to finish. The examples provided here illustrate that zeolites are far more useful than simple shape-selective catalysts.

  2. Limited data speaker identification

    Indian Academy of Sciences (India)

    H S Jayanna; S R Mahadeva Prasanna


    In this paper, the task of identifying the speaker using limited training and testing data is addressed. Speaker identification system is viewed as four stages namely, analysis, feature extraction, modelling and testing. The speaker identification performance depends on the techniques employed in these stages. As demonstrated by different experiments, in case of limited training and testing data condition, owing to less data, existing techniques in each stage will not provide good performance. This work demonstrates the following: multiple frame size and rate (MFSR) analysis provides improvement in the analysis stage, combination of mel frequency cepstral coefficients (MFCC), its temporal derivatives $(\\Delta,\\Delta \\Delta)$, linear prediction residual (LPR) and linear prediction residual phase (LPRP) features provides improvement in the feature extraction stage and combination of learning vector quantization (LVQ) and gaussian mixture model – universal background model (GMM–UBM) provides improvement in the modelling stage. The performance is further improved by integrating the proposed techniques at the respective stages and combining the evidences from them at the testing stage. To achieve this, we propose strength voting (SV), weighted borda count (WBC) and supporting systems (SS) as combining methods at the abstract, rank and measurement levels, respectively. Finally, the proposed hierarchical combination (HC) method integrating these three methods provides significant improvement in the performance. Based on these explorations, this work proposes a scheme for speaker identification under limited training and testing data.

  3. Mantle to surface degassing of carbon- and sulphur-rich alkaline magma at El Hierro, Canary Islands (United States)

    Longpré, Marc-Antoine; Stix, John; Klügel, Andreas; Shimizu, Nobumichi


    Basaltic volcanoes transfer volatiles from the mantle to the surface of the Earth. The quantification of deep volatile fluxes relies heavily on estimates of the volatile content of primitive magmas, the best archive of which is provided by melt inclusions. Available data from volcanoes producing mafic alkaline lavas in a range of tectonic settings suggest high volatile fluxes, but information remains sparse, particularly for intraplate ocean islands. Here we present measurements of volatile and trace element concentrations, as well as sulphur speciation, in olivine-hosted melt inclusions and matrix glasses from quenched basanite lava balloon samples from the 2011-2012 submarine eruption at El Hierro, Canary Islands. The results reveal remarkably high concentrations of dissolved volatiles and incompatible trace elements in this magma, with ∼80 ppm Nb and up to 3420 ppm CO2, 3.0 wt.% H2O and 5080 ppm S. Reconstructed primitive CO2 contents, considering CO2/Nb systematics and possible CO2 sequestration in shrinkage bubbles, reach weight percent levels, indicating that carbon is a major constituent of Canary Island magmas at depth and that exsolution of a CO2-rich fluid begins in the mantle at pressures in excess of 1 GPa. Correlations between sulphur concentration, sulphur speciation and water content suggest strong reduction of an initially oxidised mantle magma, likely controlled by coupled H2O and S degassing. This late-stage redox change may have triggered sulphide saturation, recorded by globular sulphide inclusions in clinopyroxene and ulvöspinel. The El Hierro basanite thus had a particularly high volatile-carrying capacity and released a minimum of 1.3-2.1 Tg CO2 and 1.8-2.9 Tg S to the environment, causing substantial stress on the local submarine ecosystem. These results highlight the important contribution of alkaline ocean island volcanoes, such as the Canary Islands, to volatile fluxes from the mantle.

  4. Tiber delta CO2-CH4 degassing: A possible hybrid, tectonically active Sediment-Hosted Geothermal System near Rome (United States)

    Ciotoli, G.; Etiope, G.; Marra, F.; Florindo, F.; Giraudi, C.; Ruggiero, L.


    Fiumicino town in the Tiber River delta, near Rome International Airport (Italy), is historically affected by large amounts of carbon dioxide (CO2) in the ground and gas eruptions triggered by shallow drilling. While it is known that CO2 originates from carbonate thermometamorphism and/or mantle degassing, the origin of methane (CH4) associated with CO2 is uncertain and the outgassing spatial distribution is unknown. Combining isotope gas geochemistry, soil gas, and structural-stratigraphic analyses, we provide evidence for a hybrid fluid source system, classifiable as Sediment-Hosted Geothermal System (SHGS), where biotic CH4 from sedimentary rocks is carried by deep geothermic CO2 through active segments of a half-graben. Molecular and isotopic composition of CH4 and concentration of heavier alkanes (ethane and propane), obtained from gas vents and soil gas throughout the delta area, reveal that thermogenic CH4 (up to 3.7 vol% in soil gas; δ13CCH4: -37 to -40‰ VPDB-Vienna Peedee Belemnite, and δ2HCH4: -162 to -203‰ VSMOW - Vienna Standard Mean Ocean Water in gas vents) prevails over possible microbial and abiotic components. The hydrocarbons likely result from known Meso-Cenozoic petroleum systems of the Latium Tyrrhenian coast. Overmaturation of source rocks or molecular fractionation induced by gas migration are likely responsible for increased C1/C2+ ratios. CO2 and CH4 soil gas anomalies are scattered along NW-SE and W-E alignments, which, based on borehole, geomorphologic, and structural-stratigraphic analyses, coincide with active faults of a half-graben that seems to have controlled the recent evolution of the Tiber delta. This SHGS can be a source of considerable greenhouse gas emissions to the atmosphere and hazards for humans and buildings.

  5. Alkali cation specific adsorption onto fcc(111) transition metal electrodes. (United States)

    Mills, J N; McCrum, I T; Janik, M J


    The presence of alkali cations in electrolyte solutions is known to impact the rate of electrocatalytic reactions, though the mechanism of such impact is not conclusively determined. We use density functional theory (DFT) to examine the specific adsorption of alkali cations to fcc(111) electrode surfaces, as specific adsorption may block catalyst sites or otherwise impact surface catalytic chemistry. Solvation of the cation-metal surface structure was investigated using explicit water models. Computed equilibrium potentials for alkali cation adsorption suggest that alkali and alkaline earth cations will specifically adsorb onto Pt(111) and Pd(111) surfaces in the potential range of hydrogen oxidation and hydrogen evolution catalysis in alkaline solutions.

  6. [Antioxidant activity of cationic whey protein isolate]. (United States)

    titova, M E; Komolov, S A; Tikhomirova, N A


    The process of lipid peroxidation (LPO) in biological membranes of cells is carried out by free radical mechanism, a feature of which is the interaction of radicals with other molecules. In this work we investigated the antioxidant activity of cationic whey protein isolate, obtained by the cation-exchange chromatography on KM-cellulose from raw cow's milk, in vitro and in vivo. In biological liquids, which are milk, blood serum, fetal fluids, contains a complex of biologically active substances with a unique multifunctional properties, and which are carrying out a protective, antimicrobial, regenerating, antioxidant, immunomodulatory, regulatory and others functions. Contents of the isolate were determined electrophoretically and by its biological activity. Cationic whey protein isolate included lactoperoxidase, lactoferrin, pancreatic RNase, lysozyme and angeogenin. The given isolate significantly has an antioxidant effect in model experimental systems in vitro and therefore may be considered as a factor that can adjust the intensity of lipid oxidation. In model solutions products of lipid oxidation were obtained by oxidation of phosphatidylcholine by hydrogen peroxide in the presence of a source of iron. The composition of the reaction mixture: 0,4 mM H2O2; 50 mcM of hemin; 2 mg/ml L-alpha-phosphatidylcholine from soybean (Sigma, German). Lipid peroxidation products were formed during the incubation of the reaction mixture for two hours at 37 degrees C. In our studies rats in the adaptation period immediately after isolation from the nest obtained from food given orally native cationic whey protein isolate at the concentration three times higher than in fresh cow's milk. On the manifestation of the antioxidant activity of cationic whey protein isolate in vivo evidence decrease of lipid peroxidation products concentration in the blood of rats from the experimental group receipt whey protein isolate in dos 0,6 mg/g for more than 20% (pwhey protein isolate has an

  7. Evolutionary and structural perspectives of plant cyclic nucleotide-gated cation channels

    KAUST Repository

    Zelman, Alice K.


    Ligand-gated cation channels are a frequent component of signaling cascades in eukaryotes. Eukaryotes contain numerous diverse gene families encoding ion channels, some of which are shared and some of which are unique to particular kingdoms. Among the many different types are cyclic nucleotide-gated channels (CNGCs). CNGCs are cation channels with varying degrees of ion conduction selectivity. They are implicated in numerous signaling pathways and permit diffusion of divalent and monovalent cations, including Ca2+ and K+. CNGCs are present in both plant and animal cells, typically in the plasma membrane; recent studies have also documented their presence in prokaryotes. All eukaryote CNGC polypeptides have a cyclic nucleotide-binding domain and a calmodulin binding domain as well as a six transmembrane/one pore tertiary structure. This review summarizes existing knowledge about the functional domains present in these cation-conducting channels, and considers the evidence indicating that plant and animal CNGCs evolved separately. Additionally, an amino acid motif that is only found in the phosphate binding cassette and hinge regions of plant CNGCs, and is present in all experimentally confirmed CNGCs but no other channels was identified. This CNGC-specific amino acid motif provides an additional diagnostic tool to identify plant CNGCs, and can increase confidence in the annotation of open reading frames in newly sequenced genomes as putative CNGCs. Conversely, the absence of the motif in some plant sequences currently identified as probable CNGCs may suggest that they are misannotated or protein fragments. 2012 Zelman, Dawe, Gehring and Berkowitz.

  8. Anion stripping as a general method to create cationic porous framework with mobile anions. (United States)

    Mao, Chengyu; Kudla, Ryan A; Zuo, Fan; Zhao, Xiang; Mueller, Leonard J; Bu, Xianhui; Feng, Pingyun


    Metal-organic frameworks (MOFs) with cationic frameworks and mobile anions have many applications from sensing, anion exchange and separation, to fast ion conductivity. Despite recent progress, the vast majority of MOFs have neutral frameworks. A common mechanism for the formation of neutral frameworks is the attachment of anionic species such as F(-) or OH(-) to the framework metal sites, neutralizing an otherwise cationic scaffolding. Here, we report a general method capable of converting such neutral frameworks directly into cationic ones with concurrent generation of mobile anions. Our method is based on the differential affinity between distinct metal ions with framework anionic species. Specifically, Al(3+) is used to strip F(-) anions away from framework Cr(3+) sites, leading to cationic frameworks with mobile Cl(-) anions. The subsequent anion exchange with OH(-) further leads to a porous network with mobile OH(-) anions. New materials prepared by anion stripping can undergo ion exchange with anionic organic dyes and also exhibit much improved ionic conductivity compared to the original unmodified MOFs.

  9. Fluctuation conductivity in cuprate superconductors

    Indian Academy of Sciences (India)

    S N Bhatia


    We have measured the in-plane resistivity of Bi2Sr2CaCu2O8+ and Tl2Ba2CaCu2O8+ single crystals in the temperature range 70–300 K. The thermodynamic fluctuations in the conductivity of both the samples start around ∼ 125 K. We find the Lawrence and Doniach [1] model to be inadequate to describe the fluctuation conductivity in these materials. The modification suggested by Ramallo et al [4] where by the conductivity is enhanced due to the presence of two superconducting layers in each unit cell is also not adequate. We suggest the fluctuation conductivity to be reduced due to the reduction in the density of states (DOS) of the quasiparticles which results due to the formation of Cooper pairs at the onset of the fluctuations. The data agrees with the theory proposed by Dorin et al [5] which takes into account this reduction in DOS.

  10. Interaction between alginates and manganese cations: identification of preferred cation binding sites. (United States)

    Emmerichs, N; Wingender, J; Flemming, H-C; Mayer, C


    Algal and bacterial alginates have been studied by means of 13C NMR spectroscopy in presence of paramagnetic manganese ions in order to reveal the nature of their interaction with bivalent cations. It is found that the mannuronate blocks bind manganese cations externally near their carboxylate groups, while guluronate blocks show the capability to integrate Mn2+ into pocket-like structures formed by adjacent guluronate residues. In alternating mannuronate-guluronate blocks, manganese ions preferentially locate in a concave structure formed by guluronate-mannuronate pairs. Partial acetylation of the alginate generally reduces its capability to interact with bivalent cations, however, the selectivity of the binding geometry is conserved. The results may serve as a hint for the better understanding of the alginate gelation in presence of calcium ions.

  11. Induction of morphogenesis in Geodermatophilus by inorganic cations and by organic nitrogenous cations. (United States)

    Ishiguro, E E; Wolfe, R S


    Morphogenesis of Geodermatophilus strain 22-68 involves two stages, a motile rod (R form) and an irregularly shaped cluster of coccoid cells (C form). A variety of mono- and divalent cations have been found to induce R-form to C-form morphogenesis and to maintain the organism in the C form. Concentration optima for all cations exceeded 100 mM. Results indicated that uptake of cations was accompanied by extrusion of intracellular protons, causing an increase in intracellular pH. A variety of organic amines also induced morphogenesis. Organic amines were taken up in the dissociated free base form, causing the intracellular pH to rise. None of these compounds was utilized as a carbon or nitrogen source.

  12. Cationic niosomes an effective gene carrier composed of novel spermine-derivative cationic lipids: effect of central core structures. (United States)

    Opanasopit, Praneet; Leksantikul, Lalita; Niyomtham, Nattisa; Rojanarata, Theerasak; Ngawhirunpat, Tanasait; Yingyongnarongkul, Boon-Ek


    Cationic niosomes formulated from Span 20, cholesterol (Chol) and novel spermine-based cationic lipids of multiple central core structures (di(oxyethyl)amino, di(oxyethyl)amino carboxy, 3-amino-1,2-dioxypropyl and 2-amino-1,3-dioxypropyl) were successfully prepared for improving transfection efficiency in vitro. The niosomes composed of spermine cationic lipid with central core structure of di(oxyethyl)amino revealed the highest gene transfection efficiency. To investigate the factors affecting gene transfection and cell viability including differences in the central core structures of cationic lipids, the composition of vesicles, molar ratio of cationic lipids in formulations and the weight ratio of niosomes to DNA. Cationic niosomes composed of nonionic surfactants (Span20), cholesterol and spermine-based cationic lipids of multiple central core structures were formulated. Gene transfection and cell viability were evaluated on a human cervical carcinoma cell line (HeLa cells) using pDNA encoding green fluorescent protein (pEGFP-C2). The morphology, size and charge were also characterized. High transfection efficiency was obtained from cationic niosomes composed of Span20:Chol:cationic lipid at the molar ratio of 2.5:2.5:0.5 mM. Cationic lipids with di(oxyethyl)amino as a central core structure exhibited highest transfection efficiency. In addition, there was also no serum effect on transfection efficiency. These novel cationic niosomes may constitute a good alternative carrier for gene transfection.

  13. Magma degassing and eruption dynamics of the Avellino pumice Plinian eruption of Somma-Vesuvius (Italy). Comparison with the Pompeii eruption (United States)

    Balcone-Boissard, H.; Boudon, G.; Ucciani, G.; Villemant, B.; Cioni, R.; Civetta, L.; Orsi, G.


    The eruptive history of Mt. Somma-Vesuvius is characterised by large explosive events: Pomici di Base eruption (22,030 ± 175 yr cal BP), Mercato (8890 ± 90 yr cal BP), Avellino (3945 ± 10 yr cal BP) and Pompeii (79 AD). Pre-eruptive conditions and sin-eruptive degassing processes of the Avellino eruption, the highest-magnitude Plinian event, have been investigated, using volatile contents (F, Cl, H2O) in melt inclusions and residual glass, and textural characteristics of pumice clasts of the 9 fallout layers sampled in detail in a representative sequence. The sequence displays an up-section sharp colour change from white to grey, corresponding to variations in both magma composition and textural characteristics. The pre-eruptive conditions have been constrained by systematic measurements of Cl content in both melt inclusions and matrix glass of pumice clasts. The pumice glass composition varies from Na-rich phonolite (white pumice) to K-rich phonolite (grey pumice). The measured Cl values constantly cluster at 5200 ± 400 ppm (buffer value), whatever the composition of the melt, suggesting that the entire magma body was saturated with sub-critical fluids. This Cl saturation constrains the pre-eruptive pressures and maximum H2O contents at 200 ± 10 MPa and 6.3 ± 0.2 wt.% H2O for the white pumice melt and 195 ± 15 MPa and 5.2 ± 0.2 wt.% H2O for the grey pumice melt. The fluid phase, mainly composed of a H2O-rich vapour phase and brine, probably accumulated at the top of the reservoir and generated an overpressure able to trigger the onset of the eruption. Magma degassing was rather homogeneous for the white and grey eruptive units, mostly occurring through closed-system processes, leading to a typical Plinian eruptive style. A steady-state withdrawal of an H2O-saturated magma may explain the establishment of a sustained Plinian column. Variation from white to grey pumice is accompanied by decrease of mean vesicularity and increase of mean microcrystallinity

  14. Modeling the consequences on late Triassic environment of intense pulse-like degassing during the Central Atlantic Magmatic Province using the GEOCLIM model

    Directory of Open Access Journals (Sweden)

    G. Paris


    Full Text Available The Triassic-Jurassic boundary (TJB is associated with one of the five largest mass extinctions of the Phanerozoic. A deep carbon cycle perturbation and a carbonate production crisis are observed during the late Triassic. The Central Atlantic Magmatic Province (CAMP, one of the most important large igneous provinces of the Phanerozoic, emplaced at the TJB. To understand the carbon cycle perturbations observed at the TJB, we investigate the consequences of CO2 degassing associated to the CAMP emplacement on atmospheric and oceanic carbon cycle. The CO2 input within the atmosphere due to volcanism has been modeled using a global biogeochemical cycle box model (COMBINE coupled with a climate model (FOAM. Weathering fluxes and CO2 equilibrium are constrained by the Rhaetian paleogeography and different scenarios of the CAMP emplacement are modeled. The study focuses (1 on the geological record and the carbonate productions crisis and (2 on the sedimentary carbon isotope record. For point (1, comparison of different modeling scenarios shows that a Gaussian CO2 emission distribution over the duration of the main activity phase of the CAMP fails in reproducing any of the geological observations, mainly the carbonate production crisis observed in the late Rhaetian sediments. Contrastingly, intense degassing peaks lead to successive decrease in carbonate production as observed in the geological record. For point (2, the perturbations of carbon cycle due to the degassing of CO2 with a mantellic carbon isotopic composition of −5‰ do not reproduce the intensity of the observed carbon isotope excursions. This was achieved in our model by assuming a mantellic carbon isotopic composition of −20‰. Even if this hypothesis requires further investigations, such low values may be associated to degassing of carbon from pools of light isotopic carbon located at the transition zone (Cartigny, 2010

  15. CO2 degassing in the Hartoušov mofette area, western Eger Rift, imaged by CO2 mapping and geoelectrical and gravity surveys (United States)

    Nickschick, Tobias; Kämpf, Horst; Flechsig, Christina; Mrlina, Jan; Heinicke, Jens


    Strong, subcontinental mantle-dominated CO2 degassing occurs in the Hartoušov and Bublák mofette fields in the western Eger Rift. The combination of CO2 gas flux and soil gas measurements as well as gravity and geoelectric surveys provides insight into the surface and subsurface of this unique mofette area. CO2 soil gas and gas flux measurements reveal that large amounts of carbon dioxide are released via channels with diameters below 1 m. Carbon dioxide emissions of several tens and up to more than 100 kg day-1 are ejected via these small seeps. Measurements with small spacings are necessary to account for the point like, focused gas discharge in the lesser degassing surrounding. We estimate that between 23 and 97 tons of CO2 are released over an area of about 350,000 m2 each day in the Hartoušov mofette field. The application of widely used geostatistical tools leads to estimations of the CO2 discharge with very high standard deviations due to the strong positive skewness of the data distribution. Geophysical investigations via electrical resistivity tomography and gravity measurements were carried out over areas of strong seepage and reveal distinct anomalies in the subsurface below mofettes, indicating rock and sediment alterations and/or sediment transport by pressurised, ascending CO2 and water mobilised by it. This study reveals that the gas emanations only occur west of a morphological step which is related to a N-S-oriented fault zone, the Počatky-Plesná fault zone. The results of CO2 mapping and the geophysical studies can track the course of this fault zone in this area. Our results fit into a tectonic model in which the mofette fields are in the centres of two independent pull-apart basin-like structures. We hypothesise that the sinistral strike-slip movement of the Počatky-Plesná fault zone leads to a pull-apart basin-like opening, at which the strong, mantle-derived CO2 degassing occurs nowadays. Since the Hartoušov and Bublák mofette fields

  16. Development of the large-size beryllium vacuum degassing furnace%大型铍材一次脱气真空炉的研制

    Institute of Scientific and Technical Information of China (English)

    张延宾; 郑侠; 戴天舒


    介绍了真空脱气炉技术性能、设备结构及特点。该设备的研制成功对铍工业的进步和发展具有重要的现实意义。%The technical parameters, mechanical structure and characteristics of the vacuum degassing furnace were introduced. The successful development of the furnace has an important practical significance for the progress and development of the beryllium industry.

  17. Pore size matters for potassium channel conductance (United States)

    Moldenhauer, Hans; Pincuntureo, Matías


    Ion channels are membrane proteins that mediate efficient ion transport across the hydrophobic core of cell membranes, an unlikely process in their absence. K+ channels discriminate K+ over cations with similar radii with extraordinary selectivity and display a wide diversity of ion transport rates, covering differences of two orders of magnitude in unitary conductance. The pore domains of large- and small-conductance K+ channels share a general architectural design comprising a conserved narrow selectivity filter, which forms intimate interactions with permeant ions, flanked by two wider vestibules toward the internal and external openings. In large-conductance K+ channels, the inner vestibule is wide, whereas in small-conductance channels it is narrow. Here we raise the idea that the physical dimensions of the hydrophobic internal vestibule limit ion transport in K+ channels, accounting for their diversity in unitary conductance. PMID:27619418

  18. Heart imaging with cationic complexes of technetium

    Energy Technology Data Exchange (ETDEWEB)

    Deutsch, E.; Bushong, W.; Glavan, K.A.; Elder, R.C.; Sodd, V.J.; Scholz, K.L.; Fortman, D.L.; Lukes, S.J.


    The cationic technetium-99 complex trans-(99TC(dmpe)2Cl2)+, where dmpe is bis(1,2-dimethylphosphino)ethane or (CH3)2P-CH2-P(CH3)2, has been prepared and characterized by single-crystal, x-ray structural analysis. The technetium-99m analog, trans-(99mTc(dmpe) 2Cl2)+, has also been prepared and shown to yield excellent gamma-ray images of the heart. The purposeful design, characterization, and synthesis of this technetium-99m radiopharmaceutical represents a striking application of fundamental inorganic chemistry to a problem in applied nuclear medicine.

  19. Aggregate Formed by a Cationic Fluorescence Probe

    Institute of Scientific and Technical Information of China (English)

    TIAN, Juan; SANG, Da-Yong; JI, Guo-Zhen


    The aggregation behavior of a cationic fluorescence probe 10-(4,7,10,13,16-pentaoxa-1-azacyclooctadecyl-methyl)anthracen-9-ylmethyl dodecanoate (1) was observed and studied by a fluorescence methodology in acidic and neutral conditions. By using the Py scale, differences between simple aggregates and micelles have been discussed. The stability of simple aggregates was discussed in terms of hydrophobic interaction and electrostatic repulsion. The absence of excimer emission of the anthrancene moiety of probe 1 in neutral condition was attributed to the photoinduced electron transfer mechanism instead of photodimerization.

  20. Spatial and temporal variations of diffuse CO_{2} degassing at the N-S volcanic rift-zone of Tenerife (Canary Islands, Spain) during 2002-2015 period (United States)

    Alonso, Mar; Ingman, Dylan; Alexander, Scott; Barrancos, José; Rodríguez, Fátima; Melián, Gladys; Pérez, Nemesio M.


