Science.gov

Sample records for alkaline solution ph

  1. Technetium recovery from high alkaline solution

    DOEpatents

    Nash, Charles A.

    2016-07-12

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

  2. Alkaline pH sensor molecules.

    PubMed

    Murayama, Takashi; Maruyama, Ichiro N

    2015-11-01

    Animals can survive only within a narrow pH range. This requires continual monitoring of environmental and body-fluid pH. Although a variety of acidic pH sensor molecules have been reported, alkaline pH sensor function is not well understood. This Review describes neuronal alkaline pH sensors, grouped according to whether they monitor extracellular or intracellular alkaline pH. Extracellular sensors include the receptor-type guanylyl cyclase, the insulin receptor-related receptor, ligand-gated Cl- channels, connexin hemichannels, two-pore-domain K+ channels, and transient receptor potential (TRP) channels. Intracellular sensors include TRP channels and gap junction channels. Identification of molecular mechanisms underlying alkaline pH sensing is crucial for understanding how animals respond to environmental alkaline pH and how body-fluid pH is maintained within a narrow range.

  3. Field measurement of alkalinity and pH

    USGS Publications Warehouse

    Barnes, Ivan

    1964-01-01

    The behavior of electrometric pH equipment under field conditions departs from the behavior predicted from Nernst's law. The response is a linear function of pH, and hence measured pH values may be corrected to true pH if the instrument is calibrated with two reference solutions for each measurement. Alkalinity titrations may also be made in terms of true pH. Standard methods, such as colorimetric titrations, were rejected as unreliable or too cumbersome for rapid field use. The true pH of the end point of the alkalinity titration as a function of temperature, ionic strength, and total alkalinity has been calculated. Total alkalinity in potable waters is the most important factor influencing the end point pH, which varies from 5.38 (0 ? C, 5 ppm (parts per million) HC0a-) to 4.32 (300 ppm HC0a-,35 ? C), for the ranges of variables considered. With proper precautions, the pH may be determined to =i:0.02 pH and the alkalinity to =i:0.6 ppm HCO3- for many naturally occurring bodies of fresh water.

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

    SciTech Connect

    Chan, M.; Yen, T.F.

    1980-11-01

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

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

    PubMed

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

    2014-10-07

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

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

    PubMed

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

    2014-10-01

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

  7. Low pH alkaline chemical formulations

    SciTech Connect

    French, T.R.; Peru, D.A.; Thornton, S.D.

    1989-01-01

    This report describes the development of a surfactant-enhanced alkaline flooding system that is applicable to specific reservoir conditions in Wilmington (California) field. The cost of the chemicals for an ASP (alkali/surfactant/polymer) flood is calculated to be $3.90/bbl of oil produced, with 78% of that cost attributable to polymer. This research included phase behavior tests, oil displacement tests, mineral dissolution tests, and adsorption measurements. It was discovered that consumption of low pH alkalis is low enough in the Wilmington field to be acceptable. In addition, alkali dramatically reduced surfactant adsorption and precipitation. A mixture of NaHCO3 and Na2CO3 was recommended for use as a preflush and in the ASP formulation. Research was also conducted on the synergistic effect that occurs when a mixture of alkali and synthetic surfactant contacts crude oil. It appears that very low IFT is predominantly a result of the activation of the natural surfactants present in the Wilmington oil, and the sustained low IFT is primarily the result of the synthetic surfactant. It also appears that removal of acids from the crude oil by the alkali renders the oil more interfacially reactive to synthetic surfactant. These phenomena help to explain the synergism that results from combining alkali and synthetic surfactant into a single oil recovery formulation. 19 refs., 24 figs., 10 tabs.

  8. Method of determining pH by the alkaline absorption of carbon dioxide

    DOEpatents

    Hobbs, David T.

    1992-01-01

    A method for measuring the concentration of hydroxides in alkaline solutions in a remote location using the tendency of hydroxides to absorb carbon dioxide. The method includes the passing of carbon dioxide over the surface of an alkaline solution in a remote tank before and after measurements of the carbon dioxide solution. A comparison of the measurements yields the absorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to absorption fraction.

  9. Alkaline solution absorption of carbon dioxide method and apparatus

    DOEpatents

    Hobbs, D.T.

    1991-01-01

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

  10. Process for extracting technetium from alkaline solutions

    DOEpatents

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

    1995-01-01

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

  11. The Alkaline Diet: Is There Evidence That an Alkaline pH Diet Benefits Health?

    PubMed Central

    Schwalfenberg, Gerry K.

    2012-01-01

    This review looks at the role of an alkaline diet in health. Pubmed was searched looking for articles on pH, potential renal acid loads, bone health, muscle, growth hormone, back pain, vitamin D and chemotherapy. Many books written in the lay literature on the alkaline diet were also reviewed and evaluated in light of the published medical literature. There may be some value in considering an alkaline diet in reducing morbidity and mortality from chronic diseases and further studies are warranted in this area of medicine. PMID:22013455

  12. The alkaline diet: is there evidence that an alkaline pH diet benefits health?

    PubMed

    Schwalfenberg, Gerry K

    2012-01-01

    This review looks at the role of an alkaline diet in health. Pubmed was searched looking for articles on pH, potential renal acid loads, bone health, muscle, growth hormone, back pain, vitamin D and chemotherapy. Many books written in the lay literature on the alkaline diet were also reviewed and evaluated in light of the published medical literature. There may be some value in considering an alkaline diet in reducing morbidity and mortality from chronic diseases and further studies are warranted in this area of medicine.

  13. Method of determining pH by the alkaline absorption of carbon dioxide

    DOEpatents

    Hobbs, D.T.

    1992-10-06

    A method is described for measuring the concentration of hydroxides in alkaline solutions in a remote location using the tendency of hydroxides to absorb carbon dioxide. The method includes the passing of carbon dioxide over the surface of an alkaline solution in a remote tank before and after measurements of the carbon dioxide solution. A comparison of the measurements yields the absorption fraction from which the hydroxide concentration can be calculated using a correlation of hydroxide or pH to absorption fraction. 2 figs.

  14. Alkaline pH Homeostasis in Bacteria: New Insights

    PubMed Central

    Padan, Etana; Bibi, Eitan; Ito, Masahiro; Krulwich, Terry A.