    Tenerife is the largest of the Canary Islands and, together with Gran Canaria Island, is the only one with a central volcanic complex that started to grow at about 3.5 Ma. Nowadays the central complex is formed by Las Cañadas caldera, a volcanic depression measuring 16×9 km that resulted from multiple vertical collapses and was partially filled by post-caldera volcanic products. Up to 297 mafic monogenetic cones have been recognized on Tenerife, and they represent the most common eruptive activity occurring on the island during the last 1 Ma (Dóniz et al., 2008). Most of the monogenetic cones are aligned following a triple junction-shaped rift system, as result of inflation produced by the concentration of emission vents and dykes in bands at 120o to one another as a result of minimum stress fracturing of the crust by a mantle upwelling. The main structural characteristic of the southern volcanic rift (N-S) of the island is an apparent absence of a distinct ridge, and a fan shaped distribution of monogenetic cones. Four main volcanic successions in the southern volcanic rift zone of Tenerife, temporally separated by longer periods (˜70 - 250 ka) without volcanic activity, have been identified (Kröchert and Buchner, 2008). Since there are currently no visible gas emissions at the N-S rift, diffuse degassing surveys have become an important geochemical tool for the surveillance of this volcanic system. We report here the last results of diffuse CO2 efflux survey at the N-S rift of Tenerife, performed using the accumulation chamber method in the summer period of 2015. The objectives of the surveys were: (i) to constrain the total CO2 output from the studied area and (ii) to evaluate occasional CO2 efflux surveys as a volcanic surveillance tool for the N-S rift of Tenerife. Soil CO2 efflux values ranged from non-detectable up to 31.7 g m-2 d-1. A spatial distribution map, constructed following the sequential Gaussian simulation (sGs) procedure, did not show an

  1. Carbon Release in Italy through Volcanic, Tectonic and Other Styles of Degassing: Implication for Carbon Dioxide Sequestration and Storage. (United States)

    Bigi, S.; Lombardi, S.; Beaubien, S.; Graziani, S.; Tartarello, M. C.; Ruggiero, L.; Ciotoli, G.; Sacco, P.; De Angelis, D.; Annunziatellis, A.


    One of the key criteria for successful geological storage of CO2 is that the target reservoir must not leak the stored gases over extended periods. Due to the peculiarity of its geological and geodynamic setting, which results in the production, accumulation, and leakage of large volumes of natural CO2, the Italian peninsula can be used as a natural laboratory as it provides to study gas migration mechanisms in large-scale geological systems, as well as to determine whether and how much sequestered CO2 could hypothetically leak from a subsurface reservoir. Moving from west to east, the Italian peninsula includes several geodynamic settings: the Tyrrhenian back arc basin and associated volcanic arcs, the Apennines fold and thrust belt, and the Adriatic foredeep. All of them are characterized by a diffuse and/or massive degassing of deeply derived CO2, which is usually emitted by vents or dissolved and transported by large aquifers. In the volcanic islands, in the south of the Tyrrhenian Sea, large areas are characterized by leakage from the sea floor. Based on the statistical and geo-spatial interpretation of more than 40,000 soil gas samples collected in central and southern Italy by the Fluid Chemistry Laboratory of "La Sapienza" University of Rome over more than 30 years of activity, different migration patterns related to the different geodynamic settings are distinguished and described. This very large database has been organised and managed in a GIS environment that allows the calculation of fundamental statistical parameters, the analysis of distribution patterns, the study of spatial autocorrelation and spatial heterogeneity, and the elaboration of maps. The interpretation of these data allow us to define background values of CO2, strongly related to geological setting, and other minor (CH4) and trace gases (He and Rn), that characterise the different geological scenarios. A common feature is that anomalous gas concentrations occur in restricted zones, both

  2. Broadband seismic measurements of degassing activity associated with lava effusion at Popocatépetl Volcano, Mexico (United States)

    Arciniega-Ceballos, Alejandra; Chouet, Bernard; Dawson, Phillip; Asch, Guenter


    From November 1999 through July 2000, a broadband seismic experiment was carried out at Popocatépetl Volcano to record seismic activity over a wide period range (0.04-100 s). We present an overview of the seismicity recorded during this experiment and discuss results of analyses of long-period (LP) and very-long-period (VLP) seismic signals recorded at stations nearest to the crater over a four-month interval December 1999-March 2000. Three families of LP signals (Types-I, II, and III) are identified based on distinctive waveform features observed periods shorter than 1 s, periods longer than 15 s, and within the period range 0.5-2.5 s. Type-I LP events have impulsive first arrivals and exhibit a characteristic harmonic wave train with dominant periods in the 1.4-1.9 s range during the first 10 s of signal. These events are also associated with a remarkable VLP wavelet with period near 30 s. Type-II LP events represent pairs of events occurring in rapid succession and whose signatures are superimposed. These are typically marked by slowly emergent first arrivals and by a characteristic VLP wave train with dominant period near 30 s, made of two successive wavelets whose shapes are quasi-identical to those of the VLP wavelets associated with Type-I events. Type-III LP events represent the most energetic signals observed during our experiment. These have an emergent first arrival and display a harmonic signature with dominant period near 1.1 s. They are dominated by periods in the 0.25-0.35 s band and contain no significant energy at periods longer than 15 s. Hypocentral locations of the three types of LP events obtained from phase picks point to shallow seismic sources clustered at depths shallower than 2 km below the crater floor. Observed variations in volcanic eruptive activity correlate with defined LP families. Most of the observed seismicity consists of Type-I events that occur in association with 1-3-min-long degassing bursts ("exhalations"). Eruptive

  3. Sixteen years monitoring of Cumbre Vieja volcano (La Palma, Canary Islands) by means of diffuse CO2 degassing surveys (United States)

    Cótchico, M. A.; Renee, L. K.; De Jongh, M. E.; Padron, E.; Hernandez Perez, P. A.; Perez, N. M.


    La Palma Island, the fifth longest (706 km2) and second highest (2,423 m asl) of the Canary Islands, is located at the northwestern end of the archipelago. Subaerial volcanic activity on La Palma started 2.0 My ago and has taken place exclusively at the southern part of the island during the last 123 ka, where Cumbre Vieja volcano, the most active basaltic volcano in the Canaries, has been constructed. Major volcano-structural and geomorphological features of Cumbre Vieja volcano are a north-south rift zone 20 km long, with vents located also at the northwest and northeast, and up to 1,950 m in elevation covering an área of 220 km2. Nowadays, there are no visible gas emissions from fumaroles or hot springs at Cumbre Vieja; therefore, diffuse CO2 degassing monitoring is important geochemical tool for its volcanic surveillance. Recent studies have shown that enhanced endogenous contributions of deep-seated CO2 might have been responsible for higher diffuse CO2 efflux values (Padrón et al., 2015). We report here the latest results of the diffuse CO2 emission survey at Cumbre Vieja volcano. The surface CO2 efflux measurements were taken using the accumulation chamber method in the period 1997- 2016 to evaluate their spatial distribution on this 220 km2 volcano and the diffuse CO2 emission rate from Cumbre Vieja volcano. Surface CO2 efflux values ranged from non-detectable up to 94 g m-2 d-1 in the last survey. Spatial distribution maps were constructed following the sequential Gaussian simulation (sGs) procedure. The spatial distribution of diffuse CO2 emission values did not seem to be controlled by the main structural features of the volcano since the highest values were measured in the southern part. The diffuse CO2 emission for the 2016 survey has been estimated about 739 ± 30 t d-1. The 2016 emission rate is slightly higher than the estimated average for Cumbre Vieja volcano (493 t d-1), but within the observed background range for this volcanic system over the

  4. Transcriptome analysis of beer-spoiling Lactobacillus brevis BSO 464 during growth in degassed and gassed beer. (United States)

    Bergsveinson, Jordyn; Friesen, Vanessa; Ziola, Barry


    Lactobacillus brevis BSO 464 (Lb464) is a beer-spoilage-related (BSR) isolate of interest given its unique physiological attributes; specifically, it is highly hop-tolerant and exhibits very rapid growth in pressurized/gassed beer. RNA sequencing was performed on Lb464 grown in pressurized and non-pressurized beer to determine important genetic mechanisms for growth in these environments. The data generated were compared against data in a previous transcriptional study of another lactic acid bacterium (LAB) during growth in beer, namely, Pediococcus claussenii ATCC BAA-344(T) (Pc344). Results revealed that the most important genetic elements for Lb464 growth in beer are related to biogenic amine metabolism, membrane transport and fortification, nutrient scavenging, and efficient transcriptional regulation. Comparison with the previous transcriptional study of Pc344 indicated that the total coding capacity (plasmid profile and genome size) of a LAB isolate allows for beer-spoilage virulence and adaptation to different beer environments, i.e., the ability to grow in degassed beer (during production) or gassed beer (packaged product). Further, differences in gene expression of Lb464 and Pc344 during mid-exponential growth in beer may dictate how rapidly each isolate exhausts particular carbon sources during. The presence of headspace pressure/dissolved CO2 was found to drive Lb464 transcription during mid-exponential growth in beer towards increasing cell wall and membrane modification, transport, osmoregulation, and DNA metabolism and transposition events. This transcriptional activity resembles transcriptional patterns or signatures observed in a viable, but non-culturable state established by non-related organisms, suggesting that Lb464 overall uses complex cellular regulation to maintain cell division and growth in the stressful beer environment. Additionally, increased expression of several hypothetical proteins, the hop-tolerance gene horC, and DNA repair and

  5. Magma transfer and degassing budget: Application to the 2009-2010 eruptive crisis of Mt Garet (Vanuatu arc) (United States)

    Métrich, N.; Bertagnini, A.; Garaebiti, E.; Vergniolle, S.; Bani, P.; Beaumais, A.; Neuville, D. R.


    Mt Garet, on Gaua Island, is one of the active volcanoes of the Vanuatu arc. We report here a new dataset on lapilli and lava erupted during Mt Garet unrest in 2009-2010 and on products of the older activity of Gaua composite volcano. The present-day magma of Mt Garet is a trachy-andesite (52 wt.% SiO2) with relatively high Rb/Th (14.6) and Ba/La (41) ratios compared to the Gaua pre- and syn-caldera series, but typical of the central part of Vanuatu arc. Its mineral assemblage is mainly composed of plagioclase (An86-56) and clinopyroxene (Fs5-16) which display significant chemical variations, patchy zones, surface dissolution, and oscillatory zoning that imply episodes of high undercooling and growth rates. The paragenesis is complemented by Fe-Ti oxides and scarce olivine (Fo72-73). The melt inclusions are ubiquitous and their compositions cover a chemical spectrum from basalt to trachy-andesite. Volatile-rich basaltic inclusions (H2O: 2.7 wt.%, S: 0.15 wt.%, and Cl: 0.22 wt.%) are preserved in Mg-rich clinopyroxene whereas the majority of the melt inclusions is volatile poorer with, ≤ 1.0 wt.% of H2O, ≤ 0.05 wt.% of S, and 0.25-0.27 wt.% of Cl. At 1100 °C the measured viscosity of anhydrous magma of Mt Garet is 103.5 Pa s. Adding 0.8 to 2.5 wt.% of H2O decreases the melt viscosity by 0.5 to two orders of magnitude. Combining data on bulk rocks, minerals, and their melt inclusions together with the very first published gas fluxes acquired during the same period of activity, we propose that the high sulfur outgassing in 2009-2010 was produced by the degassing of a basaltic magma batch ( 0.027 km3) emplaced in a shallow reservoir. This scenario would require temperature and H2O-loss driven resorption/crystallization, magma mixing, and exsolution of an early gas phase rich in H2O, and S. We suggest here the 2009-2010 activity to be sustained by the existence of thermal convection driven at the bottom of the magma reservoir by cooling, and in which the bubbles

  6. Widespread oxidized and hydrated amorphous silicates in CR chondrites matrices: Implications for alteration conditions and H2 degassing of asteroids (United States)

    Le Guillou, Corentin; Changela, Hitesh G.; Brearley, Adrian J.


    (higher temperature, longer duration, change of fluid composition). In a fully closed system, equilibrium thermodynamics suggest that the water to rock ratios, typically assumed to be low (<1) for chondrites, should primarily control the iron valency of the silicates and predict a lower Fe3+ / ∑ Fe ratio. Such a high Fe3+ / ∑ Fe value could be accounted for, however, if the system was partially open, at least with respect to H2 (and other gases as well). Rapid degassing of the fluid would have favored more oxidizing fluid conditions. Recently proposed scenarios involving some degree of water D/H increase through Rayleigh isotopic fractionation are supported by these results.

  7. Use of statistical modeling to predict the effect of formulation composition on coacervation, silicone deposition, and conditioning sensory performance of cationic cassia polymers. (United States)

    Lepilleur, Carole; Mullay, John; Kyer, Carol; McCalister, Pam; Clifford, Ted


    Formulation composition has a dramatic influence on coacervate formation in conditioning shampoo. The purpose of this study is to correlate the amount of coacervate formation of novel cationic cassia polymers to the corresponding conditioning profiles on European brown hair using silicone deposition, cationic polymer deposition and sensory evaluation. A design of experiments was conducted by varying the levels of three surfactants (sodium lauryl ether sulfate, sodium lauryl sulfate, and cocamidopropyl betaine) in formulations containing cationic cassia polymers of different cationic charge density (1.7 and 3.0m Eq/g). The results show formulation composition dramatically affects physical properties, coacervation, silicone deposition, cationic polymer deposition and hair sensory attributes. Particularly, three parameters are of importance in determining silicone deposition: polymer charge, surfactant (micelle) charge and total amount of surfactant (micelle aspect ratio). Both sensory panel testing and silicone deposition results can be predicted with a high confidence level using statistical models that incorporate these parameters.

  8. Ionic liquids based on S-alkylthiolanium cations and TFSI anion as potential electrolytes

    Institute of Scientific and Technical Information of China (English)

    ZHANG HuanQi; YANG Li; FANG ShaoHua; PENG ChengXin; LUO HongJun


    New ionic liquids based on S-alkylthiolanium cations with TFSI anions were synthesized and charac-terized.The physical and electrochemical properties,including melting point,thermal stability,solubil-ity,viscosity,conductivity and electrochemical window,were reported.Relation between these proper-ties and the structure of the cations was discussed.In this series,T4TFSI and T5TFSI have melting points below -60℃,and their conductivities are 2.10 mS/cm and 1.46 mS/cm;their electrochemical windows are 4.1 V and 4.5 V at room temperature.These cyclic alkylthiolanium-based ionic liquids are promising as novel electrolytes in various electrochemical devices,especially under low temperature condition.

  9. Studies of Fe-Co based perovskite cathodes with different A-site cations

    DEFF Research Database (Denmark)

    Kammer Hansen, K.


    Iron-cobalt based perovskite cathodes with different A-site cations ((Ln(0.6)Sr(0.4))(0.99)Fe0.8Co0.2O3-delta, where Ln is La, Pr, Sm or Gd) have been synthesised, characterised by a powder XRD, dilatometry, 4-point DC conductivity measurements, and electrochemical impedance spectroscopy (EIS......) on cone shaped electrodes. In addition to this scanning electron microscopy (SEM) was used to characterise the bars. XRD revealed that only the La-containing perovskite was hexagonal. The Pr and Sm perovskites were orthorhombic. The gadolinium-based perovskite was a two phase system consisting...... of an orthorhombic and a cubic perovskite phase. The thermal expansion coefficient (TEC) increased systematically with a decrease in the size of the A-site cation until the gadoliniurn-containing perovskite where the TEC decreases abruptly. The total electric conductivity was the highest for the La-based perovskite...

  10. Electronic absorptions of the benzylium cation (United States)

    Dryza, Viktoras; Chalyavi, Nahid; Sanelli, Julian A.; Bieske, Evan J.


    The electronic transitions of the benzylium cation (Bz+) are investigated over the 250-550 nm range by monitoring the photodissociation of mass-selected C7H7+-Arn (n = 1, 2) complexes in a tandem mass spectrometer. The Bz+-Ar spectrum displays two distinct band systems, the S1←S0 band system extending from 370 to 530 nm with an origin at 19 067 ± 15 cm-1, and a much stronger S3←S0 band system extending from 270 to 320 nm with an origin at 32 035 ± 15 cm-1. Whereas the S1←S0 absorption exhibits well resolved vibrational progressions, the S3←S0 absorption is broad and relatively structureless. Vibronic structure of the S1←S0 system, which is interpreted with the aid of time-dependent density functional theory and Franck-Condon simulations, reflects the activity of four totally symmetric ring deformation modes (ν5, ν6, ν9, ν13). We find no evidence for the ultraviolet absorption of the tropylium cation, which according to the neon matrix spectrum should occur over the 260 - 275 nm range [A. Nagy, J. Fulara, I. Garkusha, and J. Maier, Angew. Chem., Int. Ed. 50, 3022 (2011)], 10.1002/anie.201008036.

  11. Photodissociation of Cerium Oxide Nanocluster Cations. (United States)

    Akin, S T; Ard, S G; Dye, B E; Schaefer, H F; Duncan, M A


    Cerium oxide cluster cations, CexOy(+), are produced via laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. The mass spectrum displays a strongly preferred oxide stoichiometry for each cluster with a specific number of metal atoms x, with x ≤ y. Specifically, the most prominent clusters correspond to the formula CeO(CeO2)n(+). The cluster cations are mass selected and photodissociated with a Nd:YAG laser at either 532 or 355 nm. The prominent clusters dissociate to produce smaller species also having a similar CeO(CeO2)n(+) formula, always with apparent leaving groups of (CeO2). The production of CeO(CeO2)n(+) from the dissociation of many cluster sizes establishes the relative stability of these clusters. Furthermore, the consistent loss of neutral CeO2 shows that the smallest neutral clusters adopt the same oxidation state (IV) as the most common form of bulk cerium oxide. Clusters with higher oxygen content than the CeO(CeO2)n(+) masses are present with much lower abundance. These species dissociate by the loss of O2, leaving surviving clusters with the CeO(CeO2)n(+) formula. Density functional theory calculations on these clusters suggest structures composed of stable CeO(CeO2)n(+) cores with excess oxygen bound to the surface as a superoxide unit (O2(-)).

  12. Antibacterial Activity of Geminized Amphiphilic Cationic Homopolymers. (United States)

    Wang, Hui; Shi, Xuefeng; Yu, Danfeng; Zhang, Jian; Yang, Guang; Cui, Yingxian; Sun, Keji; Wang, Jinben; Yan, Haike


    The current study is aimed at investigating the effect of cationic charge density and hydrophobicity on the antibacterial and hemolytic activities. Two kinds of cationic surfmers, containing single or double hydrophobic tails (octyl chains or benzyl groups), and the corresponding homopolymers were synthesized. The antimicrobial activity of these candidate antibacterials was studied by microbial growth inhibition assays against Escherichia coli, and hemolysis activity was carried out using human red blood cells. It was interestingly found that the homopolymers were much more effective in antibacterial property than their corresponding monomers. Furthermore, the geminized homopolymers had significantly higher antibacterial activity than that of their counterparts but with single amphiphilic side chains in each repeated unit. Geminized homopolymers, with high positive charge density and moderate hydrophobicity (such as benzyl groups), combine both advantages of efficient antibacterial property and prominently high selectivity. To further explain the antibacterial performance of the novel polymer series, the molecular interaction mechanism is proposed according to experimental data which shows that these specimens are likely to kill microbes by disrupting bacterial membranes, leading them unlikely to induce resistance.

  13. Transition-Metal Hydride Radical Cations. (United States)

    Hu, Yue; Shaw, Anthony P; Estes, Deven P; Norton, Jack R


    Transition-metal hydride radical cations (TMHRCs) are involved in a variety of chemical and biochemical reactions, making a more thorough understanding of their properties essential for explaining observed reactivity and for the eventual development of new applications. Generally, these species may be treated as the ones formed by one-electron oxidation of diamagnetic analogues that are neutral or cationic. Despite the importance of TMHRCs, the generally sensitive nature of these complexes has hindered their development. However, over the last four decades, many more TMHRCs have been synthesized, characterized, isolated, or hypothesized as reaction intermediates. This comprehensive review focuses on experimental studies of TMHRCs reported through the year 2014, with an emphasis on isolated and observed species. The methods used for the generation or synthesis of TMHRCs are surveyed, followed by a discussion about the stability of these complexes. The fundamental properties of TMHRCs, especially those pertaining to the M-H bond, are described, followed by a detailed treatment of decomposition pathways. Finally, reactions involving TMHRCs as intermediates are described.

  14. Cationic Antimicrobial Polymers and Their Assemblies

    Directory of Open Access Journals (Sweden)

    Ana Maria Carmona-Ribeiro


    Full Text Available Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs. The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

  15. [Potential-dependent Cation Selective Ion Channels Formed by Peroxiredoxin 6 in the Lipid Bilayer]. (United States)

    Grigoriev, P A; Sharapov, M G; Novoselov, V I


    The antioxidant enzyme peroxiredoxin 6 forms cation selective ion cluster-type channels in the lipid bilayer. Channel clustering as oligomeric structure consists of three or more subunits--channels with conductance of about 350 pS in the 200 mM KCl. Mean dwell time of the channel's open states decreases with increasing membrane voltage. A possible molecular mechanism of the observed potential-dependent inactivation of the channel cluster is discussed.

  16. Cation hydration in hydrogelic polyacrylamide-phosphoric acid network: A study by Raman spectroscopy


    Costa, A. M. Amorim da; Amado, A. M.


    The effects upon the structure and morphology of adding lithium, calcium and magnesium chlorides to a phosphoric acid/polyacrylamide 2:1 molar ratio proton conducting hydrogel are examined by observing the changes in the vibrational features of the polyacrylamide chain, in the phosphate group and in the interstitial water molecules as a function of the concentration and the cationic nature of the additive, at 295 K. On adding H3PO4 to the polyacrylamide hydrogel matrix, the amide groups becom...

  17. Nature as a source of inspiration for cationic lipid synthesis. (United States)

    Labas, Romain; Beilvert, Fanny; Barteau, Benoit; David, Stéphanie; Chèvre, Raphaël; Pitard, Bruno


    Synthetic gene delivery systems represent an attractive alternative to viral vectors for DNA transfection. Cationic lipids are one of the most widely used non-viral vectors for the delivery of DNA into cultured cells and are easily synthesized, leading to a large variety of well-characterized molecules. This review discusses strategies for the design of efficient cationic lipids that overcome the critical barriers of in vitro transfection. A particular focus is placed on natural hydrophilic headgroups and lipophilic tails that have been used to synthesize biocompatible and non-toxic cationic lipids. We also present chemical features that have been investigated to enhance the transfection efficiency of cationic lipids by promoting the escape of lipoplexes from the endosomal compartment and DNA release from DNA-liposome complexes. Transfection efficiency studies using these strategies are likely to improve the understanding of the mechanism of cationic lipid-mediated gene delivery and to help the rational design of novel cationic lipids.