    2011-01-01

    The capacity of bacteria to survive and grow at alkaline pH values is of widespread importance in the epidemiology of pathogenic bacteria, in remediation and industrial settings, as well as in marine, plant-associated and extremely alkaline ecological niches. Alkali-tolerance and alkaliphily, in turn, strongly depend upon mechanisms for alkaline pH homeostasis, as shown in pH shift experiments and growth experiments in chemostats at different external pH values. Transcriptome and proteome analyses have recently complemented physiological and genetic studies, revealing numerous adaptations that contribute to alkaline pH homeostasis. These include elevated levels of transporters and enzymes that promote proton capture and retention (e.g. the ATP synthase and monovalent cation/proton antiporters), metabolic changes that lead to increased acid production, and changes in the cell surface layers that contribute to cytoplasmic proton retention. Targeted studies over the past decade have followed up the long-recognized importance of monovalent cations in active pH homeostasis. These studies show the centrality of monovalent cation/proton antiporters in this process while microbial genomics provides information about the constellation of such antiporters in individual strains. A comprehensive phylogenetic analysis of both eukaryotic and prokaryotic genome databases has identified orthologes from bacteria to humans that allow better understanding of the specific functions and physiological roles of the antiporters. Detailed information about the properties of multiple antiporters in individual strains is starting to explain how specific monovalent cation/proton antiporters play dominant roles in alkaline pH homeostasis in cells that have several additional antiporters catalyzing ostensibly similar reactions. New insights into the pH-dependent Na+/H+ antiporter NhaA that plays an important role in Escherichia coli have recently emerged from the determination of the structure

  15. Use of natural mordenite to remove chromium (III) and to neutralize pH of alkaline waste waters.

    PubMed

    Córdova-Rodríguez, Valduvina; Rodríguez-Iznaga, Inocente; Acosta-Chávez, Raquel María; Chávez-Rivas, Fernando; Petranovskii, Vitalii; Pestryakov, Alexey

    2016-01-01

    The natural mordenite from Palmarito de Cauto deposit (PZ), Cuba, was studied in this work as an ion exchanger to remove Cr(3+) cations from alkaline aqueous solutions at different pH and chromium concentrations. The mordenite stability under cyclic treatment processes with alkaline solutions and its capacity to decrease the pH of the solutions was also analyzed. It was shown that PZ removes Cr(3+) ions from alkaline solutions, and it happens independently of the starting chromium concentration and the pH of the exchange solution used. This material has an important neutralizing effect on alkaline solutions, expressed in a significant pH decrease from the early stages of the treatments. For solutions with initial pH equal to 11, it decreases to a value of around seven. The stability of this material is not affected significantly after continuous cyclic treatment with NaOH solution, which shows that mordenite, in particular from Palmarito de Cauto deposit, has high stability in alkaline solutions. The results are important as they suggest that natural zeolites may be of interest in treatments of alkaline industrial waste effluents.

  16. Alkaline earth cation extraction from acid solution

    DOEpatents

    Dietz, Mark; Horwitz, E. Philip

    2003-01-01

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

  17. Biochemical Stabilization of Glucagon at Alkaline pH

    PubMed Central

    Jackson, Melanie A.; Castle, Jessica R.; El Youssef, Joseph; Bakhtiani, Parkash A.; Bergstrom, Colin P.; Carroll, Julie M.; Breen, Matthew E.; Leonard, Gerald L.; David, Larry L.; Roberts, Charles T.; Ward, W. Kenneth

    2014-01-01

    Abstract Background: For patients with type 1 diabetes mellitus, a bihormonal artificial endocrine pancreas system utilizing glucagon and insulin has been found to stabilize glycemic control. However, commercially available formulations of glucagon cannot currently be used in such systems because of physical instability characterized by aggregation and chemical degradation. Storing glucagon at pH 10 blocks protein aggregation but results in chemical degradation. Reductions in pH minimize chemical degradation, but even small reductions increase protein aggregation. We hypothesized that common pharmaceutical excipients accompanied by a new excipient would inhibit glucagon aggregation at an alkaline pH. Methods and Results: As measured by tryptophan intrinsic fluorescence shift and optical density at 630 nm, protein aggregation was indeed minimized when glucagon was formulated with curcumin and albumin. This formulation also reduced chemical degradation, measured by liquid chromatography with mass spectrometry. Biological activity was retained after aging for 7 days in an in vitro cell-based bioassay and also in Yorkshire swine. Conclusions: Based on these findings, a formulation of glucagon stabilized with curcumin, polysorbate-80, l-methionine, and albumin at alkaline pH in glycine buffer may be suitable for extended use in a portable pump in the setting of a bihormonal artificial endocrine pancreas. PMID:24968220

  18. Interpretation of pH, acidity, and alkalinity in fisheries and aquaculture

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Measurements of pH, acidity, and alkalinity are commonly used to describe water quality. The three variables are interrelated and are sometimes confused. The pH of water is an intensity factor, while the acidity and alkalinity of waters are capacity factors. More precisely, acidity and alkalinity ar...

  19. Solubility of pllutonium in alkaline salt solutions

    SciTech Connect

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

    1993-02-26

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

  20. Removal of plutonium and americium from alkaline waste solutions

    DOEpatents

    Schulz, Wallace W.

    1979-01-01

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

  1. Effect of pH alkaline salts of fatty acids on the inhibition of bacteria associated with poultry processing

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The agar diffusion assay was used to examine the effect of pH on the ability of alkaline salts of three fatty acids (FA) to inhibit growth of bacteria associated with poultry processing. FA solutions were prepared by dissolving 0.5 M concentrations of caprylic, capric, or lauric acid in separate ali...

  2. Decision making in C. elegans chemotaxis to alkaline pH

    PubMed Central

    Murayama, Takashi; Maruyama, Ichi N

    2013-01-01

    Monitoring of environmental and tissue pH is critical for animal survival. The nematode, Caenorhabditis elegans (C. elegans), is attracted to mildly alkaline pH, but avoids strongly alkaline pH. However, little is known about how the behavioral switching or decision making occurs. Genetic dissection and Ca2+ imaging have previously demonstrated that ASEL and ASH are the major sensory neurons responsible for attraction and repulsion, respectively. Here we report that unlike C. elegans wild type, mutants deficient in ASEL or ASH were repelled by mildly alkaline pH, or were attracted to strongly alkaline pH, respectively. These results suggest that signals through ASEL and ASH compete to determine the animal’s alkaline-pH chemotaxis. Furthermore, mutants with 2 ASEL neurons were more efficiently attracted to mildly alkaline pH than the wild type with a single ASEL neuron, indicating that higher activity of ASEL induces stronger attraction to mildly alkaline pH. This stronger attraction was overridden by normal activity of ASH, suggesting that ASH-mediated avoidance dominates ASEL-mediated attraction. Thus, C. elegans chemotactic behaviors to alkaline pH seems to be determined by signal strengths from the sensory neurons ASEL and ASH, and the behavior decision making seems to be the result of competition between the 2 sensory neurons. PMID:24563708

  3. pH neutralization and zonation in alkaline-saline tank waste plumes.

    PubMed

    Wan, Jiamin; Larsen, Joern T; Tokunaga, Tetsu K; Zheng, Zuoping

    2004-03-01

    At the Hanford Site in Washington State, the pH values of contaminant plumes resulting from leaking of initially highly alkaline-saline radioactive waste solutions into the subsurface are now found to be substantially neutralized. However, the nature of plume pH neutralization has not previously been understood. As a master geochemical variable, pH needs to be understood in order to predict the fate and transport of contaminants carried by the waste plumes. Through this laboratory study, we found that the plume pH values spanned a broad range from 14 (within the near-source region) down to the value of 7 (lower than the pH value of the initial soil solution) while the plume was still connected to an actively leaking source. We defined two zones within a plume: the silicate dissolution zone (SDZ, pH 14-10) and the neutralized zone (NZ, pH 10-7). Quartz dissolution at elevated temperature and precipitation of secondary silicates (including sodium metasilicate, cancrinite, and zeolites) are the key reactions responsible for the pH neutralization within the SDZ. The rapid and thorough cation exchange of Na+ replacing Ca2+/Mg2+, combined with transport, resulted in a dynamic Ca2+/Mg2+-enriched plume front. Subsequent precipitation of calcite, sodium silicate, and possibly talc led to dramatically reduced pH within the plume front and the neutralized zone. During aging (after the plume source became inactive), continued quartz dissolution and the secondary silicate precipitation drove the pH value lower, toward pH 11 at equilibrium within the SDZ, whereas the pH values in the NZ remained relatively unchanged with time. A pH profile of 11 from the plume source to pH 7 at the plume front is expected for a historical plume. This laboratory-based study provided realistic plume pH profiles (consistent with that measured from borehole samples) and identified underlying mechanisms responsible for pH evolution.

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

    SciTech Connect

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

    2009-06-01

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

  5. Uranium(VI) Diffusion in Sodium-Montmorillonite at Alkaline pH Conditions

    NASA Astrophysics Data System (ADS)

    Tinnacher, R. M.; Davis, J. A.; Tournassat, C.; Birkholzer, J. T.

    2015-12-01

    Diffusive transport of uranium(VI) in montmorillonite clay and bentonite has important implications for uranium(VI) mobility in engineered barrier systems or host rocks in high level radioactive waste repositories, and clay-rich soils and sediments in the environment. The prediction of uranium(VI) adsorption and diffusion in clay-rich media, however, is complicated by (1) the complexity of the mineralogical structure of montmorillonite, in terms of its pore-size distributions and available surface site types, and (2) the complex uranium(VI) solution speciation, which can include cationic, uncharged, and anionic complexes, depending on solution conditions. For instance, a partial or full exclusion of anions from negatively charged clay interlayer spaces could change the effective 'anion-accessible' porosity and decrease the diffusive flux of these solutes under steady state conditions. In contrast, weak cation exchange reactions can result in 'surface diffusion' of adsorbed cations, such as UO2OH+, in addition to diffusion in the liquid phase, resulting in greater diffusive fluxes at steady state. In order to investigate these complex interactions, we performed two, lab-scale uranium(VI) through-diffusion experiments in lightly compacted Na-montmorillonite at slightly different, alkaline pH conditions (average pH values of 8.69 and 8.87). Observed uranium(VI) diffusive fluxes were decreased by approximately an order of magnitude in comparison to a tritium tracer. This indicates a relevance of 'anion exclusion' effects, the full or partial exclusion of anionic U(VI)-carbonato species from clay interlayer spaces. In addition, uranium(VI) sorption reactions were shown to be relevant in the diffusion experiments, even at alkaline pH values of around 8.7 and 8.9, where uranium(VI) sorption is low compared to other pH conditions. Despite the similarity of pH conditions, different degrees of uranium(VI) retardation were determined for the two systems. Additionally, we

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

    PubMed

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

    2004-02-25

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

  7. SIMPLE WAYS TO IMPROVE PH AND ALKALINITY MEASUREMENTS FOR WATER UTILITIES AND LABORATORIES

    EPA Science Inventory

    Both pH and total alkalinity determinations are critical in characterizing chemical properties of water, being important to implementing good process control, determining corrosivity and other water quality properties, and assessing changes in water characteristics. Poor charac...

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

    NASA Astrophysics Data System (ADS)

    LaFlamme, Brian D.; Murray, James W.

    1987-02-01

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

  9. Cementitious porous pavement in stormwater quality control: pH and alkalinity elevation.

    PubMed

    Kuang, Xuheng; Sansalone, John

    2011-01-01

    A certain level of alkalinity acts as a buffer and maintains the pH value in a stable range in water bodies. With rapid urban development, more and more acidic pollutants flow to watersheds with runoff and drop alkalinity to a very low level and ultimately degrade the water environment. Cementitious porous pavement is an effective tool for stormwater acidic neutralization. When stormwater infiltrates cement porous pavement (CPP) materials, alkalinity and pH will be elevated due to the basic characteristics of cement concrete. The elevated alkalinity will neutralize acids in water bodies and maintain the pH in a stable level as a buffer. It is expected that CPP materials still have a certain capability of alkalinity elevation after years of service, which is important for CPP as an effective tool for stormwater management. However, few previous studies have reported on how CPP structures would elevate runoff alkalinity and pH after being exposed to rainfall-runoff for years. In this study, three groups of CPP specimens, all exposed to rainfall-runoff for 3 years, were used to test the pH and alkalinity elevation properties. It was found that runoff pH values were elevated from 7.4 to the range of 7.8-8.6 after infiltrating through the uncoated specimens, and from 7.4 to 8.5-10.7 after infiltrating through aluminum-coated specimens. Runoff alkalinity elevation efficiencies are 11.5-14.5% for uncoated specimens and 42.2% for coated specimens. The study shows that CPP is an effective passive unit operation for stormwater acid neutralization in our built environment.

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

    SciTech Connect

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

    2012-09-15

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

  11. An alkaline active xylanase: insights into mechanisms of high pH catalytic adaptation.

    PubMed

    Mamo, Gashaw; Thunnissen, Marjolein; Hatti-Kaul, Rajni; Mattiasson, Bo

    2009-09-01

    The alkaliphilic bacterium, Bacillus halodurans S7, produces an alkaline active xylanase (EC 3.2.1.8), which differs from many other xylanases in being operationally stable under alkaline conditions as well as at elevated temperature. Compared to non-alkaline active xylanases, this enzyme has a high percent composition of acidic amino acids which results in high ratio of negatively to positively charged residues. A positive correlation was observed between the charge ratio and the pH optima of xylanases. The recombinant xylanase was crystallized using a hanging drop diffusion method. The crystals belong to the space group P2(1)2(1)2(1) and the structure was determined at a resolution of 2.1 A. The enzyme has the common eight-fold TIM-barrel structure of family 10 xylanases; however, unlike non-alkaline active xylanases, it has a highly negatively charged surface and a deeper active site cleft. Mutational analysis of non-conserved amino acids which are close to the acid/base residue has shown that Val169, Ile170 and Asp171 are important to hydrolyze xylan at high pH. Unlike the wild type xylanase which has optimum pH at 9-9.5, the triple mutant xylanase (V169A, I170F and D171N), which was constructed using sequence information of alkaline sensitive xylanses was optimally active around pH 7. Compared to non-alkaline active xylanases, the alkaline active xylanases have highly acidic surfaces and fewer solvent exposed alkali labile residues. Based on these results obtained from sequence, structural and mutational analysis, the possible mechanisms of high pH stability and catalysis are discussed. This will provide useful information to understand the mechanism of high pH adaptation and engineering of enzymes that can be operationally stable at high pH.