  18. Divalent Beta’ Aluminas: High Conductivity Solid Electrolytes for Divalent Cations. (United States)


    Seith, Z. Phys., 57, 869 (1929) 45. G. Schwab and G. Eulitz, Z. physik. Chem., 55, 179 (1967) 6. N. Toropov, C.R. Acad. Sci. URSS , I, 147 (1935) 7. K...G. Gottfried, and J. West, Z.Kristallogr., 77, 255 (1931) 10. N.A. Toropov and N.M. Stukalova, C.R. (Dok.) Acad. Sci. URSS , 24, 459 (1939) 11. N.A...Toropov and M.M. Stukalova, C.R. (Dok.) Acad. Sci. URSS , 9 27, 974 (1940) 12. D.B. McWhan, P.D. Dernier. C. Vettier, A.S. Cooper, and’J.P. Remeika, Phys

  19. Cation immobilization in pyrolyzed simulated spent ion exchange resins

    Energy Technology Data Exchange (ETDEWEB)

    Luca, Vittorio, E-mail: [Programa Nacional de Gestion de Residuos Radiactivos, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica, Av. General, Paz 1499, 1650 San Martin, Provincia de Buenos Aires (Argentina); Bianchi, Hugo L. [Gerencia de Quimica, Centro Atomico Constituyentes, Comision Nacional de Energia Atomica, Av. General, Paz 1499, 1650 San Martin, Provincia de Buenos Aires (Argentina); ECyT, Universidad Nacional de General San Martin, Campus Miguelete, Ed. Tornavias, Martin de Irigoyen 3100, 1650 San Martin (Argentina); Conicet, Av. Rivadavia 1917, 1033 Buenos Aires (Argentina); Manzini, Alberto C. [Programa Nacional de Gestion de Residuos Radiactivos, Comision Nacional de Energia Atomica, Av. Del Libertador 8250, CP 1429, Ciudad Autonoma de Buenos Aires (Argentina)


    Significant quantities of spent ion exchange resins that are contaminated by an assortment of radioactive elements are produced by the nuclear industry each year. The baseline technology for the conditioning of these spent resins is encapsulation in ordinary Portland cement which has various shortcomings none the least of which is the relatively low loading of resin in the cement and the poor immobilization of highly mobile elements such as cesium. The present study was conducted with cationic resin samples (Lewatit S100) loaded with Cs{sup +}, Sr{sup 2+}, Co{sup 2+}, Ni{sup 2+} in roughly equimolar proportions at levels at or below 30% of the total cation exchange capacity. Low temperature thermal treatment of the resins was conducted in inert (Ar), or reducing (CH{sub 4}) gas atmospheres, or supercritical ethanol to convert the hydrated polymeric resin beads into carbonaceous materials that contained no water. This pyrolytic treatment resulted in at least a 50% volume reduction to give mechanically robust spherical materials. Scanning electron microscope investigations of cross-sections of the beads combined with energy dispersive analysis showed that initially all elements were uniformly distributed through the resin matrix but that at higher temperatures the distribution of Cs became inhomogeneous. Although Cs was found in the entire cross-section, a significant proportion of the Cs occurred within internal rings while a proportion migrated toward the outer surfaces to form a crustal deposit. Leaching experiments conducted in water at 25 Degree-Sign C showed that the divalent contaminant elements were very difficult to leach from the beads heated in inert atmospheres in the range 200-600 Degree-Sign C. Cumulative fractional loses of the order of 0.001 were observed for these divalent elements for temperatures below 500 Degree-Sign C. Regardless of the processing temperature, the cumulative fractional loss of Cs in water at 25 Degree-Sign C reached a plateau or

  20. Photocatalytic Activity in Phenol Removal of Water from Graphite and Graphene Oxides: Effect of Degassing and Chemical Oxidation in the Synthesis Process

    Directory of Open Access Journals (Sweden)

    Karina Bustos-Ramirez


    Full Text Available Developing new materials or modifying the existing ones is an amply field studied in the world of research. Due to its outstanding physical and chemical properties, graphene is attractive material for new applications. The methodologies for obtaining graphene are diverse and have changed over time. Graphene oxide is a versatile form of graphene, due to the presence of oxygenated functional groups. Chemical oxidation of graphite and exfoliation by ultrasonic waves is one of the preferred methods to obtain graphene oxide; chemical oxidation time and the degassing effect in the ultrasonic bath are parameters that play an important role in the features and properties of graphene oxide. Thus, in this study, the conventional times used for the oxidation of graphite and degassing in an ultrasonic bath to obtain graphene oxide were modified. The structural changes in the carbon materials were evaluated based on their photocatalytic activity in the removal of an organic pollutant in water (removing up to 38% of phenol. The band gaps of the graphitic materials were obtained by UV-vis obtaining a value range of 1.5–4.7 eV and the structure and morphology of the carbon materials were characterized by infrared and Raman spectroscopies and transmission electron microscopy, respectively.

  1. Prodigious emission rates and magma degassing budget of major, trace and radioactive volatile species from Ambrym basaltic volcano, Vanuatu island Arc (United States)

    Allard, P.; Aiuppa, A.; Bani, P.; Métrich, N.; Bertagnini, A.; Gauthier, P.-J.; Shinohara, H.; Sawyer, G.; Parello, F.; Bagnato, E.; Pelletier, B.; Garaebiti, E.


    Ambrym volcano, in the Vanuatu arc, is one of the most active volcanoes of the Southwest Pacific region, where persistent lava lake and/or Strombolian activity sustains voluminous gas plume emissions. Here we report on the first comprehensive budget for the discharge of major, minor, trace and radioactive volatile species from Ambrym volcano, as well as the first data for volatiles dissolved in its basaltic magma (olivine-hosted melt inclusions). In situ MultiGAS analysis of H2O, CO2, SO2 and H2S in crater rim emissions, coupled with filter-pack determination of SO2, halogens, stable and radioactive metals demonstrates a common magmatic source for volcanic gases emitted by its two main active craters, Benbow and Marum. These share a high water content ( 93 mol%), similar S/Cl, Cl/F, Br/Cl molar ratios, similar (210Po/210Pb) and (210Bi/210Pb) activity ratios, as well as comparable proportions in most trace metals. Their difference in CO2/SO2 ratio (1.0 and 5.6-3.0, respectively) is attributed to deeper gas-melt separation at Marum (Strombolian explosions) than Benbow (lava lake degassing) during our measurements in 2007. Airborne UV sensing of the SO2 plume flux (90 kg s- 1 or 7800 tons d- 1) demonstrates a prevalent degassing contribution ( 65%) of Benbow crater in that period and allows us to quantify the total volatile fluxes during medium-level eruptive activity of the volcano. Results reveal that Ambrym ranks among the most powerful volcanic gas emitters on Earth, producing between 5% and 9% of current estimates for global subaerial volcanic emissions of H2O, CO2, HCl, Cu, Cr, Cd, Au, Cs and Tl, between 10% and 17% of SO2, HF, HBr, Hg, 210Po and 210Pb, and over 30% of Ag, Se and Sn. Global flux estimates thus need to integrate its contribution and be revised accordingly. Prodigious gas emission from Ambrym does not result from an anomalous volatile enrichment nor a differential excess degassing of its feeding basalt: this latter contains relatively modest

  2. Cation-π interaction of the univalent silver cation with meso-octamethylcalix[4]pyrrole: Experimental and theoretical study (United States)

    Polášek, Miroslav; Kvíčala, Jaroslav; Makrlík, Emanuel; Křížová, Věra; Vaňura, Petr


    By using electrospray ionization mass spectrometry (ESI-MS), it was proven experimentally that the univalent silver cation Ag+ forms with meso-octamethylcalix[4]pyrrole (abbrev. 1) the cationic complex species 1·Ag+. Further, applying quantum chemical DFT calculations, four different conformations of the resulting complex 1·Ag+ were derived. It means that under the present experimental conditions, this ligand 1 can be considered as a macrocyclic receptor for the silver cation.

  3. The effects of cationic contamination on the physio-chemical properties of perfluoroionomer membranes (United States)

    Molter, Trent M.

    Proton Exchange Membrane (PEM) technology cannot meet fuel cell and electrolyzer durability standards for stationary and transportation applications. Cell designs are not of sufficient maturity to demonstrate more than several thousand hours of invariant performance. One of the limiting factors is the operational lifetime of membrane electrode assemblies (MEA's) because of pin-holing, dry-out, mechanical breeches, chemical attack and contamination. This program investigated the role of contamination on the degradation of perfluorinated membranes in fuel cell and electrolysis environments. Tests were conducted to develop an understanding of the effects of cationic contaminants on fundamental design parameters for these membranes including water content, ion exchange capacity, gas diffusion, ionic conductivity, and mechanical properties. Tests showed that cations rapidly transport into the membrane and disperse throughout its structure achieving high equilibrium concentrations. Ion charge density appears to govern membrane water content with small ions demonstrating the highest water content. Permeability studies showed transport in accordance with Fick's law in the following order: H2>O2>N 2>H2O. Cations negatively affect gas and water transport, with charge density affecting transport rates. Unique diffusion coefficients were calculated for each contaminating species suggesting that the contaminant is an integral participant in the transport process. AC resistance measurements showed that size of the ion charge carrier is an important factor in the conduction mechanism and that membrane area specific resistance correlates well with water content. Increases in membrane yield strength and the modulus of elasticity were demonstrated with increased contamination. Tensile tests showed that cation size plays an important role in determining the magnitude of this increase, indicating that larger ions interfere more with strain than smaller ones. Contaminants reduced

  4. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    DEFF Research Database (Denmark)

    Ellegaard, Anne-Marie; Dehlendorff, Christian; Vind, Anna C.


    Non-small cell lung cancer (NSCLC) is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD) library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We...... then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients...... with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any...

  5. Electron spectra of radical cations of heteroanalogs

    Energy Technology Data Exchange (ETDEWEB)

    Petrushenko, K.B.; Turchaninov, V.K.; Vokin, A.I.; Ermikov, A.F.; Frolov, Yu.L.


    Radical cation spectra of indazole and benzothiophene in the visible region were obtained by laser photolysis during the reaction of photoexcited quinones with these compounds in acetonitrile. The charge transfer bands of the complexes of the test compounds with p-chloranil and 7,7,8,8-tetracyanoquinodimethane in dioxane were recorded on a Specord M-40. Photoelectron spectra were obtained on a ES-3201 electron spectrometer. The He(I) resonance band (21.21 eV) was used for excitation. Measurements were carried out in the 60-120/sup 0/C range. The energy scale was calibrated form the first ionization potentials of Ar (15.76 eV) and chlorobenzene (9.06 eV). The error in the determination of the ionization potentials for the first four photoelectron bands was 0.05 eV.

  6. Structural and cytotoxic studies of cationic thiosemicarbazones (United States)

    Sinniah, Saravana Kumar; Sim, Kae Shin; Ng, Seik Weng; Tan, Kong Wai


    Schiff bases from the thiosemicarbazones family with variable N4 substituents are known to show enhanced growth inhibitory properties. In view of these facts and as a part of our continuous interest in cationic Schiff bases, we have developed several Schiff base ligands from (3-formyl-4-hydroxyphenyl)methyltriphenylphosphonium (T) in present study. The compounds were characterized by various spectroscopic methods (infrared spectra, 1H NMR, 13C NMR, HRESIMS and X-ray crystallography). Three of the N4 substituents, namely P(tsc)T, FP(tsc)T and EP(tsc)T exerted strong growth inhibitory properties by inhibiting the highly metastasis prostate cancer growth (PC-3). The thiosemicarbazone with ethylphenyl (EP) moiety displayed most potent activity against all cell lines tested. The MTT data obtained from analysis establishes that phenyl substituent enhances the growth inhibitory properties of the compound. The result affirms that EP(tsc)T would serve as a lead scaffold for rational anticancer agent development.

  7. Heart imaging with cationic complexes of technetium

    Energy Technology Data Exchange (ETDEWEB)

    Deutsch, E. (Univ. of Cincinnati, Cincinnati, OH); Bushong, W.; Glavan, K.A.; Elder, R.C.; Sodd, V.J.; Scholz, K.L.; Fortman, D.L.; Lukes, S.J.


    The cationic technetium-99 complex trans-(/sup 99/Tc(dmpe)/sub 2/Cl/sub 2/)/sup +/, where dmpe is bis(1,2-dimethylphosphino)ethane or (CH/sub 3/)/sub 2/P-CH/sub 2/CH/sub 2/-P(CH/sub 3/)/sub 2/, has been prepared and characterized by single-crystal, x-ray structural analysis. The technetium-99m analog, trans-(/sup 99m/Tc (dmpe)/sub 2/Cl/sub 2/)/sup +/, has also been prepared and shown to yield excellent gamma-ray images of the heart. The purposeful design, characterization, and synthesis of this technetium-99m radiopharmaceutical represents a striking application of fundamental inorganic chemistry to a problem in applied nuclear medicine.

  8. Retention of Cationic Starch onto Cellulose Fibres (United States)

    Missaoui, Mohamed; Mauret, Evelyne; Belgacem, Mohamed Naceur


    Three methods of cationic starch titration were used to quantify its retention on cellulose fibres, namely: (i) the complexation of CS with iodine and measurement of the absorbency of the ensuing blue solution by UV-vis spectroscopy; (ii) hydrolysis of the starch macromolecules followed by the conversion of the resulting sugars to furan-based molecules and quantifying the ensuing mixture by measuring their absorbance at a Ι of 490 nm, using the same technique as previous one and; finally (iii) hydrolysis of starch macromolecules by trifluoro-acetic acid and quantification of the sugars in the resulting hydrolysates by high performance liquid chromatography. The three methods were found to give similar results within the range of CS addition from 0 to 50 mg per g of cellulose fibres.

  9. Capturing dynamic cation hopping in cubic pyrochlores (United States)

    Brooks Hinojosa, Beverly; Asthagiri, Aravind; Nino, Juan C.


    In direct contrast to recent reports, density functional theory predicts that the most stable structure of Bi2Ti2O7 pyrochlore is a cubic Fd3¯m space group by accounting for atomic displacements. The displaced Bi occupies the 96g(x,x,z) Wyckoff position with six equivalent sites, which create multiple local minima. Using nudged elastic band method, the transition states of Bi cation hopping between equivalent minima were investigated and an energy barrier between 0.11 and 0.21 eV was determined. Energy barriers associated with the motion of Bi between equivalent sites within the 96g Wyckoff position suggest the presence of dielectric relaxation in Bi2Ti2O7.

  10. Hydration Structure of the Quaternary Ammonium Cations

    KAUST Repository

    Babiaczyk, Wojtek Iwo


    Two indicators of the hydropathicity of small solutes are introduced and tested by molecular dynamics simulations. These indicators are defined as probabilities of the orientation of water molecules\\' dipoles and hydrogen bond vectors, conditional on a generalized distance from the solute suitable for arbitrarily shaped molecules. Using conditional probabilities, it is possible to distinguish features of the distributions in close proximity of the solute. These regions contain the most significant information on the hydration structure but cannot be adequately represented by using, as is usually done, joint distance-angle probability densities. Our calculations show that using our indicators a relative hydropathicity scale for the interesting test set of the quaternary ammonium cations can be roughly determined. © 2010 American Chemical Society.

  11. Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule. (United States)

    Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A


    With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (Kd). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (Kd) decreasing as follows: Kd(Na(+)) > Kd(NH4(+)) ≥ Kd(K(+)) > Kd(Ca(2+)) ≥ Kd(Mg(2+)) > Kd(Al(3+)). This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium Kd values, allowed for

  12. Structure and physical properties of ternary organic conductors of TCNQ, iodine, and double-charged unsymmetrical cations: PET and PESe

    Energy Technology Data Exchange (ETDEWEB)

    Abashev, G.G. [Perm State Univ. (Russian Federation). Inst. of Natural Sci.; Russkikh, V.S. [Perm State Univ. (Russian Federation). Inst. of Natural Sci.; Koshta, A. [Polska Akademia Nauk, Poznan (Poland). Inst. Fizyki Molekularnej; Lapinski, A. [Polska Akademia Nauk, Poznan (Poland). Inst. Fizyki Molekularnej; Krol, S. [Polska Akademia Nauk, Poznan (Poland). Inst. Fizyki Molekularnej; Pukacki, W. [Polska Akademia Nauk, Poznan (Poland). Inst. Fizyki Molekularnej; Graja, A. [Polska Akademia Nauk, Poznan (Poland). Inst. Fizyki Molekularnej


    Ternary organic salts of TCNQ, iodine, and double-charged unsymmetrical cations containing sulfur or selenium are investigated. The crystal structure of the salts is determined; their dc electrical conductivity, ESR, and IR spectral properties are studied. The physical properties of the investigated salts are found as typical for Q-1D organic semiconductors. (orig.)

  13. Chemically modified polymeric resins for separation of cations, organic acids, and small polar moleculea by high performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Morris, John B. [Iowa State Univ., Ames, IA (United States)


    This thesis is divided into 4 parts: a review, ion chromatography of metal cations on carboxylic resins, separation of hydrophilic organic acids and small polar compounds on macroporous resin columns, and use of eluent modifiers for liquid chromatographic separation of carboxylic acids using conductivity detection.

  14. Antiviral effect of cationic compounds on bacteriophages

    Directory of Open Access Journals (Sweden)

    Mai Huong eChatain-Ly


    Full Text Available The antiviral activity of several cationic compounds - cetytrimethylammonium (CTAB, chitosan, nisin and lysozyme - was investigated on the bacteriophage c2 (DNA head and non-contractile tail infecting Lactococcus strains and the bacteriophage MS2 (F-specific RNA infecting E.coli. Firstly, these activities were evaluated in a phosphate buffer pH 7- 10 mM. The CTAB had a virucidal effect on the Lactococcus bacteriophages, but not on the MS2. After 1 min of contact with 0.125 mM CTAB, the c2 population was reduced from 6 log(pfu/mL to 1,5 log(pfu/mL and completely deactivated at 1 mM. On the contrary, chitosan inhibited the MS2 more than it did the bacteriophages c2. No antiviral effect was observed for the nisin or the lysozyme on bacteriophages after 1 min of treatment. A 1 and 2.5 log reduction was respectively observed for nisin and lysozyme when the treatment time increased (5 or 10 min. These results showed that the antiviral effect depended both on the virus and structure of the antimicrobial compounds. The antiviral activity of these compounds was also evaluated in different physico-chemical conditions and in complex matrices. The antiviral activity of CTAB was impaired in acid pH and with an increase of the ionic strength. These results might be explained by the electrostatic interactions between cationic compounds and negatively charged particles such as bacteriophages or other compounds in a matrix. Milk proved to be protective suggesting the components of food could interfere with antimicrobial compounds.

  15. Broadband seismic measurements of degassing activity associated with lava effusion at Popocatépetl Volcano, Mexico (United States)

    Arciniega-Ceballos, Alejandra; Chouet, Bernard A.; Dawson, Phillip; Asch, Guenter


    From November 1999 through July 2000, a broadband seismic experiment was carried out at Popocatépetl Volcano to record seismic activity over a wide period range (0.04–100 s). We present an overview of the seismicity recorded during this experiment and discuss results of analyses of long-period (LP) and very-long-period (VLP) seismic signals recorded at stations nearest to the crater over a four-month interval December 1999–March 2000. Three families of LP signals (Types-I, II, and III) are identified based on distinctive waveform features observed periods shorter than 1 s, periods longer than 15 s, and within the period range 0.5–2.5 s. Type-I LP events have impulsive first arrivals and exhibit a characteristic harmonic wave train with dominant periods in the 1.4–1.9 s range during the first 10 s of signal. These events are also associated with a remarkable VLP wavelet with period near 30 s. Type-II LP events represent pairs of events occurring in rapid succession and whose signatures are superimposed. These are typically marked by slowly emergent first arrivals and by a characteristic VLP wave train with dominant period near 30 s, made of two successive wavelets whose shapes are quasi-identical to those of the VLP wavelets associated with Type-I events. Type-III LP events represent the most energetic signals observed during our experiment. These have an emergent first arrival and display a harmonic signature with dominant period near 1.1 s. They are dominated by periods in the 0.25–0.35 s band and contain no significant energy at periods longer than 15 s. Hypocentral locations of the three types of LP events obtained from phase picks point to shallow seismic sources clustered at depths shallower than 2 km below the crater floor. Observed variations in volcanic eruptive activity correlate with defined LP families. Most of the observed seismicity consists of Type-I events that occur in association with 1–3-min-long degassing bursts (

  16. Role of extracellular cations in cell motility, polarity, and chemotaxis

    Directory of Open Access Journals (Sweden)

    Soll D


    Full Text Available David R Soll1, Deborah Wessels1, Daniel F Lusche1, Spencer Kuhl1, Amanda Scherer1, Shawna Grimm1,21Monoclonal Antibody Research Institute, Developmental Studies, Hybridoma Bank, Department of Biology, University of Iowa, Iowa City; 2Mercy Medical Center, Surgical Residency Program, Des Moines, Iowa, USAAbstract: The concentration of cations in the aqueous environment of free living organisms and cells within the human body influence motility, shape, and chemotaxis. The role of extracellular cations is usually perceived to be the source for intracellular cations in the process of homeostasis. The role of surface molecules that interact with extracellular cations is believed to be that of channels, transporters, and exchangers. However, the role of Ca2+ as a signal and chemoattractant and the discovery of the Ca2+ receptor have demonstrated that extracellular cations can function as signals at the cell surface, and the plasma membrane molecules they interact with can function as bona fide receptors that activate coupled signal transduction pathways, associated molecules in the plasma membrane, or the cytoskeleton. With this perspective in mind, we have reviewed the cationic composition of aqueous environments of free living cells and cells that move in multicellular organisms, most notably humans, the range of molecules interacting with cations at the cell surface, the concept of a cell surface cation receptor, and the roles extracellular cations and plasma membrane proteins that interact with them play in the regulation of motility, shape, and chemotaxis. Hopefully, the perspective of this review will increase awareness of the roles extracellular cations play and the possibility that many of the plasma membrane proteins that interact with them could also play roles as receptors.Keywords: extracellular cations, chemotaxis, transporters, calcium, receptors

  17. The Effect of Hydration on the Cation-π Interaction Between Benzene and Various Cations

    Indian Academy of Sciences (India)



    The effect of hydration on cation-π interaction in Mq+ BmWn (B = benzene; W = water; Mq+ =Na⁺, K⁺, Mg²⁺, Ca²⁺, Al³⁺, 0 ≤ n,m ≤ 4, 1≤ m + n ≤ 4) complexes has been investigated using ab initio quantum chemical methods. Interaction energy values computed at the MP2 level of theory using the 6-31G(d,p) basis set reveal a qualitative trend in the relative affinity of different cations for benzene and water in these complexes. The π–cloud thickness values for benzene have also been estimated for these systems.


    Directory of Open Access Journals (Sweden)



    Full Text Available This study aimed to evaluate the production of castor beans, cv. „BRS Energia‟, in terms of soil chemical composition as a function of the cationic nature, and salinity levels, of the irrigation water. The experiment was carried out using lysimeters in a controlled environment at the Center of Technology and Natural Resources of the Federal University of Campina Grande, from November 2013 to February 2014. The treatments consisted of six types of salinity (S 1 - Control; S 2 - Na + ; S 3 - Ca 2+ ; S 4 - Na + + Ca 2+ ; S 5 - K + , and S 6 - Na + + Ca 2+ + Mg 2+ , distributed in randomized blocks with four replicates; each plot consisted of five plants for evaluation, totaling 120 experimental plots. Plants in the control treatment (S 1 were irrigated with water with an electrical conductivity (ECw of 0.6 dS m - 1 , and the other treatments (S 2 ; S 3 ; S 4 ; S 5 and S 6 with ECw of 4.5 dS m - 1 , but with (a different cation(s. Water salinity of 4.5 dS m - 1 hampers castor bean production, regardless of the cationic nature of the water; castor bean „BRS Energia‟ was more sensitive to salinity caused by the presence of potassium salts in the irrigation water; the mass of seeds in the primary raceme is the most sensitive variable to salinity and the cationic nature of the irrigation water; the adopted leaching fraction (0.10 was not sufficient to avoid salt accumulation in the soil; irrigation with low ECw promoted the lowest value of exchangeable sodium percentage.

  19. Evaluating Design Parameters for Breakthrough Curve Analysis and Kinetics of Fixed Bed Columns for Cu(II) Cations Using Lignocellulosic Wastes


    Zaira Zaman Chowdhury; Sharifah Bee Abd Hamid; Sharifuddin Mohd Zain


    A continuous adsorption study for removal of Cu(II) cations from wastewater using a fixed-bed column was conducted. A granular carbonaceous activated adsorbent produced by carbonization of the outer rind, or exocarp, of mangostene fruit shell was used for column packing. The effects of feed flow rate, influent cation concentration, and bed depth on the breakthrough curve were investigated at pH 5.5. Experimental analysis confirmed that the breakthrough curves were dependent on flow rate, init...