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

    PubMed

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

    2014-01-01

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

  13. Change of pH during excess sludge fermentation under alkaline, acidic and neutral conditions.

    PubMed

    Yuan, Yue; Peng, Yongzhen; Liu, Ye; Jin, Baodan; Wang, Bo; Wang, Shuying

    2014-12-01

    The change in pH during excess sludge (ES) fermentation of varying sludge concentrations was investigated in a series of reactors at alkaline, acidic, and neutral pHs. The results showed that the changes were significantly affected by fermentative conditions. Under different conditions, pH exhibited changing profiles. When ES was fermented under alkaline conditions, pH decreased in a range of (10±1). At the beginning of alkaline fermentation, pH dropped significantly, at intervals of 4h, 4h, and 5h with sludge concentrations of 8665.6mg/L, 6498.8mg/L, and 4332.5mg/L, then it would become moderate. However, under acidic conditions, pH increased from 4 to 5. Finally, under neutral conditions pH exhibited a decrease then an increase throughout entire fermentation process. Further study showed short-chain fatty acids (SCFAs), ammonia nitrogen and cations contributed to pH change under various fermentation conditions. This study presents a novel strategy based on pH change to predict whether SCFAs reach their stable stage.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  15. Effect of initial solution pH on photo-induced reductive decomposition of perfluorooctanoic acid.

    PubMed

    Qu, Yan; Zhang, Chao-Jie; Chen, Pei; Zhou, Qi; Zhang, Wei-Xian

    2014-07-01

    The effects of initial solution pH on the decomposition of perfluorooctanoic acid (PFOA) with hydrated electrons as reductant were investigated. The reductive decomposition of PFOA depends strongly on the solution pH. In the pH range of 5.0-10.0, the decomposition and defluorination rates of PFOA increased with the increase of the initial solution pH. The rate constant was 0.0295 min(-1) at pH 10.0, which was more than 49.0 times higher than that at pH 5.0. Higher pH also inhibits the generation of toxic intermediates during the PFOA decomposition. For example, the short-chain PFCAs reached a lower maximum concentration in shorter reaction time as pH increasing. The peak areas of accumulated fluorinated and iodinated hydrocarbons detected by GC/MS under acidic conditions were nearly 10-100 times more than those under alkaline conditions. In short, alkaline conditions were more favorable for photo-induced reduction of PFOA as high pH promoted the decomposition of PFOA and inhibited the accumulation of intermediate products. The concentration of hydrated electron, detected by laser flash photolysis, increased with the increase of the initial pH. This was the main reason why the decomposition of PFOA in the UV-KI system depended strongly on the initial pH.

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

    PubMed

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

    1977-09-01

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

  17. Solubility of plutonium and uranium in alkaline salt solutions

    SciTech Connect

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

    1993-02-12

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

  18. The effect of pH on phosphorus availability and speciation in an aquaponics nutrient solution.

    PubMed

    Cerozi, Brunno da Silva; Fitzsimmons, Kevin

    2016-11-01

    The interaction between the main ions in aquaponics nutrient solutions affects chemical composition and availability of nutrients, and nutrient uptake by plant roots. This study determined the effect of pH on phosphorus (P) speciation and availability in an aquaponics nutrient solution and used Visual MINTEQ to simulate P species and P activity. In both experimental and simulated results, P availability decreased with increase in pH of aquaponics nutrient solutions. According to simulations, P binds to several cations leaving less free phosphate ions available in solution. High pH values resulted in the formation of insoluble calcium phosphate species. The study also demonstrated the importance of organic matter and alkalinity in keeping free phosphate ions in solution at high pH ranges. It is recommended though that pH in aquaponics systems is maintained at a 5.5-7.2 range for optimal availability and uptake by plants.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

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

    SciTech Connect

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

    1993-12-31

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

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

    PubMed

    Chi, Quan; Chen, Wanying; He, Zhike

    2015-11-01

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

  2. Irrigation water acidification to neutralize alkalinity for nursery crop production: Substrate pH, electrical conductivity, and nutrient concentrations; and plant nutrition and growth

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Liming agents (LA) in irrigation water, typically associated with carbonates and bicarbonates of calcium (Ca) and magnesium (Mg), contribute to water alkalinity. Repeated application of LA to container crops can cause media-solution pH to rise overtime, that uncorrected, can lead to a nutrient avail...

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

    PubMed Central

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

    2011-01-01

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

  4. Extremely alkaline (pH > 12) ground water hosts diverse microbial community.

    PubMed

    Roadcap, George S; Sanford, Robert A; Jin, Qusheng; Pardinas, José R; Bethke, Craig M

    2006-01-01

    Chemically unusual ground water can provide an environment for novel communities of bacteria to develop. Here, we describe a diverse microbial community that inhabits extremely alkaline (pH > 12) ground water from the Lake Calumet area of Chicago, Illinois, where historic dumping of steel slag has filled in a wetland. Using microbial 16S ribosomal ribonucleic acid gene sequencing and microcosm experiments, we confirmed the presence and growth of a variety of alkaliphilic beta-Proteobacteria, Bacillus, and Clostridium species at pH up to 13.2. Many of the bacterial sequences most closely matched those of other alkaliphiles found in more moderately alkaline water around the world. Oxidation of dihydrogen produced by reaction of water with steel slag is likely a primary energy source to the community. The widespread occurrence of iron-oxidizing bacteria suggests that reduced iron serves as an additional energy source. These results extend upward the known range of pH tolerance for a microbial community by as much as 2 pH units. The community may provide a source of novel microbes and enzymes that can be exploited under alkaline conditions.

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

    PubMed

    Brdicka, R

    1936-07-20

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

  6. Specific molten globule conformation of stem bromelain at alkaline pH.

    PubMed

    Dave, Sandeep; Mahajan, Sahil; Chandra, Vemika; Dkhar, H Kitdorlang; Sambhavi; Gupta, Pawan

    2010-07-01

    Stem bromelain (SBM), a therapeutic protein, is rapidly absorbed across the gut epithelium. Because SBM encounters an alkaline pH at its principal site of absorption, we investigated the alkaline-induced denaturation of SBM. From pH 7 to 10, the protein's secondary structure remained the same, although a slight loss of tertiary structure was observed. Above pH 10, there was a significant and irreversible loss of secondary and tertiary structure. At pH 10, SBM showed enhanced tryptophan fluorescence, however, the number of accessible tryptophans remained the same. The thermodynamics of temperature transition at pH 7 and 10 were strikingly different, with the former showing a two-phase transition endotherm, and the latter a broad non-two-state transition. At pH 10, SBM showed a significant increase in 8-anilino-1-naphthalene-sulfonate binding relative to the native state, suggestive of a specific molten globule (SMG) state. These studies suggest a distinct conformational rearrangement in SBM, at the protein's isoelectric point.

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

    SciTech Connect

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

    2004-03-29

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

  8. Improved volatile fatty acids anaerobic production from waste activated sludge by pH regulation: Alkaline or neutral pH?

    PubMed

    Ma, Huijun; Chen, Xingchun; Liu, He; Liu, Hongbo; Fu, Bo

    2016-02-01

    In this study, the anaerobic fermentation was carried out for volatile fatty acids (VFAs) production at different pH (between 7.0 and 10.0) conditions with untreated sludge and heat-alkaline pretreated waste activated sludge. In the fermentation with untreated sludge, the extent of hydrolysis of organic matters and extent of acidification at alkaline pH are 54.37% and 30.37%, respectively, resulting in the highest VFAs yield at 235.46mg COD/gVS of three pH conditions. In the fermentation with heat-alkaline pretreated sludge, the acidification rate and VFAs yield at neutral pH are 30.98% and 240.14mg COD/gVS, respectively, which are higher than that at other pH conditions. With the glucose or bovine serum albumin as substrate for VFAs production, the neutral pH showed a higher VFAs concentration than the alkaline pH condition. The results of terminal restriction fragment length polymorphism (T-RFLP) analysis indicated that the alkaline pH caused low microbial richness. Based on the results in this study, we demonstrated that the alkaline pH is favor of hydrolysis of organic matter in sludge while neutral pH improved the acidogenesis for the VFAs production from sludge. Our finding is obvious different to the previous research and helpful for the understanding of how heat-alkaline pretreatment and alkaline fermentation influence the VFAs production, and beneficial to the development of VFAs production process.

  9. Low temperature alkaline pH hydrolysis of oxygen-free Titan tholins

    NASA Astrophysics Data System (ADS)

    Brassé, Coralie; Buch, Arnaud; Raulin, François; Coll, Patrice; Poch, Olivier; Ramirez, Sandra

    2014-05-01

    The largest moon of Saturn, Titan, is known for its dense, nitrogen-rich atmosphere. The organic aerosols which are produced in Titan's atmosphere are of great astrobiological interest, particularly because of their potential evolution when they reach the surface and may interact with putative ammonia-water cryomagma[1]. In this context we have followed the evolution of alkaline pH hydrolysis (25wt% ammonia-water) of Titan tholins (produced by an experimental setup using a plasma DC discharge named PLASMA) at low temperature. Urea has been identified as one of the main product of tholins hydrolysis along with several amino acids (alanine, glycine and aspartic acid). However, those molecules have also been detected in non-hydrolyzed tholins. One explanation is a possible oxygen leak in the PLASMA reactor during the tholins synthesis[2]. Following this preliminary study the synthesis protocol has been improved by isolating the whole device in a specially designed glove box which protect the PLASMA experiment from the laboratory atmosphere. Once we confirmed the non-presence of oxygen in tholins, we performed alkaline pH hydrolysis of oxygen-free tholins. Then we verify that the organic compounds cited above are still produced in-situ. Moreover, a recent study shows that the subsurface ocean may contain a lower fraction of ammonia (about 5wt% or less[3]), than the one used until now in this kind of experimental study[2, 4]. Thus, we have carried out new hydrolysis experiments which take this lower value into account. Additional studies have provided new highlights on the bulk composition of Titan for various gas species. Indeed, the observed Saturn's atmosphere enrichment constrains the composition of the planetesimals present in the feeding zone of Saturn. The enrichment in volatiles in Saturn's atmosphere has been reproduced by assuming the presence of specific gas species[5, 6], in particular CO2 and H2S. In the present study we assume that those gas species have

  10. Electrochemical behavior of immobilized hemoglobin in alkaline solution

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  11. Design of stability at extreme alkaline pH in streptococcal protein G.

    PubMed

    Palmer, Benjamin; Angus, Katy; Taylor, Linda; Warwicker, Jim; Derrick, Jeremy P

    2008-04-30

    Protein G (PrtG) is widely used as an affinity-based ligand for the purification of IgG. It would be desirable to improve the resistance of affinity chromatography ligands, such as PrtG, to commercial cleaning-in-place procedures using caustic alkali (0.5 M NaOH). It has been shown that Asn residues are the most susceptible at extreme alkaline pH: here, we show that replacement of all three Asn residues within the IgG-binding domain of PrtG only improves stability towards caustic alkali by about 8-fold. Study of the effects of increasing pH on PrtG by fluorescence and CD shows that the protein unfolds progressively between pH 11.5 and 13.0. Calculation of the variation in electrostatic free energy with pH indicated that deprotonation of Tyr, Lys and Arg side-chains at high pH would destabilize PrtG. Introduction of the triple mutation Y3F/T16I/T18I into PrtG stabilized it by an extra 6.8 kcal/mol and the unfolding of the protein occurred at a pH of about 13, or 1.5 pH units higher than wild type. The results show that strategies for the stabilization of proteins at extreme alkaline pH should consider thermodynamic stabilization that will retain the tertiary structure of the protein and modification of surface electrostatics, as well as mutation of alkali-susceptible residues.

  12. The Effects of Alkaline pH on Microleakage of Mineral Trioxide Aggregate and Calcium Enriched Mixture Apical Plugs

    PubMed Central

    Mirhadi, Hossein; Moazzami, Fariborz; Rangani Jahromi, Saeed; Safarzade, Sareh

    2016-01-01

    Statement of the Problem Alkaline pH can affect the physical and chemical properties and sealing ability of apical plug material. Calcium hydroxide is used as an intracanal medication to complete disinfection of root canals. It raises the pH of environment to alkaline value. Purpose The aim of this in vitro study was to evaluate and compare the effect of alkaline pH on the sealing ability of calcium-enriched mixture (CEM) cement and mineral trioxide aggregate (MTA) apical plugs. Materials and Method Seventy single-rooted human maxillary anterior teeth were randomly divided to two experimental groups for Angelus MTA and CEM cement (n=30) and two control groups (n=5). Each group was divided into two subgroups of 15 for neutral and alkaline pH, and 1 negative and 1 positive control groups of 5. The root canals were cleaned and shaped by using ProTaper rotary system (Dentsply Maillefer; Ballaigues, Switzerland) and the terminal 3mm of the roots were resected. Then, MTA and CEM cement were condensed in apical region with 3mm thickness. The samples were exposed to two environments with different pH values of 13 and 7.4. The leakage was assessed by using the fluid filtration technique at 1, 7, 14, 30 days intervals. Data were analyzed by the repeated measures MANOVA. Results There was no statistically significant difference in the rate of microleakage between neutral and alkaline pH of CEM cement and MTA (p> 0.05). The sealing ability of MTA in an alkaline pH of 13 was significantly less than CEM cement in this pH (p< 0.05). Conclusion An environment with alkaline pH had no adverse effect on the sealing ability of MTA and CEM cement used as apical plugs. CEM cement had better sealing ability in alkaline pH. PMID:26966703

  13. Corrosion of silicon nitride in high temperature alkaline solutions

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    SciTech Connect

    Filik, H.; Apak, R.