  20. Cation and anion dependence of stable geometries and stabilization energies of alkali metal cation complexes with FSA(-), FTA(-), and TFSA(-) anions: relationship with physicochemical properties of molten salts. (United States)

    Tsuzuki, Seiji; Kubota, Keigo; Matsumoto, Hajime


    Stable geometries and stabilization energies (Eform) of the alkali metal complexes with bis(fluorosulfonyl)amide, (fluorosulfonyl)(trifluoromethylslufonyl)amide and bis(trifluoromethylsulfonyl)amide (FSA(-), FTA(-) and TFSA(-)) were studied by ab initio molecular orbital calculations. The FSA(-) complexes prefer the bidentate structures in which two oxygen atoms of two SO2 groups have contact with the metal cation. The FTA(-) and TFSA(-) complexes with Li(+) and Na(+) prefer the bidentate structures, while the FTA(-) and TFSA(-) complexes with Cs(+) prefer tridentate structures in which the metal cation has contact with two oxygen atoms of an SO2 group and one oxygen atom of another SO2 group. The two structures are nearly isoenergetic in the FTA(-) and TFSA(-) complexes with K(+) and Rb(+). The magnitude of Eform depends on the alkali metal cation significantly. The Eform calculated for the most stable TFSA(-) complexes with Li(+), Na(+), K(+), Rb(+) and Cs(+) cations at the MP2/6-311G** level are -137.2, -110.5, -101.1, -89.6, and -84.1 kcal/mol, respectively. The viscosity and ionic conductivity of the alkali TFSA molten salts have strong correlation with the magnitude of the attraction. The viscosity increases and the ionic conductivity decreases with the increase of the attraction. The melting points of the alkali TFSA and alkali BETA molten salts also have correlation with the magnitude of the Eform, which strongly suggests that the magnitude of the attraction play important roles in determining the melting points of these molten salts. The anion dependence of the Eform calculated for the complexes is small (less than 2.9 kcal/mol). This shows that the magnitude of the attraction is not the cause of the low melting points of alkali FTA molten salts compared with those of corresponding alkali TFSA molten salts. The electrostatic interactions are the major source of the attraction in the complexes. The electrostatic energies for the most stable TFSA

  1. Determination of effective capacities of ion-exchangeable materials by measuring the equilibrium conductivity. (United States)

    Okabe, Toshiaki; Yokoyama, Yukio


    The effective ion-exchange capacities of ion-exchange materials were determined by measuring the change in the equilibrium conductivity of a column packed with analyte. The developed instrumental method can provide effective ion-exchange capacities for both cation and anion exchangers with simple operations. The cation-exchange capacity of a weak-acid cation-exchange resin (TSKgel SuperIC-Cation column) depended on the conditioning pH and the molar concentration of the conditioning agent. Plots of effective cation-exchange capacities over the conditioning pH exhibited three inflection points, suggesting the presence of two carboxy groups and one phenolic OH group in the resin, probably due to the inherent base polymer. This method was applied to several commercial analytical columns for ion chromatography, and could provide scientifically useful results for characterizing the resin properties.

  2. Cation-π Interaction between the Aromatic Organic Counterion and DTAB Micelle in Mixed Solvents

    Institute of Scientific and Technical Information of China (English)

    DENG,Dong-Shun(邓东顺); LI,Hao-Ran(李浩然); LIU,Di-Xia(刘迪霞); HAN,Shi-Jun(韩世钧)


    The cation-π interaction between the aromatic organic counterion potassium hydrogen phthalate (KHP) and DTAB micelle in aqueous mixture of EG was investigated, using the techniques of conductivity measurements, UV absorption spectrum and NMR spectrum. The conductivity and UV spectrum studies were with respect to the effect of KHP on DTAB and that of DTAB micelle on KHP, respectively. According to the chemical shift changes of the aromatic ring and the surfactant methylene protons, it can be assumed that KHP penetrated into DTAB micelle with its carboxylic group protruding out of the micellar surface. And the strength of the interaction became weaker with the content of EG in the mixed solvent increasing.

  3. How mobile are sorbed cations in clays and clay rocks? (United States)

    Gimmi, T; Kosakowski, G


    Diffusion of cations and other contaminants through clays is of central interest, because clays and clay rocks are widely considered as barrier materials for waste disposal sites. An intriguing experimental observation has been made in this context: Often, the diffusive flux of cations at trace concentrations is much larger and the retardation smaller than expected based on their sorption coefficients. So-called surface diffusion of sorbed cations has been invoked to explain the observations but remains a controversial issue. Moreover, the corresponding surface diffusion coefficients are largely unknown. Here we show that, by an appropriate scaling, published diffusion data covering a broad range of cations, clays, and chemical conditions can all be modeled satisfactorily by a surface diffusion model. The average mobility of sorbed cations seems to be primarily an intrinsic property of each cation that follows inversely its sorption affinity. With these surface mobilities, cation diffusion coefficients can now be estimated from those of water tracers. In pure clays at low salinities, surface diffusion can reduce the cation retardation by a factor of more than 1000.

  4. In vivo toxicity of cationic micelles and liposomes

    DEFF Research Database (Denmark)

    Knudsen, Kristina Bram; Northeved, Helle; Ek, Pramod Kumar


    This study investigated toxicity of nanocarriers comprised of cationic polymer and lipid components often used in gene and drug delivery, formulated as cationic micelles and liposomes. Rats were injected intravenously with 10, 25 or 100 mg/kg and sacrificed after 24 or 48 h, or 24 h after the last...

  5. Fault Networks in the Northwestern Albuquerque Basin and Their Potential Role in Controlling Mantle CO2 Degassing and Fluid Migration from the Valles Caldera (United States)

    Smith, J. R.; Crossey, L. J.; Karlstrom, K. E.; Fischer, T. P.; Lee, H.; McGibbon, C. J.


    The Rio Grande rift (RGR) has Quaternary and active volcanism and faulting that provide a field laboratory for examining links between mantle degassing and faults as fluid conduits. Diffuse and spring CO2 flux measurements were taken at 6 sites in the northwestern Albuquerque Basin (NWAB) and Valles caldera geothermal system. All sites progress to the southwest from the 1.25 Ma Valles caldera, down the rift-related Jemez fault network, to intersect with the Nacimiento fault system. Mantle CO2 and He degassing are well documented at 5 of 6 sites, with decreasing 3He/4He ratios away from the caldera. The instrument used to measure CO2 flux was an EGM-4 CO2 gas analyzer (PP systems) with an accumulation chamber. Carbonic springs at Penasco Springs (PS) and San Ysidro (SY), and the carbonate-cemented Sand Hill Fault (SHF) were targeted, all near the western border of the RGR. The SHF has no spring activity, had the smallest maximum flux of all the sites (8 g/m2d), but carbonate along the fault zone (<2 m wide) attest to past CO2 flux. The other two sites are equal distance (30-40 km) between the SHF site and Valles caldera sites. These sites have active carbonic springs that precipitate travertine mounds. Our work suggests these sites reflect intersections of the Nacimiento fault with NE trending faults that connect to the Jemez fault network. The maximum diffuse flux recorded at SY (297 g/m2d) and PS (25 g/m2d) are high, especially along the fault and near springs. At SY and PS the instruments capacity was exceeded (2,400 g/m2d) at 6 of 9 springs. Interpretations indicate a direct CO2 flux through a fault-related artesian aquifer system that is connected to magmatic gases from the caldera. Maximum diffuse flux measurements of Alamo Canyon (20,906 g/m2d), Sulphur Springs (2,400 g/m2d) and Soda Dam (1,882 g/m2d) at Valles caldera geothermal sites are comparable to Yellowstone geothermal systems. We use geospatial analysis and local geologic mapping to examine

  6. The Relative Rates of Secondary Hydration in Basalt and Rhyolite, and the use of δD as a Paleoclimate Indicator: Implications for Paleoenvironmental and Volcanic Degassing Studies (United States)

    Seligman, A. N.; Bindeman, I. N.


    The δD-H2O correlation is important for volcanic degassing and secondary hydration trends. We utilize the caibration of the TC/EA - MAT 253 continuous flow system, which permits us to analyze wt.% H2O and its δD extracted from 1-8 mg of glass with as little as 0.1 wt% H2O. Tephra that has been secondarily hydrated with meteoric water is widely used as a paleoenvironmental tool, but the rate of secondary hydration, the relative amounts of primary magmatic (degassed) and secondary meteoric water, and the retention of primary and secondary δD values are not well understood. To quantify these processes, we use a natural experiment involving dated Holocene tepha in Kamchatka and Oregon. Our research illustrates the drastic difference in hydration rates between silicic (hydrated after ~1.5 ka) and mafic tephra, which is not hydrated in the Holocene (similar to results for submarine volcanic glasses), and andesitic tephra with intermediate degrees of hydration. The 0.05-7.3 ka basaltic scoria from Klyuchevskoy volcano retains ≤0.45 wt.% primary magmatic H2O, with δD values from -99 to -121 ‰. Four other 0.05-7.6 ka basaltic tephra units from Kamchatka with 65 wt.% have higher (1.5 -3.4) wt.% H2O and δD values between -115 - -160 ‰. We interpret the lower δD values and higher water contents (opposite of the magmatic degassing trend) to be a characteristic of secondary hydration in regions of higher latitude such as Kamchatka and Oregon. We are also investigating 7.7 ka Mt. Mazama tephra in Oregon that are known to be fully hydrated and cover nearly 5000 km2 northeast of Crater Lake and range in elevation from ~1.3-1.9 km to understand the δD and δ18O details of the hydrated water's correspondence with local Holocene meteoric waters. In the future, we plan to use a combination of δD in mid-high latitude precipitation to delineate δD-H2O hydration trends to better understand the distinction between primary magmatic and secondary meteoric water in volcanic

  7. Interaction between cationic and conventional nonionic surfactants in the mixed micelle and monolayer formed in aqueous medium

    Directory of Open Access Journals (Sweden)

    Nabel A. Negm


    Full Text Available Mixed micellization and surface properties of cationic and nonionic surfactants dimethyl decyl-, tetradecyl- and hexadecyl phosphineoxide mixtures are studied using conductivity and surface tension measurements. The models of Rubingh, Rosen, and Clint, are used to obtain the interaction parameter, minimum area per molecule, mixed micelle composition, free energies of mixing and activity coefficients. The micellar mole fractions were always higher than ideal values indicating high contributions of cationics in mixed micelles. Activity coefficients were less than unity indicating synergism in micelles. The negative free energies of mixing showed the stability of the surfactants in the mixed micelles.

  8. Interactions between cationic liposomes and drugs or biomolecules

    Directory of Open Access Journals (Sweden)



    Full Text Available Multiple uses for synthetic cationic liposomes composed of dioctadecyldimethylammonium bromide (DODAB bilayer vesicles are presented. Drugs or biomolecules can be solubilized or incorporated in the cationic bilayers. The cationic liposomes themselves can act as antimicrobial agents causing death of bacteria and fungi at concentrations that barely affect mammalian cells in culture. Silica particles or polystyrene microspheres can be functionalized by coverage with DODAB bilayers or phospholipid monolayers. Negatively charged antigenic proteins can be carried by the cationic liposomes which generate a remarkable immunoadjuvant action. Nucleotides or DNA can be physically adsorbed to the cationic liposomes to be transferred to mammalian cells for gene therapy. An overview of the interactions between DODAB vesicles and some biomolecules or drugs clearly points out their versatility for useful applications in a near future.

  9. Interactions between cationic liposomes and drugs or biomolecules. (United States)

    Carmona-Ribeiro, A M


    Multiple uses for synthetic cationic liposomes composed of dioctadecyldimethylammonium bromide (DODAB) bilayer vesicles are presented. Drugs or biomolecules can be solubilized or incorporated in the cationic bilayers. The cationic liposomes themselves can act as antimicrobial agents causing death of bacteria and fungi at concentrations that barely affect mammalian cells in culture. Silica particles or polystyrene microspheres can be functionalized by coverage with DODAB bilayers or phospholipid monolayers. Negatively charged antigenic proteins can be carried by the cationic liposomes which generate a remarkable immunoadjuvant action. Nucleotides or DNA can be physically adsorbed to the cationic liposomes to be transferred to mammalian cells for gene therapy. An overview of the interactions between DODAB vesicles and some biomolecules or drugs clearly points out their versatility for useful applications in a near future.

  10. Do Cation-π Interactions Exist in Bacteriorhodopsin

    Institute of Scientific and Technical Information of China (English)

    HU Kun-Sheng; WANG Guang-Yu; HE Jin-An


    Metal ions are essential to the structure and physiological functions of bacteriorhodopsin. Experimental evidence suggests the existence of specific cation binding to the negatively charged groups of Asp85 and Asp212 via an electrostatic interaction. However, only using electrostatic force is not enough to explain the role of the metal cations because the carboxylate of Asp85 is well known to be protonated in the M intermediate. Considering the presence of some aromatic amino acid residues in the vicinity of the retinal pocket, the existence of cation-π interactions between the metal cation and aromatic amino acid residues is suggested. Obviously, introduction of this kind of interaction is conducive to understanding the effects of the metal cations and aromatic amino acid residues inside the protein on the structural stability and proton pumping of bacteriorhodopsin.

  11. Kinetic Monte Carlo Simulation of Cation Diffusion in Low-K Ceramics (United States)

    Good, Brian


    Low thermal conductivity (low-K) ceramic materials are of interest to the aerospace community for use as the thermal barrier component of coating systems for turbine engine components. In particular, zirconia-based materials exhibit both low thermal conductivity and structural stability at high temperature, making them suitable for such applications. Because creep is one of the potential failure modes, and because diffusion is a mechanism by which creep takes place, we have performed computer simulations of cation diffusion in a variety of zirconia-based low-K materials. The kinetic Monte Carlo simulation method is an alternative to the more widely known molecular dynamics (MD) method. It is designed to study "infrequent-event" processes, such as diffusion, for which MD simulation can be highly inefficient. We describe the results of kinetic Monte Carlo computer simulations of cation diffusion in several zirconia-based materials, specifically, zirconia doped with Y, Gd, Nb and Yb. Diffusion paths are identified, and migration energy barriers are obtained from density functional calculations and from the literature. We present results on the temperature dependence of the diffusivity, and on the effects of the presence of oxygen vacancies in cation diffusion barrier complexes as well.

  12. Electronic structures of one-dimensional poly-fused selenophene radical cations: density functional theory study

    Directory of Open Access Journals (Sweden)

    Hiroshi Kawabata et al


    Full Text Available Hybrid density functional theory (DFT calculations have been carried out for neutral and radical cation species of a fused selenophene oligomer, denoted by Se(n, where n represents the number of selenophene rings in the oligomer, to elucidate the electronic structures at ground and low-lying excited states. A polymer of fused selenophene was also investigated using one-dimensional periodic boundary conditions (PBC for comparison. It was found that the reorganization energy of a radical cation of Se(n from a vertical hole trapping point to its relaxed structure is significantly small. Also, the reorganization energy decreased gradually with increasing n, indicating that Se(n has an effective intramolecular hole transport property. It was found that the radical cation species of Se(n has a low-energy band in the near-IR region, which is strongly correlated to hole conductivity. The relationship between the electronic states and intramolecular hole conductivity was discussed on the basis of theoretical calculations.


    Directory of Open Access Journals (Sweden)

    Marija Tomasic


    Full Text Available The study was conducted on 18 locations and 11 dominant soil types in the Republic of Croatia including their evolution-genetic horizons. In total, 51 soil samples were examined. Analysis of soil was done by saturating patterns using barium chloride solution in three replications. Descriptive statistics of the analyzed data was conducted. Basic statistical parameters were calculated, and functional dependence between the base saturation (V% of analyzed soil samples and their pH was observed. The correlation coefficient (r between base saturation (V% and pH for all examined soils was r=0.79 (n=51; very strong correlation. For acid soils it was r=0.82 (n=17; very strong correlation, for neutral soils r=0.75 (n=8; very strong correlation, and finally for alkaline soils r=0.15 (n=26; very weak correlation. Cation exchange capacity values ranged from 2.39 cmol+*kg-1 to 33.8 cmol+*kg-1 depending on soil type, pH, organic content and other soil parameters. The content of exchangeable cations in the sum of basic cations ranged from: Ca2+ (16% - 94%, Mg2+ (2% - 41%, K+ (1% - 68% and Na+ (<0.01% also depending on soil type, depth, location and other physical and chemical soil parameters.

  14. Mathematical modeling of fluid flow and thermal analysis in ladle of R H degasser process; Modelamento matematico do escoamento e analise termica na panela do processo de desgaseificacao a vacuo do tipo RH

    Energy Technology Data Exchange (ETDEWEB)

    Cerqueira, Osvane L.; Silva, Alexandre J. da; Costa e Silva, Andre L.V. da [Universidade Federal Fluminense (UFF), Volta Redonda, RJ (Brazil). Escola de Engenharia Industrial Metalurgica


    This work presents a numerical analysis of the fluid flow and thermal analysis in the ladle of R H vacuum degassing process. As a result of this analysis, a better understanding of the fluid flow patterns and of the turbulence regions inside the ladle. (author) 4 refs., 7 figs., 3 tabs.

  15. Low conductivity and sintering-resistant thermal barrier coatings (United States)

    Zhu, Dongming (Inventor); Miller, Robert A. (Inventor)


    A thermal barrier coating composition is provided. The composition has a base oxide, a primary stabilizer, and at least two additional cationic oxide dopants. Preferably, a pair of group A and group B defect cluster-promoting oxides is used in conjunction with the base and primary stabilizer oxides. The new thermal barrier coating is found to have significantly lower thermal conductivity and better sintering resistance. In preferred embodiments, the base oxide is selected from zirconia and hafnia. The group A and group B cluster-promoting oxide dopants preferably are selected such that the group A dopant has a smaller cationic radius than the primary stabilizer oxide, and so that the primary stabilizer oxide has a small cationic radius than that of the group B dopant.

  16. Radical cations from dipyridinium derivatives: a combined EPR and DFT study. (United States)

    Stipa, Pierluigi


    The monoelectronic reduction of 1,1'-dimethyl-2,2'-dicyano-4,4'-bipyridinium (DCMV++) bis-methylsulphate, conducted directly in the cavity of the electron paramagnetic resonance (EPR) spectrometer at room temperature and in DMSO solution, gave the signal of the corresponding radical cation (DCMV.+) whose interpretation has been carried out with the aid of density functional theory (DFT) calculations run at different levels. The model chemistries considered yielded in general hyperfine coupling constants (hfcc) in good agreement with the experimental ones, except for the methyl protons directly bonded to the pyridinium nitrogens. The use of various computational methods accounting for solvent-solute interactions did not give significant improvements with respect to the gas phase results, while the geometry optimizations performed showed that the two pyridinium rings are coplanar in the radical cation but staggered in the parent dication, although the corresponding energy barrier involved is very low.

  17. The Flocculating Cationic Polypetide from Moringa oleifera Seeds Damages Bacterial Cell Membranes by Causing Membrane Fusion. (United States)

    Shebek, Kevin; Schantz, Allen B; Sines, Ian; Lauser, Kathleen; Velegol, Stephanie; Kumar, Manish


    A cationic protein isolated from the seeds of the Moringa oleifera tree has been extensively studied for use in water treatment in developing countries and has been proposed for use in antimicrobial and therapeutic applications. However, the molecular basis for the antimicrobial action of this peptide, Moringa oleifera cationic protein (MOCP), has not been previously elucidated. We demonstrate here that a dominant mechanism of MOCP antimicrobial activity is membrane fusion. We used a combination of cryogenic electron microscopy (cryo-EM) and fluorescence assays to observe and study the kinetics of fusion of membranes in liposomes representing model microbial cells. We also conducted cryo-EM experiments on E. coli cells where MOCP was seen to fuse the inner and outer membranes. Coarse-grained molecular dynamics simulations of membrane vesicles with MOCP molecules were used to elucidate steps in peptide adsorption, stalk formation, and fusion between membranes.

  18. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. (United States)

    Lukatskaya, Maria R; Mashtalir, Olha; Ren, Chang E; Dall'Agnese, Yohan; Rozier, Patrick; Taberna, Pierre Louis; Naguib, Michael; Simon, Patrice; Barsoum, Michel W; Gogotsi, Yury


    The intercalation of ions into layered compounds has long been exploited in energy storage devices such as batteries and electrochemical capacitors. However, few host materials are known for ions much larger than lithium. We demonstrate the spontaneous intercalation of cations from aqueous salt solutions between two-dimensional (2D) Ti3C2 MXene layers. MXenes combine 2D conductive carbide layers with a hydrophilic, primarily hydroxyl-terminated surface. A variety of cations, including Na(+), K(+), NH4(+), Mg(2+), and Al(3+), can also be intercalated electrochemically, offering capacitance in excess of 300 farads per cubic centimeter (much higher than that of porous carbons). This study provides a basis for exploring a large family of 2D carbides and carbonitrides in electrochemical energy storage applications using single- and multivalent ions.

  19. Ionic conduction in the solid state

    Indian Academy of Sciences (India)

    P Padma Kumar; S Yashonath


    Solid state ionic conductors are important from an industrial viewpoint. A variety of such conductors have been found. In order to understand the reasons for high ionic conductivity in these solids, there have been a number of experimental, theoretical and computational studies in the literature. We provide here a survey of these investigations with focus on what is known and elaborate on issues that still remain unresolved. Conductivity depends on a number of factors such as presence of interstitial sites, ion size, temperature, crystal structure etc. We discuss the recent results from atomistic computer simulations on the dependence of conductivity in NASICONs as a function of composition, temperature, phase change and cation among others. A new potential for modelling of NASICON structure that has been proposed is also discussed.

  20. IRMPD Action Spectroscopy of Alkali Metal Cation-Cytosine Complexes: Effects of Alkali Metal Cation Size on Gas Phase Conformation

    NARCIS (Netherlands)

    Yang, B.; Wu, R.R.; Polfer, N.C.; Berden, G.; Oomens, J.; Rodgers, M.T.


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both simi

  1. Anaerobic toxicity of cationic silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Gitipour, Alireza; Thiel, Stephen W. [Biomedical, Chemical, and Environmental Engineering, University of Cincinnati, Cincinnati, OH (United States); Scheckel, Kirk G. [USEPA, Office of Research and Development, Cincinnati, OH (United States); Tolaymat, Thabet, E-mail: [USEPA, Office of Research and Development, Cincinnati, OH (United States)


    The microbial toxicity of silver nanoparticles (AgNPs) stabilized with different capping agents was compared to that of Ag{sup +} under anaerobic conditions. Three AgNPs were investigated: (1) negatively charged citrate-coated AgNPs (citrate-AgNPs), (2) minimally charged polyvinylpyrrolidone coated AgNPs (PVP-AgNPs) and (3) positively charged branched polyethyleneimine coated AgNPs (BPEI-AgNPs). The AgNPs investigated in this experiment were similar in size (10–15 nm), spherical in shape, but varied in surface charge which ranged from highly negative to highly positive. While, at AgNPs concentrations lower than 5 mg L{sup −1}, the anaerobic decomposition process was not influenced by the presence of the nanoparticles, there was an observed impact on the diversity of the microbial community. At elevated concentrations (100 mg L{sup −1} as silver), only the cationic BPEI-AgNPs demonstrated toxicity similar in magnitude to that of Ag{sup +}. Both citrate and PVP-AgNPs did not exhibit toxicity at the 100 mg L{sup −1} as measured by biogas evolution. These findings further indicate the varying modes of action for nanoparticle toxicity and represent one of the few studies that evaluate end-of-life management concerns with regards to the increasing use of nanomaterials in our everyday life. These findings also highlight some of the concerns with a one size fits all approach to the evaluation of environmental health and safety concerns associated with the use of nanoparticles. - Highlights: • At concentrations -1 the anaerobic decomposition process was not impacted. • An impact on the microbial community at concentrations -1 were observed. • At high concentrations (100 mg L{sup −1}), the cationic BPEI-AgNPs demonstrated toxicity. • Toxicity was demonstrated without the presence of oxidative dissolution of silver. • A one size fits all approach for the evaluation of NPs may not be accurate.