    1998-06-01

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

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

    SciTech Connect

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

    2013-08-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

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

  17. Properties of hydroxyapatite crystallized from high temperature alkaline solutions

    NASA Astrophysics Data System (ADS)

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

    1996-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  19. Anoxic Biodegradation of Isosaccharinic Acids at Alkaline pH by Natural Microbial Communities

    PubMed Central

    Rout, Simon P.; Charles, Christopher J.; Doulgeris, Charalampos; McCarthy, Alan J.; Rooks, Dave J.; Loughnane, J. Paul; Laws, Andrew P.; Humphreys, Paul N.

    2015-01-01

    One design concept for the long-term management of the UK’s intermediate level radioactive wastes (ILW) is disposal to a cementitious geological disposal facility (GDF). Under the alkaline (10.0<pH>13.0) anoxic conditions expected within a GDF, cellulosic wastes will undergo chemical hydrolysis. The resulting cellulose degradation products (CDP) are dominated by α- and β-isosaccharinic acids (ISA), which present an organic carbon source that may enable subsequent microbial colonisation of a GDF. Microcosms established from neutral, near-surface sediments demonstrated complete ISA degradation under methanogenic conditions up to pH 10.0. Degradation decreased as pH increased, with β-ISA fermentation more heavily influenced than α-ISA. This reduction in degradation rate was accompanied by a shift in microbial population away from organisms related to Clostridium sporosphaeroides to a more diverse Clostridial community. The increase in pH to 10.0 saw an increase in detection of Alcaligenes aquatilis and a dominance of hydrogenotrophic methanogens within the Archaeal population. Methane was generated up to pH 10.0 with acetate accumulation at higher pH values reflecting a reduced detection of acetoclastic methanogens. An increase in pH to 11.0 resulted in the accumulation of ISA, the absence of methanogenesis and the loss of biomass from the system. This study is the first to demonstrate methanogenesis from ISA by near surface microbial communities not previously exposed to these compounds up to and including pH 10.0. PMID:26367005

  20. Transcriptome Profiling of Shewanella oneidensis Gene Expressionfollowing Exposure to Acidic and Alkaline pH

    SciTech Connect

    Leaphart, Adam B.; Thompson, Dorothea K.; Huang, Katherine; Alm,Eric; Wan, Xiu-Feng; Arkin, Adam P.; Brown, Steven D.; Wu, Liyou; Yan,Tingfen; Liu, Xueduan; Wickham, Gene S.; Zhou, Jizhong

    2007-04-02

    The molecular response of Shewanella oneidensis MR-1 tovariations in extracellular pH was investigated based on genomewide geneexpression profiling. Microarray analysis revealed that cells elicitedboth general and specific transcriptome responses when challenged withenvironmental acid (pH 4) or base (pH 10) conditions over a 60-minperiod. Global responses included the differential expression of genesfunctionally linked to amino acid metabolism, transcriptional regulationand signal transduction, transport, cell membrane structure, andoxidative stress protection. Response to acid stress included theelevated expression of genes encoding glycogen biosynthetic enzymes,phosphate transporters, and the RNA polymerase sigma-38 factor (rpoS),whereas the molecular response to alkaline pH was characterized byupregulation of nhaA and nhaR, which are predicted to encode an Na+/H+antiporter and transcriptional activator, respectively, as well assulfate transport and sulfur metabolism genes. Collectively, theseresults suggest that S. oneidensis modulates multiple transporters, cellenvelope components, and pathways of amino acid consumption and centralintermediary metabolism as part of its transcriptome response to changingexternal pH conditions.

  1. PMBP extraction and TPE separation in alkaline pyrophosphate solutions

    SciTech Connect

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

    1988-11-01

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

  2. Improved methane production from waste activated sludge with low organic content by alkaline pretreatment at pH 10.

    PubMed

    Feng, L Y; Yang, L Q; Zhang, L X; Chen, H L; Chen, J

    2013-01-01

    Sludge with low organic content always results in an unsatisfactory performance, even failure of anaerobic digestion. The alkaline pretreatment effect on anaerobic digestion of sludge with low organic content has seldom been studied although it gives many benefits for sludge with high organic content. In this study the influence of alkaline pretreatment (pH 10, an effective alkaline pH) on the solubilization and methane production from waste activated sludge (WAS) with low organic content was investigated. Results from biochemical methane potential (BMP) experiments showed that anaerobic biodegradability of WAS was greatly improved by alkaline pretreatment at pH 10. Methane production from the current WAS under conditions of pretreatment time 4 h and digestion time 15 d was 139.6 mL/g VS (volatile solids), much higher than that from the unpretreated WAS with digestion time of 20 d (75.2 mL/g VS). Also, the solubilization of WAS was significantly accelerated by alkaline pretreatment. Mechanism exploration indicated that the general activities of anaerobic microorganisms, specific activities of key enzymes and the amounts of methanogens were enhanced by alkaline pretreatment at pH 10, showing good agreement with methane production.

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

    PubMed

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

    2015-01-01

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

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

    PubMed

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

    2012-11-15

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

  5. Effect of Treatment pH on the End Products of the Alkaline Hydrolysis of TNT and RDX

    DTIC Science & Technology

    2007-06-01

    Comparison of final TOC of TNT alkaline hydrolysis solutions at three pHs........................19 Table 7. Results of ion chromatographic analysis ...25 Table 12. Results of ion chromatographic analysis of unlabeled RDX solutions following extended alkaline hydrolysis at three...8330 explo- sives analysis TOC IC Lime Control ERDC/EL TR-07-4 7 3 Materials and Methods Chemicals Chemicals used in this study included

  6. Influence of pH of spray solution on optoelectronic properties of cadmium oxide thin films

    NASA Astrophysics Data System (ADS)

    Hodlur, R. M.; Rabinal, M. K.

    2015-03-01

    Highly conducting transparent cadmium oxide thin films were prepared by the conventional spray pyrolysis technique. The pH of the spray solution is varied by adding ammonia/hydrochloric acid. The effect of pH on the morphology, crystallinity and optoelectronic properties of these films is studied. The structural analysis showed all the films in the cubic phase. For the films with pH < 7 (acidic condition), the preferred orientation is along the (111) direction and for those with pH >7 (alkaline condition), the preferred orientation is along the (200) direction. A lowest resistivity of 9.9 × 10-4 Ω·cm (with carrier concentration = 5.1 × 1020 cm-3, mobility = 12.4 cm2/(V·s)) is observed for pH ≈ 12. The resistivity is tuned almost by three orders of magnitude by controlling the bath pH with optical transmittance more than 70%. Thus, the electrical conductivity of CdO films could be easily tuned by simply varying the pH of the spray solution without compromising the optical transparency.

  7. High external pH enables more efficient secretion of alkaline α-amylase AmyK38 by Bacillus subtilis

    PubMed Central

    2012-01-01

    Background Bacillus subtilis genome-reduced strain MGB874 exhibits enhanced production of exogenous extracellular alkaline cellulase Egl-237 and subtilisin-like alkaline protease M-protease. Here, we investigated the suitability of strain MGB874 for the production of α-amylase, which was anticipated to provoke secretion stress responses involving the CssRS (Control secretion stress Regulator and Sensor) system. Results Compared to wild-type strain 168, the production of a novel alkaline α-amylase, AmyK38, was severely decreased in strain MGB874 and higher secretion stress responses were also induced. Genetic analyses revealed that these phenomena were attributable to the decreased pH of growth medium as a result of the lowered expression of rocG, encoding glutamate dehydrogenase, whose activity leads to NH3 production. Notably, in both the genome-reduced and wild-type strains, an up-shift of the external pH by the addition of an alkaline solution improved AmyK38 production, which was associated with alleviation of the secretion stress response. These results suggest that the optimal external pH for the secretion of AmyK38 is higher than the typical external pH of growth medium used to culture B. subtilis. Under controlled pH conditions, the highest production level (1.08 g l-1) of AmyK38 was obtained using strain MGB874. Conclusions We demonstrated for the first time that RocG is an important factor for secretory enzyme production in B. subtilis through its role in preventing acidification of the growth medium. As expected, a higher external pH enabled a more efficient secretion of the alkaline α-amylase AmyK38 in B. subtilis. Under controlled pH conditions, the reduced-genome strain MGB874 was demonstrated to be a beneficial host for the production of AmyK38. PMID:22681752

  8. Low temperature alkaline pH hydrolysis of oxygen-free Titan tholins

    NASA Astrophysics Data System (ADS)

    Brassé, C.; Buch, A.; Raulin, F.; Coll, P.; Poch, O.; Ramirez, S.

    2013-09-01

    Titan, the largest moon of Saturn, is known for its dense and nitrogen-rich atmosphere. The organic aerosols which are produced in Titan's atmosphere are objects of astrobiological interest. In this paper we focus on their potential chemical evolution when they reach the surface and interact with putative ammonia-water cryomagma[1]. In this context we have studied the evolution of alkaline pH hydrolysis of Titan tholins (produced by an experimental setup using a plasma DC discharge named PLASMA) at ambient and low temperature. However, we identified oxygenated molecules in non-hydrolyzed tholins meaning that oxygen gets in the PLASMA reactor during the tholins synthesis [2]. Following this preliminary study the synthesis protocol has been improved by isolating the whole device in a specially designed glove box which protect the PLASMA experiment from the laboratory atmosphere. After confirming the non-presence of oxygen in tholins produced with this new experimental setup, the study of oxygen-free tholins' evolution has been carried out. A recent study shows that the subsurface ocean may contain a lower fraction of ammonia (about 5wt% or less [3]), as previously described by other teams [2,4]. Thus new hydrolysis experiments will take this lower value into account. Additionally, a new report [5] provides upper and lower limits for the bulk content of Titan's interior for various gas species. It also shows that most of them are likely stored and dissolved in the subsurface water ocean. But considering the plausible acido-alkaline properties of the ammonia-water ocean, additional species could be dissolved in the ocean and present in the magma. They were also included in our hydrolysis experiments. Taking into account these new data, four different hydrolysis have been applied to oxygen-free tholins. For each type of hydrolysis, we also follow the influence of the hydrolysis temperature on the organic molecules production. The preliminary qualitative and quantitative

  9. The fluorescence properties of the phenylated fullerenes C 70Ph 4, C 70Ph 6, C 70Ph 8, and C 70Ph 10 in room temperature solutions

    NASA Astrophysics Data System (ADS)

    Schwell, Martin; Gustavsson, Thomas; Marguet, Sylvie; Vaissière, Benoı̂t de La; Wachter, Norbert K.; Birkett, Paul R.; Mialocq, Jean-Claude; Leach, Sydney

    2001-12-01

    The emission and excitation spectra of four phenylated [70] fullerenes, C 70Ph 4, C 70Ph 6, C 70Ph 8, and C 70Ph 10 in cyclohexane and toluene solutions have been measured. The fluorescence spectra and related excited state properties are found to depend strongly on the number of attached phenyl groups, but with no systematic trends. Quantum yields and fluorescence lifetimes were measured for C 70Ph 6, C 70Ph 8, and C 70Ph 10, allowing the determination of S1 → S0 radiative transition rates kR. It is found that kR for C 70Ph 10 is about six times larger than for the other compounds. This is consistent with measured absorbtivities for these compounds. The particular character of C 70Ph 10 is also manifested by its higher intersystem crossing rate kISC.

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

    PubMed

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

    2010-01-01

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

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

    SciTech Connect

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

    1997-02-11

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

  12. Quaternary structure of partially liganded intermediates of sheep carbon monoxide hemoglobin at alkaline pH.

    PubMed

    Gray, R D

    1975-01-25

    A rapid change in absorbance was observed in the Soret region during the interval between photolysis of sheep carbon monoxide hemoglobin and the subsequent reassociation of CO in the dark. The rate constant for this spectral change was about 4000 s--1 at 20 degrees in 0.05 M solium borate, pH 9.3. The wavelength dependence of the amplitude of the absorbance change is similar to that observed when deoxygenated alpha and theta chains are allowed to recombine (Brunori, M., Antonini, E., Wyman, J., and Anderson, S. R. (1968) J. Mol. Biol. 34, 357-359), and therefore reflects changes in the quanternary structure of the hemoglobin tetramer induced by ligand displacement. The amplitude of this conformation-dependent spectral change was not a linear function of the fraction of bound CO removed by photolysis. The results suggest that of the possible intermediate species present after partial photolysis, only Hb4 and Hb4(CO) change from the ligand-bound to the ligand-free sturcture prior to CO reassociation under these alkaline conditions.

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

    SciTech Connect

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

    2009-01-01

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

  14. Titrimetric determination of hydrogen peroxide in alkaline solution.

    PubMed

    McCurdy, W H; Bell, H F

    1966-07-01

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

  15. Primary radical yields in pulse irradiated alkaline aqueous solution

    NASA Technical Reports Server (NTRS)

    Fielden, E. M.; Hart, E. J.

    1969-01-01

    Primary radical yields of hydrated electrons, H atoms, and OH radicals are determined by measuring hydrated electron formation following a 4 microsecond pulse of X rays. The pH dependence of free radical yields beyond pH 12 is determined by observation of the hydrated electrons.

  16. Sewage sludge pretreatment by microwave irradiation combined with activated carbon fibre at alkaline pH for anaerobic digestion.