  2. Degassing vs. eruptive styles at Mt. Etna volcano (Sicily, Italy): Volatile stocking, gas fluxing, and the shift from low-energy to highly-explosive basaltic eruptions (United States)

    Moretti, Roberto; Métrich, Nicole; Di Renzo, Valeria; Aiuppa, Alessandro; Allard, Patrick; Arienzo, Ilenia


    Basaltic magmas can transport and release large amounts of volatiles into the atmosphere, especially in subduction zones, where slab-derived fluids enrich the mantle wedge. Depending on magma volatile content, basaltic volcanoes thus display a wide spectrum of eruptive styles, from common Strombolian-type activity to Plinian events. Mt. Etna in Sicily, is a typical basaltic volcano where the volatile control on such a variable activity can be investigated. Based on a melt inclusion study in products from Strombolian or lava-fountain activity to Plinian eruptions, here we show that for the same initial volatile content, different eruptive styles reflect variable degassing paths throughout the composite Etnean plumbing system. The combined influence of i) crystallization, ii) deep degassing and iii) CO2 gas fluxing can explain the evolution of H2O, CO2, S and Cl in products from such a spectrum of activity. Deep crystallization produces the CO2-rich gas fluxing the upward magma portions, which will become buoyant and easily mobilized in small gas-rich batches stored within the plumbing system. When reaching gas dominated conditions (i.e., a gas/melt mass ratio of 0.3 and CO2,gas/H2Ogas molar ratio 5 ), these will erupt effusively or mildly explosively, whilst in case of the 122 BC Plinian eruption, open-system degassing conditions took place within the plumbing system, such that continuous CO2-fluxing determined gas accumulation on top of the magmatic system. The emission of such a cap in the early eruptive phase triggered the arrival of deep H2O-rich whose fast decompression and bubble nucleation lead to the highly explosive character, enhanced by abundant microlite crystallization and consequent increase of magma effective viscosity. This could explain why open system basaltic systems like Etna may experience highly explosive or even Plinian episodes during eruptions that start with effusive to mildly explosive phases. The proposed mechanism also determines a

  3. Environmental impact of CO2, Rn, Hg degassing from the rupture zones produced by Wenchuan M s 8.0 earthquake in western Sichuan, China. (United States)

    Zhou, Xiaocheng; Chen, Zhi; Cui, Yueju


    The concentrations and flux of CO2, (222)Radon (Rn), and gaseous elemental mercury (Hg) in soil gas were investigated based on the field measurements in June 2010 at ten sites along the seismic rupture zones produced by the May 12, 2008, Wenchuan M s 8.0 earthquake in order to assess the environmental impact of degassing of CO2, Rn and Hg. Soil gas concentrations of 344 sampling points were obtained. Seventy measurements of CO2, Rn and Hg flux by the static accumulation chamber method were performed. The results of risk assessment of CO2, Rn and Hg concentration in soil gas showed that (1) the concentration of CO2 in the epicenter of Wenchuan M s 8.0 earthquake and north end of seismic ruptures had low risk of asphyxia; (2) the concentrations of Rn in the north segment of seismic ruptures had high levels of radon, Maximum was up to level 4, according to Chinese code (GB 50325-2001); (3) the average geoaccumulation index I geo of soil Hg denoted the lack of soil contamination, and maximum values classified the soil gas as moderately to strongly polluted in the epicenter. The investigation of soil gas CO2, Rn and Hg degassing rate indicated that (1) the CO2 in soil gas was characterized by a mean [Formula: see text] of -20.4 ‰ and by a mean CO2 flux of 88.1 g m(-2) day(-1), which were in the range of the typical values for biologic CO2 degassing. The maximum of soil CO2 flux reached values of 399 g m(-2) day(-1) in the epicenter; (2) the soil Rn had higher exhalation in the north segment of seismic ruptures, the maximum reached value of 1976 m Bq m(-2) s(-1); (3) the soil Hg flux was lower, ranging from -2.5 to 18.7 n g m(-2) h(-1) and increased from south to north. The mean flux over the all profiles was 4.2 n g m(-2) h(-1). The total output of CO2 and Hg degassing estimated along seismic ruptures for a survey area of 18.17 km(2) were approximately 0.57 Mt year(-1) and 688.19 g year(-1). It is recommended that land-use planners should

  4. Chlorine isotope composition of volcanic rocks and gases at Stromboli volcano (Aeolian Islands, Italy): Inferences on magmatic degassing prior to 2014 eruption (United States)

    Liotta, Marcello; Rizzo, Andrea L.; Barnes, Jaime D.; D'Auria, Luca; Martelli, Mauro; Bobrowski, Nicole; Wittmer, Julian


    Among the magmatic volatiles, chlorine (Cl) is degassed at shallow depths offering the opportunity to investigate the behavior of magmatic degassing close to the surface, and the possible occurrence of chemical and isotopic fractionation related to gas/melt partitioning. However, it is still unclear if the isotopic composition of Cl (δ37Cl) can be used as a proxy of magmatic degassing. In this work, we investigate the concentrations of chlorine and sulfur, and the Cl isotope composition of rocks and plume gases collected at Stromboli volcano, Aeolian Islands, Italy. This volcano was chosen because it is characterized by persistent eruptive activity (i.e., Strombolian explosions) and by the presence of magma at very shallow levels in the conduits. Rocks belonging to the different magmatic series erupted throughout the formation of the volcano have δ37Cl values ranging between - 1.0 and + 0.7‰. The isotopic composition seems independent of the Cl concentration of the rocks, but shows a negative correlation with SiO2 content. Plume gases have a greater isotopic compositional variability than the rocks (- 2.2‰ ≤ δ37Cl ≤ + 1.5‰) and the composition seems related to the level of volcanic activity at Stromboli. Gases collected in 2011-2013 during days of ordinary eruptive activity are characterized by δ37Cl values ranging from + 0.3 to + 1.5‰ and S/Cl molar ratios between 1.4 and 2.2, similar to previous S/Cl measurements performed at Stromboli with other techniques. Plume gases collected in July 2014, in days of high-level eruptive activity preceding the onset of the 2014 effusive eruption, have negative δ37Cl values (- 2.2‰ ≤ δ37Cl ≤ - 0.1‰) and S/Cl between 0.9 and 1.2, which are among the lowest S/Cl values measured at this volcano. The amplitude of the volcanic tremor and the variation in the inclination of very long period (VLP) seismic signal polarization clearly indicate that in July 2014 the intensity and frequency of Strombolian

  5. Dipicolinate complexes of main group metals with hydrazinium cation

    Indian Academy of Sciences (India)

    K Saravanan; S Govindarajan


    Some new coordination complexes of hydrazinium main group metal dipicolinate hydrates of formulae (N2H5)2M(dip)2.H2O (where, M =Ca, Sr, Ba or Pb and = 0, 2, 4 and 3 respectively and dip = dipicolinate), N2H5Bi(dip)2.3H2O and (N2H5)3Bi(dip)3.4H2O have been prepared and characterized by physico-chemical techniques. The infrared spectra of the complexes reveal the presence of tridentate dipicolinate dianions and non-coordinating hydrazinium cations. Conductance measurements show that the mono, di and trihydrazinium complexes behave as 1:1, 2:1 and 3:1 electrolytes respectively, in aqueous solution. Thermal decomposition studies show that these compounds lose water followed by endothermic decomposition of hydrazine to give respective metal hydrogendipicolinate intermediates, which further decompose exothermically to the final product of either metal carbonates (Ca, Sr, Ba and Pb) or metal oxycarbonates (Bi). The coordination numbers around the metal ions differ from compound to compound. The various coordination numbers exhibited by these metals are six (Ca), seven (Ba), eight (Sr) and nine (Pb and Bi). In all the complexes the above coordination number is attained by tridentate dipicolinate dianions and water molecules. The X-ray diffraction patterns of these compounds differ from one another suggesting that they are not isomorphous.

  6. Hydrogen motion in proton sponge cations: a theoretical study. (United States)

    Horbatenko, Yevhen; Vyboishchikov, Sergei F


    This work presents a study of intramolecular NHN hydrogen bonds in cations of the following proton sponges: 2,7-bis(trimethylsilyl)-1,8-bis(dimethylamino)naphthalene (1), 1,6-diazabicyclo[4.4.4.]tetradecane (2), 1,9-bis(dimethylamino)dibenzoselenophene (3), 1,9-bis(dimethylamino)dibenzothiophene (4), 4,5-bis(dimethylamino)fluorene (5), quino[7,8-h]quinoline (6) 1,2-bis(dimethylamino)benzene (7), and 1,12-bis(dimethylamino)benzo[c]phenantrene (8). Three different patterns were found for proton motion: systems with a single-well potential (cations 1-2), systems with a double-well potential and low proton transfer barrier, ΔEe (cations 3-5), and those with a double-well potential and a high barrier (cations 6-8). Tests of several density functionals indicate that the PBEPBE functional reproduces the potential-energy surface (PES) obtained at the MP2 level well, whereas the B3LYP, MPWB1K, and MPW1B95 functionals overestimate the barrier. Three-dimensional PESs were constructed and the vibrational Schrödinger equation was solved for selected cases of cation 1 (with a single-well potential), cation 4 (with a ΔEe value of 0.1 kcal mol(-1) at the MP2 level), and cations 6 (ΔEe = 2.4 kcal mol(-1)) and 7 (ΔEe=3.4 kcal mol(-1)). The PES is highly anharmonic in all of these cases. The analysis of the three-dimensional ground-state vibrational wave function shows that the proton is delocalized in cations 1 and 4, but is rather localized around the energy minima for cation 7. Cation 6 is an intermediate case, with two weakly pronounced maxima and substantial tunneling. This allows for classification of proton sponge cations into those with localized and those with delocalized proton behavior, with the borderline between them at ΔEe values of about 1.5 kcal mol(-1). The excited vibrational states of proton sponge cations with a low barrier can be described within the framework of a simple particle-in-a-box model. Each cation can be assigned an effective box width.

  7. Emission Rates, Pre-eruption Gas-Saturation and Ascent Degassing During the 2004-2005 Eruption of Mount St. Helens (United States)

    Gerlach, T. M.; McGee, K. A.; Doukas, M. P.


    Intermittent airborne measurements of volcanic gases began on 27 September 2004 during the initial unrest. Target gases included CO2, SO2 and H2S. The average emission rates through the end of July 2005 were approximately 650 metric tons/day (t/d) CO2 and 100 t/d SO2; H2S was always released and the estimated amount of melt supplied from depth (46 Mt) indicate the dacite would have been gas-saturated at plausible chamber depths. Data on the S content of melt inclusions and matrix glasses underestimate observed SO2 emissions by over a factor of five, corroborating pre-eruption gas saturation of the dacite. Using the 1980 magma equilibration depth (8 km) for comparison and assuming a similar water content (5 wt%) for the rhyolitic melt fraction (Rutherford, 1993; Blundy and Cashman, 2001) give a gas fraction constrained by H2O-CO2 solubility data of 1-2 vol% for the dacite. This compares with an estimate of 10-15 vol% for the 1980 dacite prior to eruption and of 5-30 vol% for common intermediate to silicic magmas (Wallace, 2003). Closed system ascent degassing calculations show that the volume fraction of gas increases to 8 vol% at 4-5 km and reaches 50 vol% at 1 km, where final solidification begins. The gas fraction can potentially increase to >60 vol% during solidification. Allowing for gas separation during extrusion, these results are consistent with observed dacite vesicle fractions averaging 25 vol% (Pallister et al. this session). Ascent degassing calculations also predict melt water contents similar to values measured on rare glassy dacite fragments last equilibrated at depths of 1.2-1.8 km (Mandeville this session).

  8. Level of carbon dioxide diffuse degassing from the ground of Vesuvio: comparison between extensive surveys and inferences on the gas source

    Directory of Open Access Journals (Sweden)

    Domenico Granieri


    Full Text Available An extensive campaign of diffuse CO2 soil flux was carried out at the cone of Vesuvio in October 2006 with two main objectives: 1 to provide an estimation of CO2 diffusely discharged through the soils in the summit area and 2 to evidence those sectors of the volcano where structural and morphological conditions could favour the gas output. The survey consisted of 502 measurements of soil CO2 flux homogenously distributed over an area of about 1.8 km2. Results of this survey were compared with those obtained during a similar campaign carried out by Frondini et al. in 2000, from which we have taken and reinterpreted a subset of data belonging to the common investigated area. Graphical statistical analysis showed three overlapping populations in both surveys, evidencing the contribution of three different sources feeding the soil CO2 degassing process. The overall CO2 emission pattern of 2006 is coherent with that observed in 2000 and suggests that a value between 120 and 140 t/day of CO2 is representative of the total CO2 discharged by diffuse degassing from the summit area of Vesuvio. The preferential exhaling area lies in the inner crater, whose contribution resulted in 45.3% of the total CO2 emission in 2006 (with 62.8 t/day and in 57.4% (with 70.3 t/day in 2000, although its extension is only 13% of the investigated area. This highly emissive area correlated closely with the structural discontinuities of Vesuvio cone, mainly suggesting that the NW-SE trending tectonic line is actually an active fault leaking deep gas to the bottom of the crater. The drainage action of the fault could be enhanced by the “aspiration” effect of the volcanic conduit.

  9. Erosion and assimilation of substrate by Martian low-viscosity lava flows: implications for sulphur degassing and the genesis of orthomagmatic Ni-Cu±(PGE) sulphide mineralisation (United States)

    Baratoux, D.; Baumgartner, R. J.; Gaillard, F.; Fiorentini, M. L.


    Archean and Proterozoic komatiites and ferropicrites are mantle plume-related, low-viscosity, high-temperature, mafic to ultramafic lava flows. They are hosts to Ni-Cu±(PGE) sulphide mineralisation, which generally formed due to the segregation of sulphides following thermo-mechanical erosion and assimilation of sulphur-rich crustal rocks. We numerically simulated erosion and assimilation during the turbulent emplacement of iron-rich Martian lavas displaying chemical and rheological analogies with terrestrial mafic to ultramafic lavas, on a variety of basaltic and sedimentary sulphate-rich substratum. With the adoption of the lava flow and erosion model of Williams et al. (JGR, 1998), thermodynamic simulations were implemented to (semi-) quantify the potential changes in melt parameter (i.e., chemistry, temperature, and oxygen fugacity) that dictate the sulphur capacity of silicate melts. Modelling was also performed to assess the role of volatile degassing (Gaillard et al., SSR, 2013) on the sulphur inventory of Martian lavas. Our modelling show that lavas emplacing over basaltic crust are governed by low cooling rates, as well as low erosion and assimilation capacities, thus resulting in calculated near-cotectic proportions of sulphides segregating relatively late upon lava emplacement (usually > 100 km flow distance). The rapid assimilation of highly erodible and sulphate-rich Martian regolith may trigger sulphide supersaturation and batch segregation of sulphides well above cotectic proportions relatively early during the establishment of magmatic flow (<100 km flow distance). However, the assimilation of sulphate, which serves as a strongly oxidising agent, could result in dramatic sulphur loss due to increased volatile degassing rates. This process may limit or even counteract the overall positive effect of sulphate assimilation on achieving sulphide supersaturation, sulphide segregation and the genesis of Ni-Cu±(PGE) sulphide mineralisation.

  10. Structure and temporal variations of a magmatic CO2 degassing site in the Bohemian Massif (Europe): an integrated geophysical-geochemical-sedimentological study (United States)

    Flechsig, C.; Nickschick, T.; Kaempf, H. W.; Mrlina, J.; Bussert, R.


    The Bohemian Massif, as a part of the Variscan orogenic belt, is one of the largest stable intracontinental zone of pre-Permian rocks in Central and Western Europe. Its geodynamically most active western part, the West Bohemia/Vogtland region, shows persistent seismic activity of recurring earthquake swarms (up to M 4.5) and intense CO2 degassing at the surface (mofettes) with mantle-derived He-isotope signatures. To understand the fluid migration in the subsurface and its control by tectonics is one research issue which must be addressed to clarify the possible link to the earthquake generation. We present results of an interdisciplinary study of near-surface sediments in a mofette field. The study comprises geophysical (gravimetry and geoelectrics), geochemical (CO2 soil gas and gas flux measurements), and sedimentological investigations. The investigations reveal a positive correlation between areas of high soil gas (CO2) concentration and flux with geophysical anomalies (negative self potential, positive structures of low electrical resistivity, decreased density) as well as with specific sediment properties (content of pyrite and organic material, occurrence of dispersed pebbles, uplifted clay layer). These features are thought to be directly or indirectly related to the magmatic caused fluid flow. Soil gas (CO2) flux and concentration anomalies spread out with a linear trend, suggesting the fault control on gas ascent. Negative self potential anomalies at the degassing spots were interpreted considering as having been caused by a downward movement of the meteoric water balancing the upward CO2 gas flux. The model of the active mofettes has to consider its bonding to deep-seated faults and can be tracked. The results fit into a tectonic model in which the mofette fields are in the centers of two independent pull-apart basin-like structures.

  11. The influence of cationic lipid type on in-vitro release kinetic profiles of antisense oligonucleotide from cationic nanoemulsions. (United States)

    Hagigit, Tal; Nassar, Taher; Behar-Cohen, Francine; Lambert, Gregory; Benita, Simon


    Novel formulations of cationic nanoemulsions based on three different lipids were developed to strengthen the attraction of the polyanionic oligonucleotide (ODN) macromolecules to the cationic moieties on the oil nanodroplets. These formulations were developed to prolong the release of the ODN from the nanoemulsion under appropriate physiological dilutions as encountered in the eye following topical application. Increasing the concentration of the new cationic lipid exhibiting two cationic amine groups (AOA) in the emulsion from 0.05% to 0.4% did not alter markedly the particle size or zeta potential value of the blank cationic nanoemulsion. The extent of ODN association did not vary significantly when the initial concentration of ODN remained constant at 10 microM irrespective of the cationic lipid nature. However, the zeta potential value dropped consistently with the low concentrations of 0.05% and 0.1% of AOA in the emulsions suggesting that an electrostatic attraction occurred between the cationic lipids and the polyanionic ODN molecules at the o/w interface. Only the nanoemulsion prepared with N-[1-(2,3-dioleoyloxy)propyl]-N,N,N-trimethylammonium salts (DOTAP) remained physically stable over time. DOTAP cationic lipid nanoemulsion was the most efficient formulation capable of retaining the ODN despite the high dilution of 1:100 with simulated tear solution (STS). Less than 10% of the ODN was exchanged in contrast to 40-50% with the other cationic nanoemulsions. The in-vitro release kinetic behavior of ODN exchange with physiological anions present in the STS appears to be complex and difficult to characterize using mathematical fitting model equations. Further pharmacokinetic studies are needed to verify our kinetic assumptions and confirm the in-vitro ODN release profile from DOTAP cationic nanoemulsions.

  12. Repurposing Cationic Amphiphilic Antihistamines for Cancer Treatment

    Directory of Open Access Journals (Sweden)

    Anne-Marie Ellegaard


    Full Text Available Non-small cell lung cancer (NSCLC is one of the deadliest cancers worldwide. In search for new NSCLC treatment options, we screened a cationic amphiphilic drug (CAD library for cytotoxicity against NSCLC cells and identified several CAD antihistamines as inducers of lysosomal cell death. We then performed a cohort study on the effect of CAD antihistamine use on mortality of patients diagnosed with non-localized cancer in Denmark between 1995 and 2011. The use of the most commonly prescribed CAD antihistamine, loratadine, was associated with significantly reduced all-cause mortality among patients with non-localized NSCLC or any non-localized cancer when compared with use of non-CAD antihistamines and adjusted for potential confounders. Of the less frequently described CAD antihistamines, astemizole showed a similar significant association with reduced mortality as loratadine among patients with any non-localized cancer, and ebastine use showed a similar tendency. The association between CAD antihistamine use and reduced mortality was stronger among patients with records of concurrent chemotherapy than among those without such records. In line with this, sub-micromolar concentrations of loratadine, astemizole and ebastine sensitized NSCLC cells to chemotherapy and reverted multidrug resistance in NSCLC, breast and prostate cancer cells. Thus, CAD antihistamines may improve the efficacy of cancer chemotherapy.

  13. Cationic Noncovalent Interactions: Energetics and Periodic Trends. (United States)

    Rodgers, M T; Armentrout, P B


    In this review, noncovalent interactions of ions with neutral molecules are discussed. After defining the scope of the article, which excludes anionic and most protonated systems, methods associated with measuring thermodynamic information for such systems are briefly recounted. An extensive set of tables detailing available thermodynamic information for the noncovalent interactions of metal cations with a host of ligands is provided. Ligands include small molecules (H2, NH3, CO, CS, H2O, CH3CN, and others), organic ligands (O- and N-donors, crown ethers and related molecules, MALDI matrix molecules), π-ligands (alkenes, alkynes, benzene, and substituted benzenes), miscellaneous inorganic ligands, and biological systems (amino acids, peptides, sugars, nucleobases, nucleosides, and nucleotides). Hydration of metalated biological systems is also included along with selected proton-based systems: 18-crown-6 polyether with protonated peptides and base-pairing energies of nucleobases. In all cases, the literature thermochemistry is evaluated and, in many cases, reanchored or adjusted to 0 K bond dissociation energies. Trends in these values are discussed and related to a variety of simple molecular concepts.


    Directory of Open Access Journals (Sweden)

    Elina Orblin


    Full Text Available Papermaking pulps are a mixture of fibres, fibre fragments, and small cells (parenchyma or ray cells, usually called pulp fines. The interactions between pulp fines and a cationic copolymer of acrylamide and acryloxyethyltrimethyl ammonium chloride were investigated based on solid-liquid isotherms prepared under different turbulence, and subsequent advanced surface characterization using X-ray photoelectron spectroscopy (XPS and time-of-flight secondary ion mass spectrometry (ToF-SIMS. The surface charge and surface area of pulp fine substrates were measured by methylene blue sorption-XPS analysis and nitrogen adsorption combined with mercury porosimetry, respectively. The driving force behind polyelectrolyte adsorption was the amount of the surface anionic charge, whereas surface area appeared to be of less importance. Based on a comparison of solid-liquid and XPS sorption isotherms, different polyelectrolyte conformations were suggested, depending on the types of fines: A flatter conformation and partial cell-wall penetration of polyelectrolytes on kraft fines from freshly prepared pulp, and a more free conformation with extended loops and tails on lignocellulosic fines from recycled pulp. Additionally, ToF-SIMS imaging proved that recycled pulp fines contained residual de-inking chemicals (primarily palmitic acid salts that possibly hinder the electrostatic interactions with polyelectrolytes.

  15. Inactivation of Heparin by Cationically Modified Chitosan

    Directory of Open Access Journals (Sweden)

    Barbara Lorkowska-Zawicka


    Full Text Available This study was performed to evaluate the ability of N-(2-hydroxypropyl-3-tri methylammonium chitosan chloride (HTCC, the cationically modified chitosan, to form biologically inactive complexes with unfractionated heparin and thereby blocking its anticoagulant activity. Experiments were carried out in rats in vivo and in vitro using the activated partial thromboplastin time (APTT and prothrombin time (PT tests for evaluation of heparin anticoagulant activity. For the first time we have found that HTCC effectively neutralizes anticoagulant action of heparin in rat blood in vitro as well as in rats in vivo. The effect of HTCC on suppression of heparin activity is dose-dependent and its efficacy can be comparable to that of protamine-the only agent used in clinic for heparin neutralization. HTCC administered i.v. alone had no direct effect on any of the coagulation tests used. The potential adverse effects of HTCC were further explored using rat experimental model of acute toxicity. When administered i.p. at high doses (250 and 500 mg/kg body weight, HTCC induced some significant dose-dependent structural abnormalities in the liver. However, when HTCC was administered at low doses, comparable to those used for neutralization of anticoagulant effect of heparin, no histopathological abnormalities in liver were observed.

  16. Competitive Effects of 2+ and 3+ Cations on DNA Compaction

    CERN Document Server

    Tongu, C; Yoshikawa, Y; Zinchenko, A A; Chen, N; Yoshikawa, K


    By using single-DNA observation with fluorescence microscopy, we observed the effects of divalent and trivalent cations on the higher-order structure of giant DNA (T4 DNA with 166 kbp). It was found that divalent cations, such as Mg(2+) and Ca(2+), inhibit DNA compaction induced by a trivalent cation, spermidine (SPD(3+)). On the other hand, in the absence of SPD(3+), divalent cations cause the shrinkage of DNA. These experimental observations are inconsistent with the well-established Debye-Huckel scheme regarding the shielding effect of counter ions, which is given as the additivity of contributions of cations with different valences. We interpreted the competition between 2+ and 3+ cations in terms of the change in the translational entropy of the counter ions before and after the folding transition of DNA. For the compaction with SPD(3+), we considered the increase in translational entropy due to the ion-exchange of the intrinsic monovalent cations condensing on a highly-charged polyelectrolyte, double-st...

  17. Neutron diffraction investigations of kesterites: cation order and disorder

    Energy Technology Data Exchange (ETDEWEB)

    Schorr, Susan [Free University Berlin, Institute of Geological Sciences (Germany); Tovar, Michael [Helmholtz Zentrum Berlin fuer Materialien und Energie (Germany); Levcenco, Sergej; Napetrov, Alexander; Arushanov, Ernest [Academy of Sciences of Moldova Republic, Institute of Applied Physics, Chisinau (Moldova)


    The quaternary chalcogenides Cu{sub 2}ZnSnS{sub 4} and Cu{sub 2}ZnSnSe{sub 4} have newly attracted attention as possible absorber materials in thin film solar cells. They crystallize in the kesterite type (space group I anti 4) or stannite type structure (space group I anti 42m), which are described as an ordered distribution of the cations on different structural sites. Cation disorder may cause site defects and hence influences the electronic properties of the material. Thus the degree of cation order/disorder plays a crucial role and was therefor in the focus of the presented investigations. A differentiation between the isoelectronic cations Cu{sup +} and Zn{sup 2+} is not possible using X-ray diffraction due to their similar scattering power. But their neutron scattering lengths are different, thus neutron diffraction opens the possibility to determine the cation distribution in these compounds. A simultaneous Rietveld analysis of neutron and X-ray powder diffraction data revealed that in dependence on the thermal history of the samples cation disorder appears. The correlation trend between cation order/disorder and the sample growth method (solid state synthesis, Bridgman method) are discussed.

  18. Cation exchange properties of zeolites in hyper alkaline aqueous media. (United States)

    Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric


    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.

  19. Lipopolysaccharide Neutralization by Cationic-Amphiphilic Polymers through Pseudoaggregate Formation. (United States)

    Uppu, Divakara S S M; Haldar, Jayanta


    Synthetic polymers incorporating the cationic charge and hydrophobicity to mimic the function of antimicrobial peptides (AMPs) have been developed. These cationic-amphiphilic polymers bind to bacterial membranes that generally contain negatively charged phospholipids and cause membrane disintegration resulting in cell death; however, cationic-amphiphilic antibacterial polymers with endotoxin neutralization properties, to the best of our knowledge, have not been reported. Bacterial endotoxins such as lipopolysaccharide (LPS) cause sepsis that is responsible for a great amount of mortality worldwide. These cationic-amphiphilic polymers can also bind to negatively charged and hydrophobic LPS and cause detoxification. Hence, we envisaged that cationic-amphiphilic polymers can have both antibacterial as well as LPS binding properties. Here we report synthetic amphiphilic polymers with both antibacterial as well as endotoxin neutralizing properties. Levels of proinflammatory cytokines in human monocytes caused by LPS stimulation were inhibited by >80% when coincubated with these polymers. These reductions were found to be dependent on concentration and, more importantly, on the side-chain chemical structure due to variations in the hydrophobicity profiles of these polymers. These cationic-amphiphilic polymers bind and cause LPS neutralization and detoxification. Investigations of polymer interaction with LPS using fluorescence spectroscopy and dynamic light scattering (DLS) showed that these polymers bind but neither dissociate nor promote LPS aggregation. We show that polymer binding to LPS leads to sort of a pseudoaggregate formation resulting in LPS neutralization/detoxification. These findings provide an unusual mechanism of LPS neutralization using novel synthetic cationic-amphiphilic polymers.

  20. Atmospheric CO2 enrichment facilitates cation release from soil. (United States)

    Cheng, L; Zhu, J; Chen, G; Zheng, X; Oh, N-H; Rufty, T W; Richter, D deB; Hu, S


    Atmospheric CO(2) enrichment generally stimulates plant photosynthesis and nutrient uptake, modifying the local and global cycling of bioactive elements. Although nutrient cations affect the long-term productivity and carbon balance of terrestrial ecosystems, little is known about the effect of CO(2) enrichment on cation availability in soil. In this study, we present evidence for a novel mechanism of CO(2)-enhancement of cation release from soil in rice agricultural systems. Elevated CO(2) increased organic C allocation belowground and net H(+) excretion from roots, and stimulated root and microbial respiration, reducing soil redox potential and increasing Fe(2+) and Mn(2+) in soil solutions. Increased H(+), Fe(2+), and Mn(2+) promoted Ca(2+) and Mg(2+) release from soil cation exchange sites. These results indicate that over the short term, elevated CO(2) may stimulate cation release from soil and enhance plant growth. Over the long-term, however, CO(2)-induced cation release may facilitate cation losses and soil acidification, negatively feeding back to the productivity of terrestrial ecosystems.

  1. Cations bind only weakly to amides in aqueous solutions. (United States)

    Okur, Halil I; Kherb, Jaibir; Cremer, Paul S


    We investigated salt interactions with butyramide as a simple mimic of cation interactions with protein backbones. The experiments were performed in aqueous metal chloride solutions using two spectroscopic techniques. In the first, which provided information about contact pair formation, the response of the amide I band to the nature and concentration of salt was monitored in bulk aqueous solutions via attenuated total reflection Fourier transform infrared spectroscopy. It was found that molar concentrations of well-hydrated metal cations (Ca(2+), Mg(2+), Li(+)) led to the rise of a peak assigned to metal cation-bound amides (1645 cm(-1)) and a decrease in the peak associated with purely water-bound amides (1620 cm(-1)). In a complementary set of experiments, the effect of cation identity and concentration was investigated at the air/butyramide/water interface via vibrational sum frequency spectroscopy. In these studies, metal ion-amide binding led to the ordering of the adjacent water layer. Such experiments were sensitive to the interfacial partitioning of cations in either a contact pair with the amide or as a solvent separated pair. In both experiments, the ordering of the interactions of the cations was: Ca(2+) > Mg(2+) > Li(+) > Na(+) ≈ K(+). This is a direct cationic Hofmeister series. Even for Ca(2+), however, the apparent equilibrium dissociation constant of the cation with the amide carbonyl oxygen was no tighter than ∼8.5 M. For Na(+) and K(+), no evidence was found for any binding. As such, the interactions of metal cations with amides are far weaker than the analogous binding of weakly hydrated anions.

  2. Cation Exchange Capacity of Biochar: An urgent method modification (United States)

    Munera, Jose; Martinsen, Vegard; Mulder, Jan; Tau Strand, Line; Cornelissen, Gerard


    A better understanding of the cation exchange capacity (CEC) values of biochar and its acid neutralizing capacity (ANC) is crucial when tailoring a single biochar for a particular soil and crop. Literature values for the CEC of biochar are surprisingly variable, commonly ranging from 5 to 50 cmol+/Kg even as high as 69 to 204 cmol+/Kg and often poorly reproducible, suggesting methodological problems. Ashes and very fine pores in biochar may complicate the analysis and thus compromise the results. Here, we modify and critically assess different steps in a common method for CEC determination in biochar and investigate how the measured CEC may be affected by slow cation diffusion from micro-pores. We modified the existing ammonium acetate (NH4-OAc) method (buffered at pH 7), based on displaced ammonium (NH4+) in potassium chloride (KCl) extracts after removing excess NH4-OAc with alcohol in batch mode. We used pigeon pea biochar (produced at 350 ˚C; particle size 0.5mm to 2mm) to develop the method and we tested its reproducibility in biochars with different ANC. The biochar sample (1.00g) was pH-adjusted to 7 after 2 days of equilibration, using hydrochloric acid (HCl), and washed with water until the conductivity of the water was removed the soluble ash component, while simultaneously allowing the NH4-OAc to buffer at pH 7. To assess the importance of diffusion limitation of replacing cations (NH4+ and K+) in micro-pores, we equilibrated the biochar with NH4-OAc for 1 and 7 days, and after washing with alcohol, for 1, 3 and 7 days with KCl. The effects of the washing volume of alcohol (15, 30 and 45 ml) and of the biochar to NH4OAc solution ratio (1:15, 1:30 and 1:45) were also tested. The CEC values were corrected for dry matter content and mass losses during the process. Results indicate that the measured CEC values of the modified method were highly reproducible and that 1 day shaking with NH4OAc and KCl is enough to saturate the exchange sites with NH4+ and

  3. Multidimensional Heat Conduction

    DEFF Research Database (Denmark)

    Rode, Carsten


    Analytical theory of multidimensional heat conduction. General heat conduction equation in three dimensions. Steay state, analytical solutions. The Laplace equation. Method of separation of variables. Principle of superposition. Shape factors. Transient, multidimensional heat conduction....

  4. Competitive Solvation of the Imidazolium Cation by Water and Methanol

    CERN Document Server

    Chaban, Vitaly


    Imidazolium-based ionic liquids are widely used in conjunction with molecular liquids for various applications. Solvation, miscibility and similar properties are of fundamental importance for successful implementation of theoretical schemes. This work reports competitive solvation of the 1,3-dimethylimidazolium cation by water and methanol. Employing molecular dynamics simulations powered by semiempirical Hamiltonian (electronic structure level of description), the local structure nearly imidazolium cation is described in terms of radial distribution functions. Although water and methanol are chemically similar, water appears systematically more successful in solvating the 1,3-dimethylimidazolium cation. This result fosters construction of future applications of the ternary ion-molecular systems.

  5. Infrared Spectroscopic Study for the Hydrated Clusters of Pentane Cation (United States)

    Endo, Tomoya; Matsuda, Yoshiyuki; Fujii, Asuka


    We performed infrared predissociation spectroscopy of size-selected pentane-water cluster cations, [pentane-(H2O)n]+, n=1-3, generated through the vacuum-ultraviolet photoionization. In the infrared spectra of the di- and tri-hydrated clusters, there appear broad features which spread to the lower frequency region from 2800 cm-1. These broad features are assigned to vibrations of a proton, which is transferred from CH of the pentane cation to the water molecules. These results indicate that the pentane cation has high proton donor ability. We will discuss these results based on theoretical conputations.

  6. Cation Transport in Polymer Electrolytes: A Microscopic Approach (United States)

    Maitra, A.; Heuer, A.


    A microscopic theory for cation diffusion in polymer electrolytes is presented. Based on a thorough analysis of molecular dynamics simulations on poly(ethylene) oxide with LiBF4, the mechanisms of cation dynamics are characterized. Cation jumps between polymer chains can be identified as renewal processes. This allows us to obtain an explicit expression for the lithium ion diffusion constant DLi by invoking polymer-specific properties such as the Rouse dynamics. This extends previous phenomenological and numerical approaches. In particular, the chain length dependence of DLi can be predicted and compared with experimental data. This dependence can be fully understood without referring to entanglement effects.

  7. Electrostatic charge confinement using bulky tetraoctylammonium cation and four anions (United States)

    Andreeva, Nadezhda A.; Chaban, Vitaly V.


    Thanks to large opposite electrostatic charges, cations and anions establish strong ionic bonds. However, applications of ionic systems - electrolytes, gas capture, solubilization, etc. - benefit from weaker non-covalent bonds. The common approaches are addition of cosolvents and delocalization of electron charge density via functionalization of ions. We report fine tuning of closest-approach distances, effective radii, and cation geometry by different anions using the semi-empirical molecular dynamics simulations. We found that long fatty acid chains employed in the tetraalkylammonium cation are largely inefficient and new substituents must be developed. The reported results foster progress of task-specific ionic liquids.

  8. Pyridine radical cation and its fluorine substituted derivatives (United States)

    Bondybey, V.E.; English, J.H.; Shiley, R.H.


    The spectra and relaxation of the pyridine cation and of several of its fluorinated derivatives are studied in low temperature Ne matrices. The ions are generated by direct photoionization of the parent compounds. Of the compounds studied, laser induced → and → fluorescence is observed only for the 2, 6‐difluoropyridine cation. The analysis of the spectrum indicates that the ion is planar both in the and states. The large variety in the spectroscopic and relaxation behavior of fluoropyridine radical cations is explained in terms of their electronic structure and of the differential shifts of the individual electronic states caused by the fluorine substitution.

  9. Cationic starches on cellulose surfaces. A study of polyelectrolyte adsorption.


    Steeg, van der, P.A.H.


    Cationic starches are used on a large scale in paper industry as wet-end additives. They improve dry strength. retention of fines and fillers, and drainage. Closure of the white water systems in the paper mills hase increased the concentration of detrimental substances. This might be the reason for the poor retention of cationic starches observed in the last few years.The purpose of the research described in this thesis was to obtain a better understanding of the adsorption of cationic starch...

  10. Endomembrane Cation Transporters and Membrane Trafficking

    Energy Technology Data Exchange (ETDEWEB)

    Sze, Heven [Univ. of Maryland, College Park, MD (United States). Dept. of Cell Biology & Molecular Genetics


    Multicellular, as well as unicellular, organisms have evolved mechanisms to regulate ion and pH homeostasis in response to developmental cues and to a changing environment. The working hypothesis is that the balance of fluxes mediated by diverse transporters at the plasma membrane and in subcellular organelles determines ionic cellular distribution, which is critical for maintenance of membrane potential, pH control, osmolality, transport of nutrients, and protein activity. An emerging theme in plant cell biology is that cells respond and adapt to diverse cues through changes of the dynamic endomembrane system. Yet we know very little about the transporters that might influence the operation of the secretory system in plants. Here we focus on transporters that influence alkali cation and pH homeostasis, mainly in the endomembrane/ secretory system. The endomembrane system of eukaryote cells serves several major functions: i) sort cargo (e.g. enzymes, transporters or receptors) to specific destinations, ii) modulate the protein and lipid composition of membrane domains through remodeling, and iii) determine and alter the properties of the cell wall through synthesis and remodeling. We had uncovered a novel family of predicted cation/H+ exchangers (CHX) and K+ efflux antiporters (KEA) that are prevalent in higher plants, but rare in metazoans. We combined phylogenetic and transcriptomic analyses with molecular genetic, cell biological and biochemical studies, and have published the first reports on functions of plant CHXs and KEAs. CHX studied to date act at the endomembrane system where their actions are distinct from the better-studied NHX (Na/K-H+ exchangers). Arabidopsis thaliana CHX20 in guard cells modulate stomatal opening, and thus is significant for vegetative survival. Other CHXs ensure reproductive success on dry land, as they participate in organizing pollen walls, targeting of pollen tubes to the ovule or promoting

  11. Role of Metal Cations on the corrosion behaviour of 8090-T851 in a pH 2.0 solution

    DEFF Research Database (Denmark)

    Murthy, K.S.N.; Ambat, Rajan; Dwarakadasa, E.S.


    The influence of cations such as Cu2+, Al3+ and Li+ on the corrosion behaviour of 8090-T851(Al-Li) alloy in a pH 2.0 HCl solution was investigated by weight loss and polarisation techniques. Weight loss experiments showed that the effect of cation is a strong function of its nature and concentrat......The influence of cations such as Cu2+, Al3+ and Li+ on the corrosion behaviour of 8090-T851(Al-Li) alloy in a pH 2.0 HCl solution was investigated by weight loss and polarisation techniques. Weight loss experiments showed that the effect of cation is a strong function of its nature...... indicated that the corrosion activation by Al3+ ions is due to their chemical reactivity with the corroding substrate. Little enhancement in corrosion by Li+ ions is attributed to the increase in solution conductivity in their presence....

  12. Novel cationic polyelectrolyte coatings for capillary electrophoresis. (United States)

    Duša, Filip; Witos, Joanna; Karjalainen, Erno; Viitala, Tapani; Tenhu, Heikki; Wiedmer, Susanne K


    The use of bare fused silica capillary in CE can sometimes be inconvenient due to undesirable effects including adsorption of sample or instability of the EOF. This can often be avoided by coating the inner surface of the capillary. In this work, we present and characterize two novel polyelectrolyte coatings (PECs) poly(2-(methacryloyloxy)ethyl trimethylammonium iodide) (PMOTAI) and poly(3-methyl-1-(4-vinylbenzyl)-imidazolium chloride) (PIL-1) for CE. The coated capillaries were studied using a series of aqueous buffers of varying pH, ionic strength, and composition. Our results show that the investigated polyelectrolytes are usable as semi-permanent (physically adsorbed) coatings with at least five runs stability before a short coating regeneration is necessary. Both PECs showed a considerably decreased stability at pH 11.0. The EOF was higher using Good's buffers than with sodium phosphate buffer at the same pH and ionic strength. The thickness of the PEC layers studied by quartz crystal microbalance was 0.83 and 0.52 nm for PMOTAI and PIL-1, respectively. The hydrophobicity of the PEC layers was determined by analysis of a homologous series of alkyl benzoates and expressed as the distribution constants. Our result demonstrates that both PECs had comparable hydrophobicity, which enabled separation of compounds with log Po/w > 2. The ability to separate cationic drugs was shown with β-blockers, compounds often misused in doping. Both coatings were also able to separate hydrolysis products of the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-ene acetate at highly acidic conditions, where bare fused silica capillaries failed to accomplish the separation.

  13. IRMPD action spectroscopy of alkali metal cation-cytosine complexes: effects of alkali metal cation size on gas phase conformation. (United States)

    Yang, Bo; Wu, R R; Polfer, N C; Berden, G; Oomens, J; Rodgers, M T


    The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation-cytosine complexes exhibit both similar and distinctive spectral features over the range of ~1000-1900 cm(-1). The IRMPD spectra of the Li(+)(cytosine), Na(+)(cytosine), and K(+)(cytosine) complexes are relatively simple but exhibit changes in the shape and shifts in the positions of several bands that correlate with the size of the alkali metal cation. The IRMPD spectra of the Rb(+)(cytosine) and Cs(+)(cytosine) complexes are much richer as distinctive new IR bands are observed, and the positions of several bands continue to shift in relation to the size of the metal cation. The measured IRMPD spectra are compared to linear IR spectra of stable low-energy tautomeric conformations calculated at the B3LYP/def2-TZVPPD level of theory to identify the conformations accessed in the experiments. These comparisons suggest that the evolution in the features in the IRMPD action spectra with the size of the metal cation, and the appearance of new bands for the larger metal cations, are the result of the variations in the intensities at which these complexes can be generated and the strength of the alkali metal cation-cytosine binding interaction, not the presence of multiple tautomeric conformations. Only a single tautomeric conformation is accessed for all five alkali metal cation-cytosine complexes, where the alkali metal cation binds to the O2 and N3 atoms of the canonical amino-oxo tautomer of cytosine, M(+)(C1).

  14. Nanostructure-thermal conductivity relationships in protic ionic liquids. (United States)

    Murphy, Thomas; Varela, Luis M; Webber, Grant B; Warr, Gregory G; Atkin, Rob


    The thermal conductivities of nine protic ionic liquids (ILs) have been investigated between 293 and 340 K. Within this range, the thermal conductivities are between 0.18 and 0.30 W · m(-1) · K(-1). These values are higher than those typically associated with oils and aprotic ILs, but lower than those of strongly hydrogen bonding solvents like water. Weak linear decreases in thermal conductivity with temperature are noted, with the exception of ethanolammonium nitrate (EtAN) where the thermal conductivity increases with temperature. The dependence of thermal conductivity on IL type is analyzed with use of the Bahe-Varela pseudolattice theory. This theory treats the bulk IL as an array of ordered domains with intervening domains of uncorrelated structure which enable and provide barriers to heat propagation (respectively) via allowed vibrational modes. For the protic ILs investigated, thermal conductivity depends strongly on the IL cation alkyl chain length. This is because the cation alkyl chain controls the dimensions of the IL bulk nanostructure, which consists of charged (ordered domains) and uncharged regions (disordered domains). As the cation alkyl chain controls the dimensions of the disordered domains, it thus limits the thermal conductivity. To test the generality of this interpretation, the thermal conductivities of propylammonium nitrate (PAN) and PAN-octanol mixtures were examined; water selectively swells the PAN charged domain, while octanol swells the uncharged regions. Up to a certain concentration, adding water increases thermal conduction and octanol decreases it, as expected. However, at high solute concentrations the IL nanostructure is broken. When additional solvent is added above this concentration the rate of change in thermal conductivity is greatly reduced. This is because, in the absence of nanostructure, the added solvent only serves to dilute the salt solution.

  15. Cation size effects in mixed-ion metaphosphate glasses: structural characterization by multinuclear solid state NMR spectroscopy. (United States)

    Schneider, J; Tsuchida, J; Eckert, H


    Metaphosphate glasses with two monovalent species A(1-x)B(x)PO3 (0 ≤x≤ 1) show mixed-ion effects (MIE) in the dc conductivities and glass transition temperatures, which are strongly dependent on the cation size mismatch between the two mobile species. In the present contribution, mixed-ion metaphosphate glasses based on the cation combinations Cs-Li, Rb-Li, and Cs-Ag, exhibiting particularly large size mismatches, are analyzed by (31)P, (87)Rb, (109)Ag and (133)Cs NMR to determine possible correlations between this mismatch and some of the structural properties critical to the development of the MIE: the local environments around the mobile species and their spatial distribution relative to each other. The results are compared with those obtained in the Na-Ag metaphosphate series, which serves as a reference system, with minimized cation mismatch MIE. The local coordination environments of the Ag(+), Rb(+) and Cs(+) ions follow analogous compositional trends as previously observed in Na-based mixed-ion metaphosphate glasses: for a given cation species A, the average A-O distance shows an expansion/compression when this cation is replaced by a second species B with smaller/bigger ionic radius, respectively. This compositional differentiation of the structural sites for the mobile species may contribute to the MIE. Concerning the relative spatial distribution of the mobile ions, results from (7)Li-(133)Cs (SEDOR) experiments indicate a random mixture of Cs and Li in Cs-Li metaphosphate glasses. While this result is in agreement with one of the fundamental hypotheses of the models proposed to describe the MIE, it is at variance with the observation of various partial cation segregation phenomena observed in Na-based mixed alkali glasses. This result suggests that cation size mismatch is not the decisive parameter in determining segregation or non-statistical mixing of cations in the glass. In the Cs-Ag and Na-Ag glasses, (109)Ag spin-echo NMR reveals a progressive

  16. Synthesis and characterization of the first 2 d neptunyl structure stabilized by side-on cation-cation interactions

    Energy Technology Data Exchange (ETDEWEB)

    Vlaisavljevich, Bess; Miro, Pere; Ma, Dongxia; Cramer, Christopher J.; Gagliardi, Laura [Department of Chemistry, Supercomputing Institute and Chemical Theory Center, University of Minnesota, Minneapolis, MN (United States); Sigmon, Ginger E.; Burns, Peter C. [Department of Civil and Environmental Engineering and Earth Sciences, and Department of Chemistry and Biochemistry, University of Notre Dame, IN (United States)


    A new 2 D sheet structure containing a side-on cation-cation interaction (CCI) has been synthesized and characterized. Unprecedentedly, no chelating ligands between the cations are present. The nature of the side-on interaction and ligand effects has been explored by using a variety of quantum chemical methods. The spin-orbit-coupled ground state mixes singlet, triplet, and quintet-pure spin states. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Cation-Cation Interactions in [(UO2)2(OH)n](4-n) Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Odoh, Samuel O.; Govind, Niranjan; Schreckenbach, Georg; De Jong, Wibe A.


    The structures and bonding of gas-phase [(UO2)2(OH)n]4-n (n=2-6) complexes have been studied using density functional theory (DFT), MP2 and CCSD(T) methods with particular emphasis on ground state structures featuring cation-cation interactions (CCIs) between the uranyl groups. An interesting trend is observed in the stabilities of members of this series of complexes. The structures of [(UO2)2(OH)2]2+, [(UO2)2(OH)4] and [(UO2)2(OH)6]2- featuring CCIs are found at higher energies (by 3-20 kcal/mol) in comparison to their conventional μ2-dihydroxo structures. In contrast, the CCI structures of [(UO2)2(OH)3]+ and [(UO2)2(OH)5]- are respectively almost degenerate with and lower in energy than the structures with the μ2-dihydroxo format. The origin of this trend lies in the ‘symmetry’-based need to balance the coordination numbers and effective atomic charges of each uranium center. The calculated IR vibrational frequencies provide signature probes that can be used in differentiating the lowenergy structures and in experimentally confirming the existence of the structures featuring CCIs. Analysis of the bonding in the structures of [(UO2)2(OH)3]+ and [(UO2)2(OH)5]- shows that the CCIs and bridging hydroxo between the dioxo-uranium units are mainly electrostatic in nature.

  18. Isomerization of propargyl cation to cyclopropenyl cation: Mechanistic elucidations and effects of lone pair donors

    Indian Academy of Sciences (India)

    Zodinpuia Pachuau; Kiew S Kharnaior; R H Duncan Lyngdoh


    This ab initio study examines two pathways (one concerted and the other two-step) for isomerization of the linear propargyl cation to the aromatic cyclopropenyl cation, also probing the phenomenon of solvation of this reaction by simple lone pair donors (NH3, H2O, H2S and HF) which bind to the substrate at two sites. Fully optimized geometries at the B3LYP/6-31G(d) level were used, along with single point QCISD(T)/6-311+G(d,p) and accurate G3 level calculations upon the DFT optimized geometries. For the unsolvated reaction, the two-step second pathway is energetically favoured over the one-step first pathway. Lone pair donor affinity for the various C3H$^{+}_{3}$ species follows the uniform order NH3 > H2S>H2O>HF. The activation barriers for the solvated isomerizations decrease in the order HF>H2O>H2S>NH3 for both pathways. The number of lone pairs on the donor heteroatom as well as the heteroatom electronegativity are factors related to both these trends. Compared to the unsolvated cases, the solvated reactions have transition states which are usually ‘later’ in position along the reaction coordinate, validating the Hammond postulate.

  19. Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process. (United States)

    Reshetnikov, Roman V; Sponer, Jiri; Rassokhina, Olga I; Kopylov, Alexei M; Tsvetkov, Philipp O; Makarov, Alexander A; Golovin, Andrey V


    A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange.

  20. Solution Versus Gas-Phase Modification of Peptide Cations with NHS-Ester Reagents (United States)

    Mentinova, Marija; Barefoot, Nathan Z.; McLuckey, Scott A.


    A comparison between solution and gas phase modification of primary amine sites in model peptide cations with N-hydroxysuccinimide (NHS) ester reagents is presented. In all peptides, the site of modification in solution was directed to the N-terminus by conducting reactions at pH = 5, whereas for the same peptides, a lysine residue was preferentially modified in the gas phase. The difference in pKa values of the N-terminus and ɛ-amino group of the lysine allows for a degree of control over sites of protonation of the peptides in aqueous solution. With removal of the dielectric and multiple charging of the peptide ions in the gas phase, the accommodation of excess charge can affect the preferred sites of reaction. Interaction of the lone pair of the primary nitrogen with a proton reduces its nucleophilicity and, as a result, its reactivity towards NHS-esters. While no evidence for reaction of the N-terminus with sulfo-NHS-acetate was noted in the model peptide cations, a charge inversion experiment using bis[sulfosuccinimidyl] suberate, a cross-linking reagent with two sulfo-NHS-ester functionalities, showed modification of the N-terminus. Hence, an unprotonated N-terminus can serve as a nucleophile to displace NHS, which suggests that its lack of reactivity with the peptide cations is likely due to the participation of the N-terminus in solvating excess charge.

  1. DFT study on the cycloreversion of thietane radical cations. (United States)

    Domingo, Luis R; Pérez-Ruiz, Raúl; Argüello, Juan E; Miranda, Miguel A


    The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4+2] cycloadducts are obtained. Thus, the CR of radical cations 1a,b(•+) is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b(•+) (ii). Calculations support that 1a(•+) follows reaction pathway ii (leading to the formal [4+2] cycloadducts 5a). By contrast, 1b(•+) follows pathway i, leading to trans-stilbene radical cation (2b(•+)) and thiobenzophenone.


    African Journals Online (AJOL)

    B. S. Chandravanshi

    cation exchange-solid phase extraction (SCX-SPE) was investigated as an .... Stock solutions, with a concentration of 1.00 mg/mL were prepared ... Johannesburg, South Africa) connected to a vacuum pump (Vacuubrand, GMBH, Germany).

  3. Degradation Mechanism of Cationic Red X-GRL by Ozonation

    Institute of Scientific and Technical Information of China (English)

    Wei Rong ZHAO; Xin Hua XU; Hui Xiang SHI; Da Hui WANG


    The degradation mechanism of Cationic Red X-GRL was investigated when the intermediates, the nitrate ion and the pH were analyzed in the ozonation. The degradation of the Cationic Red X-GRL includes the de-auxochrome stage, the decolour stage, and the decomposition of fragment stage. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one becomes the form of an amine compound, and the rest four are transformed into two molecules of nitrogen. In the course of the ozonation of Cationic Red X-GRL, the direct attack of ozone is the main decolour effect.

  4. Silica surfaces lubrication by hydrated cations adsorption from electrolyte solutions. (United States)

    Donose, Bogdan C; Vakarelski, Ivan U; Higashitani, Ko


    Adsorption of hydrated cations on hydrophilic surfaces has been related to a variety of phenomena associated with the short-range interaction forces and mechanisms of the adhesive contact between the surfaces. Here we have investigated the effect of the adsorption of cations on the lateral interaction. Using lateral force microscopy (LFM), we have measured the friction force between a silica particle and silica wafer in pure water and in electrolyte solutions of LiCl, NaCl, and CsCl salts. A significant lubrication effect was demonstrated for solutions of high electrolyte concentrations. It was found that the adsorbed layers of smaller and more hydrated cations have a higher lubrication capacity than the layers of larger and less hydrated cations. Additionally, we have demonstrated a characteristic dependence of the friction force on the sliding velocity of surfaces. A mechanism for the observed phenomena based on the microstructures of the adsorbed layers is proposed.

  5. Cationic polymers for successful flocculation of marine microalgae

    NARCIS (Netherlands)

    Lam, 't G.P.; Vermuë, M.H.; Olivieri, G.; Broek, van den L.A.M.; Barbosa, M.J.; Eppink, M.H.M.; Wijffels, R.H.; Kleinegris, D.M.M.


    Flocculation of microalgae is a promising technique to reduce the costs and energy required for harvesting microalgae. Harvesting marine microalgae requires suitable flocculants to induce the flocculation under marine conditions. This study demonstrates that cationic polymeric flocculants can be

  6. Infrared spectrum of the chloromethylene hydroperoxide cation in solid argon (United States)

    Chen, Mohua; Zhou, Mingfei


    Infrared spectrum of the chloromethylene hydroperoxide cation, HC(Cl)OOH+ in solid argon is reported. The cation is produced by co-condensation of dichloromethane and dioxygen mixtures with high-frequency discharged argon at 4 K followed by visible light excitation. On the basis of isotopic substitutions as well as quantum chemical frequency calculations, absorptions at 3452.7, 3052.0, 1499.6, 976.9, 855.4 and 956.1 cm-1 are assigned to the O-H, C-H, Cdbnd O, C-Cl and O-O stretching and out-of-plane CH wagging vibrations of the chloromethylene hydroperoxy cation. The cation was predicted to have a singlet ground state with planar Cs symmetry.

  7. Condensation of nonstochiometric DNA/polycation complexes by divalent cations. (United States)

    Budker, Vladimir; Trubetskoy, Vladimir; Wolff, Jon A


    This study found that divalent cations induced the further condensation of partially condensed DNA within nonstochiometric polycation complexes. The addition of a few mmol of a divalent cation such as calcium reduced by half the inflection point at which DNA became fully condensed by poly-L-lysine (PLL) and a variety of other polycations. The effect on DNA condensation was initially observed using a new method, which is based on the concentration-dependent self-quenching of fluorescent moieties (e.g., rhodamine) covalently linked to the DNA backbone at relatively high densities. Additional analyses, which employed ultracentrifugation, dynamic light scattering, agarose gel electrophoresis, and atomic force microscopy, confirmed the effect of divalent cations. These results provide an additional accounting of the process by which divalent cations induce greater chromatin compaction that is based on the representation of chromatin fibers as a nonstoichiometric polyelectrolyte complex. They also offer a new approach to assemble nonviral vectors for gene therapy.

  8. Methylene blue (cationic dye) adsorption into Salvadora persica ...

    African Journals Online (AJOL)

    Methylene blue (cationic dye) adsorption into Salvadora persica stems ash. ... African Journal of Biotechnology. Journal Home · ABOUT ... Abstract. Methylene blue (MB) is the most commonly used substance for dyeing cotton, wood and silk.

  9. Competition by meperidine for the organic cation renal excretory system. (United States)

    Acara, M; Gessner, T; Trudnowski, R J


    Renal tubular excretory transport of meperidine was studied using the Sperber preparation in chickens. When urine samples from infused and uninfused kidneys were analyzed for meperidine by gas chromatography, meperidine was always present in greater amounts in the urine from the infused kidney, demonstrating active tubular excretion. Meperidine at an infusion rate of 1 mumole/min, also inhibited the excretion of the organic cations choline and acetylcholine, indicating occupation of the renal organic cation excretory system in the chicken.

  10. Mercury release from deforested soils triggered by base cation enrichment

    Energy Technology Data Exchange (ETDEWEB)

    Farella, N. [Institut des sciences de l' environnement, Universite du Quebec a Montreal, CP 8888 Succ. Centre-Ville, Montreal (Quebec), H3C 3P8 (Canada)]. E-mail:; Lucotte, M. [Institut des sciences de l' environnement, Universite du Quebec a Montreal, CP 8888 Succ. Centre-Ville, Montreal (Quebec), H3C 3P8 (Canada)]. E-mail:; Davidson, R. [Institut des sciences de l' environnement, Universite du Quebec a Montreal, CP 8888 Succ. Centre-Ville, Montreal (Quebec), H3C 3P8 (Canada) and Biodome de Montreal, 4777 Pierre-De Coubertin, Montreal (Quebec), HIV 1B3 (Canada)]. E-mail:; Daigle, S. [Institut de recherche en biologie vegetale, 4101 Sherbrooke est, Montreal (Quebec), H1X 2B2 (Canada)]. E-mail:


    The Brazilian Amazon has experienced considerable colonization in the last few decades. Family agriculture based on slash-and-burn enables millions of people to live in that region. However, the poor nutrient content of most Amazonian soils requires cation-rich ashes from the burning of the vegetation biomass for cultivation to be successful, which leads to forest ecosystem degradation, soil erosion and mercury contamination. While recent studies have suggested that mercury present in soils was transferred towards rivers upon deforestation, little is known about the dynamics between agricultural land-use and mercury leaching. In this context, the present study proposes an explanation that illustrates how agricultural land-use triggers mercury loss from soils. This explanation lies in the competition between base cations and mercury in soils which are characterized by a low adsorption capacity. Since these soils are naturally very poor in base cations, the burning of the forest biomass suddenly brings high quantities of base cations to soils, destabilizing the previous equilibrium amongst cations. Base cation enrichment triggers mobility in soil cations, rapidly dislocating mercury atoms. This conclusion comes from principal component analyses illustrating that agricultural land-use was associated with base cation enrichment and mercury depletion. The overall conclusions highlight a pernicious cycle: while soil nutrient enrichment actually occurs through biomass burning, although on a temporary basis, there is a loss in Hg content, which is leached to rivers, entering the aquatic chain, and posing a potential health threat to local populations. Data presented here reflects three decades of deforestation activities, but little is known about the long-term impact of such a disequilibrium. These findings may have repercussions on our understanding of the complex dynamics of deforestation and agriculture worldwide.

  11. Focused fluorescent probe library for metal cations and biological anions. (United States)

    Rhee, Hyun-Woo; Lee, Sang Wook; Lee, Jun-Seok; Chang, Young-Tae; Hong, Jong-In


    A focused fluorescent probe library for metal cations was developed by combining metal chelators and picolinium/quinolinium moieties as combinatorial blocks connected through a styryl group. Furthermore, metal complexes derived from metal chelators having high binding affinities for metal cations were used to construct a focused probe library for phosphorylated biomolecules. More than 250 fluorescent probes were screened for identifying an ultraselective probe for dTTP.


    Institute of Scientific and Technical Information of China (English)

    W. Liu; Y. Ni; H. Xiao


    Hydrophilic and cationic montmorillonite is desirable for pitch control in the pulp and paper industry. In this paper, polyaminoamide - epichlorohydrin (PAE)modified montmorillonite was prepared. The modified montmorillonite was characterized using X-ray diffraction, FTIR and thermal gravimetric analysis. The amount of PAE intercalated and cationic charge densities of the modified montmorillonite were determined. Finally, it was found that both the solution and melt-intercalated samples with different charge densities exhibited strong interactions with dispersed colloidal rosin acid.

  13. Conductivity Measurements of Silverpastes

    Directory of Open Access Journals (Sweden)

    M. Dirix


    Full Text Available The development of three-dimensional printed circuit boards requires research on new materials which can easily be deformed. Conducting pastes are well suited for deformation even after they are applied to the dielectric carrier. This paper deals with measurements of the electrical conductivity of these conducting pastes. Two different conductivity measurement techniques are explained and carried out. The resulting measurements give an overview of the conductivity of several measured samples.

  14. Synthesis and characterisation of cationically modified phospholipid polymers. (United States)

    Lewis, Andrew L; Berwick, James; Davies, Martyn C; Roberts, Clive J; Wang, Jin-Hai; Small, Sharon; Dunn, Anthony; O'Byrne, Vincent; Redman, Richard P; Jones, Stephen A


    Phospholipid-like copolymers based on 2-(methacryloyloxyethyl) phosphorylcholine were synthesised using monomer-starved free radical polymerisation methods and incorporating cationic charge in the form of the choline methacrylate monomer in amounts varying from 0 to 30 wt%, together with a 5 wt% silyl cross-linking agent in order to render them water-insoluble once thermally cured. Characterisation using a variety of techniques including nuclear magnetic resonance spectroscopy, high-pressure liquid chromatography and gel permeation chromatography showed the cationic monomer did not interfere with the polymerisation and that the desired amount of charge had been incorporated. Gravimetric and differential scanning calorimetry methods were used to evaluate the water contents of polymer membranes cured at 70 degrees C, which was seen to increase with increasing cation content, producing materials with water contents ranging from 50% to 98%. Surface plasmon resonance indicated that the coatings swelled rapidly in water, the rate and extent of swelling increasing with increasing cation level. Dynamic contact angle showed that coatings of all the polymers possessed a hydrophobic surface when dry in air, characteristic of the alkyl chains expressed at the surface (>100 degrees advancing angle). Rearrangement of the hydrophilic groups to the surface occurred once wet, to produce highly wettable surfaces with a decrease in advancing angle with increasing cation content. Atomic force microscopy showed all polymer films to be smooth with no features in topographical or phase imaging. Mechanical properties of the dry films were also unaffected by the increase in cation content.

  15. Modulatory role of bivalent cations on reward system. (United States)

    Nechifor, M; Chelărescu, D


    Bivalent cations (Ca, Mg, Zn, Mn etc.) modulate activity of reward system (RS). At physiologic levels they may influence all components of RS. There are influenced behavioral reactions at physiological stimuli and all essential elements of drug dependence (compulsive intake of substance, craving, reinforcement, withdrawal syndrom, relapse and reinstatement of intake) The fact that some cations (e.g. calcium) enhance some of the aspects of drug dependence and others (e.g. magnesium, zinc) decrease intensity of this process show that ratio between intra- and extracellular in the brain of these cations is important for the function of RS. Among actions of different cations at the level of RS there are important differences. Their mecahanism of action are common in part and specific in other. It is important the fact that modulatory action appear at physiologic cation concentrations (that could be reached at therapeutic doses). Modulatory action is related to ratio between concetrations of different bivalent cations and is exerted both in normal or pathologic conditions.

  16. Complexation Between Cationic Diblock Copolymers and Plasmid DNA (United States)

    Jung, Seyoung; Reineke, Theresa; Lodge, Timothy

    Deoxyribonucleic acids (DNA), as polyanions, can spontaneously bind with polycations to form polyelectrolyte complexes. When the polycation is a diblock copolymer with one cationic block and one uncharged hydrophilic block, the polyelectrolyte complexes formed with plasmid DNA (pDNA) are often colloidally stable, and show great promise in the field of polymeric gene therapy. While the resulting properties (size, stability, and toxicity to biological systems) of the complexes have been studied for numerous cationic diblocks, the fundamentals of the pDNA-diblock binding process have not been extensively investigated. Herein, we report how the cationic block content of a diblock influences the pDNA-diblock interactions. pDNA with 7164 base pairs and poly(2-deoxy-2-methacrylamido glucopyranose)-block-poly(N-(2-aminoethyl) methacrylamide) (PMAG-b-PAEMA) are used as the model pDNA and cationic diblock, respectively. To vary the cationic block content, two PMAG-b-PAEMA copolymers with similar PMAG block lengths but distinct PAEMA block lengths and a PAEMA homopolymer are utilized. We show that the enthalpy change from pDNA-diblock interactions is dependent on the cationic diblock composition, and is closely associated with both the binding strength and the pDNA tertiary structure.

  17. Tunable states of interlayer cations in two-dimensional materials

    Energy Technology Data Exchange (ETDEWEB)

    Sato, K.; Numata, K. [Department of Environmental Sciences, Tokyo Gakugei University, Koganei, Tokyo 184-8501 (Japan); Dai, W. [Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 (China); Hunger, M. [Institute of Chemical Technology, University of Stuttgart, 70550 Stuttgart (Germany)


    The local state of cations inside the Ångstrom-scale interlayer spaces is one of the controlling factors for designing sophisticated two-dimensional (2D) materials consisting of 2D nanosheets. In the present work, the molecular mechanism on how the interlayer cation states are induced by the local structures of the 2D nanosheets is highlighted. For this purpose, the local states of Na cations in inorganic 2D materials, in which the compositional fluctuations of a few percent are introduced in the tetrahedral and octahedral units of the 2D nanosheets, were systematically studied by means of {sup 23}Na magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) and {sup 23}Na multiple-quantum MAS (MQMAS) NMR spectroscopy. In contrast with an uniform distribution of Na cations expected so far, various well-defined cation states sensitive to the local structures of the 2D nanosheets were identified. The tunability of the interlayer cation states along with the local structure of the 2D nanosheets, as the smallest structural unit of the 2D material, is discussed.

  18. Photochemical generation, isomerization, and oxygenation of stilbene cation radicals

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, F.D.; Bedell, A.M.; Dykstra, R.E.; Elbert, J.E. (Northwestern Univ., Evanston, IL (USA)); Gould, I.R.; Farid, S. (Eastman Kodak Co., Rochester, NY (USA))


    The cation radicals of cis- and trans-stilbene and several of their ring-substituted derivatives have been generated in solution directly by means of pulsed-laser-induced electron transfer to singlet cyanoanthracenes or indirectly via electron transfer from biphenyl to the singlet cyanoanthracene followed by secondary electron transfer from the stilbenes to the biphenyl cation radical. Transient absorption spectra of the cis- and trans-stilbene cation radicals generated by secondary electron transfer are similar to those previously obtained in 77 K matrices. Quantum yields for radical ion-pair cage escape have been measured for direct electron transfer from the stilbenes to three neutral and one charged singlet acceptor. These values increase as the ion-pair energy increases due to decreased rate constants for radical ion-pair return electron transfer, in accord with the predictions of Marcus theory for highly exergonic electron transfer. Cage-escape efficiencies are larger for trans- vs cis-stilbene cation radicals, possibly due to the greater extent of charge delocalization in the planar trans vs nonpolar cis cation radicals. Cage-escape stilbene cation radicals can initiate a concentration-dependent one way cis- {yields} trans-stilbene isomerization reaction.

  19. Computer simulation of alkali metal cation-montmorillonite hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Fang-Ru Chou [Columbia Univ., Palisades, NY (United States); Skipper, N.T. [Univ. College, London (United Kingdom); Sposito, G. [Lawrence Berkeley National Lab., CA (United States)


    Molecular structure in the interlayers of Li-, Na-, or K-Wyoming montmorillonite with one, two, or three adsorbed water layers was investigated for the first time by concurrent Monte Carlo and molecular dynamics (MD) simulation, based on the Matsouka-Clementi-Yoshimine, (MCY) model of water-water interactions. Calculated layer spacings, as well as interlayer-species self-diffusion coefficients, were in good agreement with available experimental data. Inner-sphere surface complexes of the cations with tetrahedral charge sites were observed for all hydrates, whereas outer-sphere surface complexes of the cations with octahedral charge sites, found also in the one-layer hydrate, tended to dissociate from the clay mineral basal planes into a diffuse layer in the two- and three-layer hydrates. Differences in the interlayer water structure among the hydrates mainly reflected cation solvation, although some water molecules were entrapped within cavities in the montmorillonite surface. All of the interlayer cation and water species exchanged on the time scale (0.2 ns) of the MD simulations. Comparisons with results obtained using, instead of the MCY model, the TIP4P model for water-water, cation-water, and cation-clay interactions indicated that layer spacings and interlayer species mobilities tend to be under-predicted by the TIP4P model.

  20. Cloning and first functional characterization of a plant cyclic nucleotide-gated cation channel

    Energy Technology Data Exchange (ETDEWEB)

    Leng, Q.; Mercier, R.W.; Yao, W.; Berkowitz, G.A.


    Cyclic nucleotide-gated (cng) non-selective cation channels have been cloned from a number of animal systems. These channels are characterized by direct gating upon cAMO or cGMO binding to the intracellular portion of the channel protein, which leads to an increase in channel conductance. Animal cng channels are involved in signal transduction systems; they translate stimulus-induced changes in cytosolic cyclic nucleotide into altered cell membrane potential and/or cation flux as part of a signal cascade pathway. Putative plant homologs of animal cng channels have been identified. However, functional characterization (i.e., demonstration of cyclic-nucleotide-dependent ion currents) of a plant cng channel has not yet been accomplished. The authors report the cloning and first functional characterization of a plant member of this family of ion channels. The Arabidopsis cDNA AtCNGC2 encodes a polypeptide with deduced homology to the {alpha}-subunit of animal channels, and facilitates cyclic nucleotide-dependent cation currents upon expression in a number of heterologous systems. AtCNGC2 expression in a yeast mutant lacking a low-affinity K{sup +} uptake system complements growth inhibition only when lipophilic nucleotides are present in the culture medium. Voltage clamp analysis indicates that Xenopus lawvis oocytes injected with AtCNGC2 cRNA demonstrate cyclic-nucleotide-dependent, inward-rectifying K{sup +} currents. Human embryonic kidney cells (HEK293) transfected with AtCNGC2 cDNA demonstrate increased permeability to Ca{sup 2+} only in the presence of lipophilic cyclic nucleotides. The evidence presented here supports the functional classification of AtCNGC2 as a cyclic-nucleotide-gated cation channel, and presents the first direct evidence identifying a plant member of this ion channel family.

  1. Changes in the Vibrational Spectra of Zeolites Due to Sorption of Heavy Metal Cations (United States)

    Król, M.; Mozgawa, W.; Barczyk, K.; Bajda, T.; Kozanecki, M.


    This work presents the results of spectroscopic (MIR and Raman) studies of zeolite structures after immobilization of heavy metal cations from aqueous solutions. The sorption of Ag+, Cu2+, Cd2+, Pb2+, Zn2+, and Cr3+ ions has been conducted on zeolites belonging to different structural groups, i.e., sodium forms of natural chabazite, mordenite, ferrierite, and clinoptilolite, as well as on synthetic zeolite Y. Systematic changes in intensities and positions of the bands corresponding to the characteristic ring vibrations have been observed in the measured spectra. The most visible changes are observed in the FT-IR spectra of the samples in the range of 850-450 cm-1, and in the Raman spectra in the range of 600-250 cm-1. Depending on the zeolite structure, the bands, which can be regarded as a kind of indicator of ion exchange, were indentifi ed. For example, in the case of IR spectra, these bands are at 766, 703, 648, 578, and 506 cm-1 for zeolite Y, at 733 and 560 cm-1 for mordenite, at 675 cm-1 for clinoptilolite, etc. The degree of changes depends on both the type of cation and its concentration in the initial solution. This is connected with the way of binding of metal ions to the zeolite aluminosilicate framework, i.e., a proportion of the ion exchange and chemisorption in the process. Cations mainly undergoing ion exchange, such as Cd2+ or Pb2+, have the greatest impact on the character of the spectra. On the other hand, Cr3+ ions practically do not modify the spectra of zeolites. Results of IR and Raman spectroscopic studies have been compared with those obtained by atomic absorption spectroscopy (AAS), from which the proportion of ion exchange to chemisorption in the process and the effective cation exchange capacity of the individual samples have been estimated.

  2. Development of Bioavailable Pools of Base Cations and P after Afforestation of Volcanic Soils in Iceland

    DEFF Research Database (Denmark)

    Ritter, Eva


    Few long-term studies have been conducted on changes in soil nutrients after afforestation in Iceland, a country with a young history of forest management. While fertilization was shown to improve survival of seedlings in the first years after planting on the nutrient limited soils, knowledge about...... sodium (Na) decreased only in the upper soil layer. Only Olsen-P and K concentrations were higher in the upper soil layer as compared to 10–20 cm depth. This indicates a higher biotic control as opposed to the geochemical control of the other base cations....

  3. Does the cation really matter? The effect of modifying an ionic liquid cation on an SN2 process. (United States)

    Tanner, Eden E L; Yau, Hon Man; Hawker, Rebecca R; Croft, Anna K; Harper, Jason B


    The rate of reaction of a Menschutkin process in a range of ionic liquids with different cations was investigated, with temperature-dependent kinetic data giving access to activation parameters for the process in each solvent. These data, along with molecular dynamics simulations, demonstrate the importance of accessibility of the charged centre on the cation and that the key interactions are of a generalised electrostatic nature.

  4. Native sulfur, sulfates and sulfides from the active Campi Flegrei volcano (southern Italy): Genetic environments and degassing dynamics revealed by mineralogy and isotope geochemistry (United States)

    Piochi, Monica; Mormone, Angela; Balassone, Giuseppina; Strauss, Harald; Troise, Claudia; De Natale, Giuseppe


    We investigated sulfur-bearing minerals from the Campi Flegrei caldera, southern Italy, in relation to the increase of hydrothermal activity phenomena since 2006, aimed at providing insights into the volcanic system dynamics. Mineral encrustations and muds were sampled between 2013 and 2015 at the long-standing degassing crater of the Solfatara tuff cone and its recently restless north-eastern Pisciarelli slope. Deep-seated sulfides were further separated from two drill cores (AGIP's Mofete boreholes: 1500 m and 2695 m depth). The mineral assemblage and texture of sampled encrustations were determined by X-ray diffraction, optical and scanning electron microscopy and X-ray microanalysis by energy dispersive spectrometry. Native sulfur and alunite dominate among the newly formed mineral phases. Other minerals are mostly alunogen, and locally pickeringite, potassium alum, hematite and pyrite. Mereiterite and amarillite sporadically occur. The mud pools are rich in gypsum, potassium alum and pyrite. Quartz and argillic phases, locally with analcime, are dispersed in the outcropping rocks. δ34S values were determined for shallow subsurface native sulfur (- 5.5 to 0.0‰) and alunite (- 1.7 to - 0.2‰), as well as for the deep-seated pyrite (3.3 to 7.4‰ in the depth range:1500-2695 m). δ18O values were measured for shallow native alunite (4.2 to 7.0‰). Pisciarelli alunite was finally analyzed for its 87Sr/86Sr ratio and 143Nd/144Nd ratios (0.707517 ± 6 and 0.512459 ± 6, respectively). Textural and isotopic data constrain the genesis of alunite at the expense of K-feldspars through rock alteration by hydrothermal fluids. We suggest that the caldera is a low-sulfidation system hosting acid-sulfate deposits in its active degassing area. The acid-sulfate environment developed on an argillitic facies that thins outwards and is characteristic for steam-heated and magmatic-steam environments. These environments developed in relation to the fractured settings that

  5. The conduction bands of MgO, MgS and HfO2

    NARCIS (Netherlands)

    Boer, P.K. de; Groot, R.A. de


    Electronic structure calculations for MgO, MgS and HfO2 are reported. It is shown that the conduction bands of MgO and MgS have predominantly anion character, contrary to the common picture of the conduction band being derived from cation states. In transition metal oxides, unoccupied anion states a

  6. Lack of association between a cationic protein and a cationic fluorosurfactant. (United States)

    Macakova, Lubica; Nordstierna, Lars; Karlsson, Göran; Blomberg, Eva; Furó, István


    Surface tension, 19F and 1H NMR spectroscopy, and cryotransmission electron microscopy are used to characterize the state of association in aqueous solutions of a fluorosurfactant CF3(CF2)nSO2NH(CH2)3-4N(CH3)3+ I- (n = 8, 6) with and without lysozyme added. In the absence of lysozyme, we find monomers, small aggregates, and large vesicles to coexist, with the individual fluorosurfactant molecules exchanging slowly (>1 ms) among those states. When both lysozyme and fluorosurfactant are present in the solution, they have no measurable influence on the physical state of the other. In contrast, a hydrogenated cationic surfactant with the same headgroup, hexadecyltrimethylammonium bromide, is shown to associate to lysozyme.

  7. Steam and gas emission rates from La Soufrière of Guadeloupe (Antilles arc): implications for the magmatic supply degassing during unrest (United States)

    Allard, Patrick; Aiuppa, Alessandro; Beauducel, François; Calabrese, Sergio; Di Napoli, Rossella; Crispi, Olivier; Gaudin, Damien; Parello, Franceso; Hammouya, Gilbert; Tamburello, Giancarlo


    Since its last magmatic eruption in 1530 AD, La Soufrière andesitic volcano in Guadeloupe has displayed intense hydrothermal activity and six phreatic eruptive crises (the last of which, in 1976-1977, with 73000 evacuees). Here we report on the first direct quantification of gas plume emissions from La Soufrière summit vents, which gradually intensified during the past 20 years. Gas fluxes were determined in 2006 then 2012 [1] by measuring the horizontal and vertical distribution of volcanic gas concentrations in the air-diluted plume, the composition of the hot fumarolic fluid at exit (108°C), and scaling to the speed of plume transport (in situ measurements and FLIR imaging). We first demonstrate that all fumarolic vents of La Soufrière are fed by a common H2O-rich (97-98 mol %) fluid end-member, emitted almost unmodified at the most active South Crater while affected by secondary alterations (steam condensation, sulphur scrubbing) at other vents. Daily fluxes in 2012 (200 tons of H2O, 15 tons of CO2, ~4 tons of H2S and 1 ton of HCl) were augmented by a factor ~3 compared to 2006, in agreement with increasing activity. Summit fumarolic degassing contributes most of the bulk volatile and heat budget (8 MW) of the volcano. Isotopic evidences demonstrate that La Soufrière hydrothermal emissions are sustained by continuous heat and gas supply from an andesitic magma reservoir confined at 6-7 km depth. This magmatic supply mixes with abundant groundwater of tropical meteoric origin in the hydrothermal system. Based on petro-geochemical data for the erupted magma(s), we assess that the volcanic gas fluxes in 2012 can be accounted for by the release of free magmatic gas derived from about 1000 m3 per day of the basaltic melt replenishing the reservoir at depth. In terms of mass budget, the current degassing unrest is compatible with enhanced free gas release from that reservoir, without requiring any (actually undetected) magma intrusion. We recommend a regular

  8. Mineralogical and sulfur isotopic characterization of the sulfur-bearing mineralization from the active degassing area of Campi Flegrei caldera (southern Italy) (United States)

    Mormone, Angela; Piochi, Monica; Balassone, Giuseppina; Strauss, Harald; Troise, Claudia; De Natale, Giuseppe


    The Campi Flegrei caldera is a site of persistent hydrothermal circulation and gaseous emissions inside the Pozzuoli town and nearby the city of Napoli (Italy). The solfataric phenomena are associated with episodes of low-magnitude seismicity and vertical ground displacement since Roman times, evolving to the Monte Nuovo eruption in the 1538 AD. Pronounced geochemical anomalies, uplift rates up to 1 m/y and up to ten thousands microearthquakes per year also characterized the four most recent decades of unrest. The degassing phenomena are concentrated within the Solfatara crater, although, since 2006, the hydrothermal activity strongly increased in the Pisciarelli district, i.e. on the north-east slope of the tuff. We investigated sulfur-bearing mineral precipitates sampled from the active fumaroles both within the Solfatara and along the Pisciarelli slope. Mineral assemblage, texture and chemistry were determined for the efflorescence precipitated nearby the fumaroles and along the mud pool by x-ray diffraction, back-scattered electron microscope and electron diffuse microanalysis. δ34S compositions were also determined on separated sulfur-minerals. The new data have been compared with scattered literature data, including few existing for the previous '70 and '80 unrest episodes. Native sulfur and alunite are the main mineral phases that associate with alunogene, and, locally, pickeringite and potassium alum. Sporadically mereiterite, amarillite, and pyrite have been found as neogenesis mineralization along the outcropping rocks. The mud pool is rich in gypsum, potassium alum and pyrite. δ34S values range from -5.48 to 0.0‰, being slightly lower than previous data. The obtained results suggest that the Pisciarelli area is characterized by magmatic-hydrothermal, magmatic-steam and steam-heated environments, developed on a argillitic hydrothermal facies that thickens in correspondence of the degassing area. These environments develop and continuously evolve in

  9. Cation selectivity by the CorA Mg2+ channel requires a fully hydrated cation. (United States)

    Moomaw, Andrea S; Maguire, Michael E


    The CorA Mg(2+) channel is the primary uptake system in about half of all bacteria and archaea. However, the basis for its Mg(2+) selectivity is unknown. Previous data suggested that CorA binds a fully hydrated Mg(2+) ion, unlike other ion channels. The crystal structure of Thermotoga maritima CorA shows a homopentamer with two transmembrane segments per monomer connected by a short periplasmic loop. This highly conserved loop, (281)EFMPELKWS(289) in Salmonella enterica serovar Typhimurium CorA, is the only portion of the channel outside of the cell, suggesting a role in cation selectivity. Mutation of charged residues in the loop, E281 and K287, to any of several amino acids had little effect, demonstrating that despite conservation electrostatic interactions with these residues are not essential. While mutation of the universally conserved E285 gave a minimally functional channel, E285A and E285K mutants were the most functional, again indicating that the negative charge at this position is not a determining factor. Several mutations at K287 and W288 behaved anomalously in a transport assay. Analysis indicated that mutation of K287 and W288 disrupts cooperative interactions between distinct Mg(2+) binding sites. Overall, these results are not compatible with electrostatic interaction of the Mg(2+) ion with the periplasmic loop. Instead, the loop appears to form an initial binding site for hydrated Mg(2+), not for the dehydrated cation. The loop residues may function to accelerate dehydration of the before entry of Mg(2+) into the pore of the channel.

  10. Conducting Polymeric Materials

    DEFF Research Database (Denmark)

    Hvilsted, Søren


    The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons...

  11. The Conductivity of Solutions. (United States)

    Rayner-Canham, Geoff


    Presents historical background and modern explanations for the popular demonstration of showing conductivity of solutions through the insertion of a light-bulb conductivity tester into deionized water and water with salt in it. (PR)

  12. High-performance cation-exchange chromatofocusing of proteins. (United States)

    Kang, Xuezhen; Frey, Douglas D


    Chromatofocusing using high-performance cation-exchange column packings, as opposed to the more commonly used anion-exchange column packings, is investigated with regard to the performance achieved and the range of applications possible. Linear or convex gradients in the range from pH 2.6 to 9 were formed using a variety of commercially available column packings that provide a buffering capacity in different pH ranges, and either polyampholytes or simple mixtures having a small number (three or fewer) of buffering species as the elution buffer. The resolutions achieved using cation-exchange or anion-exchange chromatofocusing were in general comparable, although for certain pairs of proteins better resolution could be achieved using one type of packing as compared to the other, evidently due to the way electrostatic charges are distributed on the protein surface. Several chromatofocusing methods were investigated that take advantage of the acid-base properties of commercially available cation-exchange column packings. These include the use of gradients with a composite shape, the use of very low pH ranges, and the use of elution buffers containing a single buffering species. The advantages of chromatofocusing over ion-exchange chromatography using a salt gradient at constant pH were illustrated by employing the former method and a cation-exchange column packing to separate beta-lactoglobulins A and B, which is a separation reported to be impossible using the latter method and a cation-exchange column packing. Trends in the apparent isoelectric points determined using cation- and anion-exchange chromatofocusing were interpreted using applicable theories. Results of this study indicate that cation-exchange chromatofocusing is a useful technique which is complementary to anion-exchange chromatofocusing and isoelectric focusing for separating proteins at both the analytical and preparative scales.

  13. Conductive paper from lignocellulose wood microfibers coated with a nanocomposite of carbon nanotubes and conductive polymers

    Energy Technology Data Exchange (ETDEWEB)

    Agarwal, Mangilal; Xing Qi; Lvov, Yuri [Institute for Micromanufacturing, Louisiana Tech University, Ruston, LA 71272 (United States); Shim, Bong Sup; Kotov, Nicholas [Chemical Engineering Department, University of Michigan, Ann Arbor, MI 48109 (United States); Varahramyan, Kody [Electrical and Computer Engineering Department, Indiana University-Purdue University Indianapolis, Indianapolis, IN 46202 (United States)], E-mail:


    Composite nanocoating of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) and aqueous dispersion of carbon nanotubes (CNT-PSS) on lignocellulose wood microfibers has been developed to make conductive microfibers and paper sheets. To construct the multilayers on wood microfibers, cationic poly(ethyleneimine) (PEI) has been used in alternate deposition with anionic conductive PEDOT-PSS and solubilized CNT-PSS. Using a Keithley microprobe measurement system, current-voltage measurements have been carried out on single composite microfibers after deposition of each layer to optimize the electrical properties of the coated microfibers. The conductivity of the resultant wood microfibers was in the range of 10{sup -2}-2 S cm{sup -1} depending on the architecture of the coated layer. Further, the conductivity of the coated wood microfibers increased up to 20 S cm{sup -1} by sandwiching multilayers of conductive co-polymer PEDOT-PSS with CNT-PSS through a polycation (PEI) interlayer. Moreover, paper hand sheets were manufactured from these coated wood microfibers with conductivity ranging from 1 to 20 S cm{sup -1}. A paper composite structure consisting of conductive/dielectric/conductive layers that acts as a capacitor has also been fabricated and is reported.

  14. Limits of proton conductivity. (United States)

    Kreuer, Klaus-Dieter; Wohlfarth, Andreas


    Parasitic current seems to be the cause for the "highest proton conductivity" of a material reported to date. Kreuer and Wohlfarth verify this hypothesis by measuring the conductivity of the same materials after preparing them in a different way. They further explain the limits of proton conductivity and comment on the problems of determining the conductivity of small objects (e.g., whiskers, see picture).

  15. Modeling of the thermal state of Mount Vesuvius from 1631 A.D. to present and the role of CO2 degassing on the volcanic conduit closure after the 1944 A.D. eruption (United States)

    Quareni, Francesca; Moretti, Roberto; Piochi, Monica; Chiodini, Giovanni


    The last eruptive event at Mount Vesuvius occurred in 1944 A.D., ending a cycle of continuous eruptive activity started with the sub-Plinian event of 1631 A.D. The aim of this research is (1) to model the thermal evolution of the volcanic system from 1631 A.D. up to the present and (2) to investigate the possible process leading the volcano to the current state of quiescence. A finite element software is employed to solve the time-dependent energy equation and obtain the thermal field in the volcanic edifice and the surrounding medium. Volcanological, petrological, and geophysical constraints are used to define the crustal structure beneath the volcanic edifice, the magma supply system active since 1631 A.D., and the physico-chemical conditions of magma. Thermodynamic properties of magma and wall rocks have been evaluated from well-established thermo-chemical compilations and data from the literature. It is shown that heat transfer due to magma degassing is required in addition to the heat conduction in order to obtain transient depth-temperature fields consistent with geochemical observations, high crustal magnetization, and rigid behavior of the shallow crust as indicated by geophysical data. Surface data of carbon dioxide soil flux coming out from the Mount Vesuvius crater are taken to constrain such an additional heat flux. The agreement between modeled and measured temperatures at the crater since 1944 A.D. proves the consistency of the model. It is concluded that the present state of quiescence of Mount Vesuvius is mostly a consequence of the absence of magma supply from the deep reservoir into the shallower system. This allows the cooling of residual magma left within the volcanic conduit and the transition from continuous eruptive activity to the condition of conduit obstruction. In this scenario, the hydrothermal system may have developed subsequent to the cooling of the magma within the conduit. Our findings are a direct consequence of the high

  16. Conducting polymer materials

    Directory of Open Access Journals (Sweden)

    Jovanović Slobodan M.


    Full Text Available Conducting polymers represent a very interesting group of polymer materials Investigation of the synthesis, structure and properties of these materials has been the subject of considerable research efforts in the last twenty years. A short presentating of newer results obtained by investigating of the synthesis, structure and properties of two basic groups of conducting polymers: a conducting polymers the conductivity of which is the result of their molecular structure, and b conducting polymer composites (EPC, is given in this paper. The applications and future development of this group of polymer materials is also discussed.

  17. Mind the bubbles: achieving stable measurements of maximum hydraulic conductivity through woody plant samples. (United States)

    Espino, Susana; Schenk, H Jochen


    The maximum specific hydraulic conductivity (k(max)) of a plant sample is a measure of the ability of a plants' vascular system to transport water and dissolved nutrients under optimum conditions. Precise measurements of k(max) are needed in comparative studies of hydraulic conductivity, as well as for measuring the formation and repair of xylem embolisms. Unstable measurements of k(max) are a common problem when measuring woody plant samples and it is commonly observed that k(max) declines from initially high values, especially when positive water pressure is used to flush out embolisms. This study was designed to test five hypotheses that could potentially explain declines in k(max) under positive pressure: (i) non-steady-state flow; (ii) swelling of pectin hydrogels in inter-vessel pit membranes; (iii) nucleation and coalescence of bubbles at constrictions in the xylem; (iv) physiological wounding responses; and (v) passive wounding responses, such as clogging of the xylem by debris. Prehydrated woody stems from Laurus nobilis (Lauraceae) and Encelia farinosa (Asteraceae) collected from plants grown in the Fullerton Arboretum in Southern California, were used to test these hypotheses using a xylem embolism meter (XYL'EM). Treatments included simultaneous measurements of stem inflow and outflow, enzyme inhibitors, stem-debarking, low water temperatures, different water degassing techniques, and varied concentrations of calcium, potassium, magnesium, and copper salts in aqueous measurement solutions. Stable measurements of k(max) were observed at concentrations of calcium, potassium, and magnesium salts high enough to suppress bubble coalescence, as well as with deionized water that was degassed using a membrane contactor under strong vacuum. Bubble formation and coalescence under positive pressure in the xylem therefore appear to be the main cause for declining k(max) values. Our findings suggest that degassing of water is essential for achieving stable and

  18. Enhanced Mixed Electronic-Ionic Conductors through Cation Ordering

    Energy Technology Data Exchange (ETDEWEB)

    Jacobson, Allan J. [Univ. of Houston, TX (United States); Morgan, Dane [Univ. of Wisconsin, Madison, WI (United States); Grey, Clare [Stony Brook Univ., NY (United States)


    The performance of many energy conversion and storage devices depend on the properties of mixed ionic-electronic conducting (miec) materials. Mixed or ambipolar conductors simultaneously transport ions and electrons and provide the critical interface between chemical and electrical energy in devices such as fuel cells, ion transport membranes, and batteries. Enhancements in storage capacity, reversibility, power density and device lifetime all require new materials and a better understanding of the fundamentals of ambipolar conductivity and surface reactivity.The high temperature properties of the ordered perovksites AA’B2O5+x, where A = rare earth ion, Y and B = Ba, Sr were studied. The work was motivated by the high oxygen transport and surface exchange rates observed for members of this class of mixed ionic and electronic conductors. A combined experimental and computational approach, including structural, electrochemical, and transport characterization and modeling was used. The approach attacks the problem simultaneously at global (e.g., neutron diffraction and impedance spectroscopy), local (e.g., pair distribution function, nuclear magnetic resonance) and molecular (ab initio thermokinetic modeling) length scales. The objectives of the work were to understand how the cation and associated anion order lead to exceptional ionic and electronic transport properties and surface reactivity in AA’B2O5+x perovskites. A variety of compounds were studied by X-ray and neutron diffraction, measurements of thermodynamics and transport and theoretically. These included PrBaCo2O5+x and NdBaCo2O5+x, PrBaCo2-xFexO6- δ (x = 0, 0.5, 1.0, 1.5 and 2) and LnBaCoFeO6- δ (Ln = La, Pr, Nd, Sm, Eu and Gd), Sr3YCo4O10.5, YBaMn2O5+x. A0.5A’0.5BO3 (where A=Y, Sc, La, Ce, Pr, Nd, Pm, Sm; A’= Sr

  19. Inkjet printed organic electrochemical transistors with highly conducting polymer electrolytes (United States)

    Afonso, Mónica; Morgado, Jorge; Alcácer, Luís


    Organic Electrochemical Transistors (OECTs) were fabricated with two kinds of highly conducting polymer electrolytes, one with cations of small dimensions (Li+) and the other with cations of large dimensions (1-ethyl-3-methylimidazolium, EMI+). All OECTs exhibit transconductance values in the millisiemens range. Those with the larger EMI+ cations reach higher transconductance values and the saturated region of their I(V) characteristics extends to drain negative voltages of the order of -2 V without breakdown. These OECTs aim at potential applications for which it is relevant to use a solid polymer electrolyte instead of an aqueous electrolyte, namely, for integration in complex devices or in sensors and transducers where the electrolyte film may act as a membrane to prevent direct contact of the active material (PEDOT:PSS) with the biological media. The choice of electrolytes with cations of disparate sizes aims at assessing the nature (Faradaic or capacitive) of the processes occurring at the electrolyte/channel interface. The results obtained are consistent with a Faradaic-based operation mechanism.

  20. Independent Generation and Reactivity of Thymidine Radical Cations. (United States)

    Sun, Huabing; Taverna Porro, Marisa L; Greenberg, Marc M


    Thymidine radical cation (1) is produced by ionizing radiation and has been invoked as an intermediate in electron transfer in DNA. Previous studies on its structure and reactivity have utilized thymidine as a precursor, which limits quantitative product analysis because thymidine is readily reformed from 1. In this investigation, radical cation 1 is independently generated via β-heterolysis of a pyrimidine radical generated photochemically from an aryl sulfide. Thymidine is the major product (33%) from 1 at pH 7.2. Diastereomeric mixtures of thymidine glycol and the corresponding 5-hydroxperoxides resulting from water trapping of 1 are formed. Significantly lower yields of products such as 5-formyl-2'-deoxyuridine that are ascribable to deprotonation from the C5-methyl group of 1 are observed. Independent generation of the N3-methyl analogue of 1 (NMe-1) produces considerably higher yields of products derived from water trapping, and these products are formed in much higher yields than those attributable to the C5-methyl group deprotonation in NMe-1. N3-Methyl-thymidine is, however, the major product and is produced in as high as 70% yield when the radical cation is produced in the presence of excess thiol. The effects of exogenous reagents on product distributions are consistent with the formation of diffusively free radical cations (1, NMe-1). This method should be compatible with producing radical cations at defined positions within DNA.

  1. Extreme environments in the critical zone: Linking acidification hazard of acid sulfate soils in mound spring discharge zones to groundwater evolution and mantle degassing. (United States)

    Shand, Paul; Gotch, Travis; Love, Andrew; Raven, Mark; Priestley, Stacey; Grocke, Sonia


    A decrease in flow from the iconic travertine mound springs of the Great Artesian Basin in South Australia has led to the oxidation of hypersulfidic soils and extreme soil acidification, impacting their unique groundwater dependent ecosystems. The build-up of pyrite in these systems occurred over millennia by the discharge of deep artesian sulfate-containing groundwaters through organic-rich subaqueous soils. Rare iron and aluminium hydroxysulfate minerals form thick efflorescences due to high evaporation rates in this arid zone environment, and the oxidised soils pose a significant risk to local aquatic and terrestrial ecosystems. The distribution of extreme acidification hazard is controlled by regional variations in the hydrochemistry of groundwater. Geochemical processes fractionate acidity and alkalinity into separate parts of the discharge zone allowing potentially extreme environments to form locally. Differences in groundwater chemistry in the aquifer along flow pathways towards the spring discharge zone are related to a range of processes including mineral dissolution and redox reactions, which in turn are strongly influenced by degassing of the mantle along deep crustal fractures. There is thus a connection between shallow critical zone ecosystems and deep crustal/mantle processes which ultimately control the formation of hypersulfidic soils and the potential for extreme geochemical environments.

  2. Soil temperature and CO2 degassing, SO2 fluxes and field observations before and after the February 29, 2016 new vent inside Nyiragongo crater (United States)

    Balagizi, Charles M.; Yalire, Mathieu M.; Ciraba, Honoré M.; Kajeje, Vicky B.; Minani, Abel S.; Kinja, Annie B.; Kasereka, Marcellin M.


    Nyiragongo volcano threatens ˜1.5 million inhabitants of Goma (DR Congo) and Gisenyi (Rwanda) cities and people living in the surrounding villages. In 2002, the volcano produced lava flows which invaded Goma and destroyed the economic district of the city, forced a mass exodus of the population and caused the loss of several lives. Nyiragongo volcanic activity is therefore closely followed by the inhabitants, and any news related to increased activity agitates people in the area, especially those in Goma. Here, we report a short time series of soil temperature and carbon dioxide degassing for four locations, and plume sulphur dioxide fluxes preceding and following the opening of a new vent inside the main Nyiragongo crater on February 29, 2016. The observed sudden and unexpected changes in Nyiragongo activity raised the fear of a new volcanic eruption and led to panic in Goma and the surrounding