    PubMed

    Sun, Dedong; Guo, Sixiao; Ma, Nina; Wang, Guowen; Ma, Chun; Hao, Jun; Xue, Mang; Zhang, Xinxin

    2016-01-01

    This research focuses on the effects of microwave-assisted activated carbon fibre (ACF) (MW-ACF) treatment on sewage sludge at alkaline pH. The disintegration and biodegradability of sewage sludge were studied. It was found that the MW-ACF process at alkaline pH provided a rapid and efficient process to disrupt the microbial cells in the sludge. The results suggested that when irradiated at 800 W MW for 110 s with a dose of 1.0 g ACF/g solid concentration (SS) at pH 10.5, the MW-ACF pretreatment achieved 55% SS disintegration, 23% greater than the value of MW alone (32%). The concentration of total nitrogen, total phosphorus, supernatant soluble chemical oxygen demand, protein, and polysaccharide increased by 60%, 144%, 145%, 74%, and 77%, respectively. An increase in biogas production by 63.7% was achieved after 20 days of anaerobic digestion (AD), compared to the control. The results indicated that the MW-ACF pretreatment process at alkaline pH provides novel sludge management options in disintegration of sewage sludge for further AD.

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

    SciTech Connect

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

    2010-08-15

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

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

    SciTech Connect

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

    1999-05-01

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

  19. Evaluation of pH, alkalinity and temperature during air stripping process for ammonia removal from landfill leachate.

    PubMed

    Campos, Juacyara Carbonelli; Moura, Denise; Costa, Ana Paula; Yokoyama, Lidia; Araujo, Fabiana Valeria da Fonseca; Cammarota, Magali Christe; Cardillo, Luigi

    2013-01-01

    The objective of this research was to evaluate the air stripping technology for the removal of ammonia from landfill leachates. In this process, pH, temperature, airflow rate and operation time were investigated. Furthermore, the relationship between the leachate alkalinity and the ammonia removal efficiency during the process was studied. The leachate used in the tests was generated in the Gramacho Municipal Solid Waste Landfill (Rio de Janeiro State, Brazil). The best results were obtained with a temperature of 60(o)C, and they were independent of the pH value for 7 h of operation (the ammonia nitrogen removal was greater than 95%). A strong influence of the leachate alkalinity on the ammonia nitrogen removal was observed; as the alkalinity decreased, the ammonia concentration also decreased because of prior CO2 removal, which increased the pH and consequently favored the NH3 stripping. The air flow rate, in the values evaluated (73, 96 and 120 L air.h(-1).L(-1) of leachate), did not influence the results.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  1. Measurement and control of pH in hydrothermal solutions

    SciTech Connect

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

    1995-12-31

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

  2. Relationship between the pH of enema solutions and intestinal damage in rabbits.

    PubMed

    Zhang, Feng; Li, Xia; Xu, Xujuan; Cai, Duanying; Zhang, Jianguo

    2015-01-01

    Mechanical enemas can lead to intestinal mucosal injuries and bowel barrier damage, presenting as electrolyte disturbances and functional intestinal disorders. Most researchers believe that the mechanism of injury is related to osmolality, volume and temperature of the solution, infusion pressure, and the composition of the enema tube. We hypothesized that the pH of the enema solution may also contribute to intestinal damage. We administered enema solutions--normal saline, soapsuds, or vinegar (neutral, alkaline, or acidic solutions, respectively)--to three groups of rabbits (n = 20 per group). The solutions were standardized for volume and temperature and the soapsuds and vinegar solutions were adjusted to be isotonic with normal saline or deionized water. We also included a control group (n = 20) in which the enema tubes were inserted but no solution was administered. We biopsied 3 sites (rectum and distal and proximal colon). Damage to intestinal mucosa was observed by light microscopy and transmission electron microscopy. In order to explore the detection of damage using noninvasive methods, cyclooxygenase (COX)-2 gene expression was measured in the exfoliated cells gathered from postenema defecation. Epithelial loss, inflammatory reaction, and cellular microstructure damage was increased in the vinegar and soapsuds groups. Also, exfoliated cells in these groups had higher COX-2 expression than the normal saline group. The acidic and alkaline enema solutions thus caused more severe damage to the intestinal mucosa compared to the neutral liquid, supporting our hypothesis. Further, the detection of COX-2 expression shows promise as a noninvasive method for estimating enema-induced damage.

  3. Upper ocean carbon cycling inferred from direct pH observations made by profiling floats and estimated alkalinity

    NASA Astrophysics Data System (ADS)

    Johnson, K. S.; Plant, J. N.; Jannasch, H. W.; Coletti, L. J.; Elrod, V.; Sakamoto, C.; Riser, S.

    2015-12-01

    The annual cycle of dissolved inorganic carbon (DIC) is a key tracer of net community production and carbon export in the upper ocean. In particular, the DIC concentration is much less sensitive to air-sea gas exchange, when compared to oxygen, another key tracer of upper ocean metabolism. However, the annual DIC cycle is observed with a seasonal resolution at only a few time-series stations in the open ocean. Here, we consider the annual carbon cycle that has been observed using profiling floats equipped with pH sensors. Deep-Sea DuraFET pH sensors have been deployed on profiling floats for over three years and they can provide temporal and spatial resolution of 5 to 10 days and 5 to 10 m in the upper ocean over multi-year periods. In addition to pH, a second carbon system parameter is required to compute DIC. Total alkalinity can be derived from the float observations of temperature, salinity and oxygen using equations in these variables that are fitted to shipboard observations of alkalinity obtained in the global repeat hydrography programs (e.g., Juranek et al., GRL, doi:10.1029/2011GL048580, 2011), as the relationships should be stable in time in the open ocean. Profiling floats with pH have been deployed from Hawaii Ocean Time-series (HOT) cruises since late 2012 and an array of floats with pH have been deployed since early 2014 in the Southern Ocean as part of the SOCCOM program. The SOCCOM array should grow to nearly 200 floats over the next 5 years. The sensor data was quality controlled and adjusted by comparing observations at 1500 m depth to the deep climatology of pH (derived from DIC and alkalinity) computed with the GLODAP data set. After adjustment, the surface DIC concentrations were calculated from pH and alkalinity. This yields a data set that is used to examine annual net community production in the oligotrophic North Pacific and in the South Pacific near 150 West from 40 South to 65 South.

  4. The immobilization of all spermatozoa in vitro by bitter lemon drink and the effect of alkaline pH.

    PubMed

    Nwoha, P U

    1992-12-01

    Researchers at Obafemi Awolowo University in Ile-Ife, Nigeria, collected semen samples from 7 healthy men 25-30 years old who had abstained from sex for at least 5 days in order to examine the spermicidal action of 4 soft drinks (Krest bitter lemon, Afri-Cola, Coca-Cola, and Pepsi-Cola), the effect of increased temperature of the drinks on spermicidal action, and the effect of changing the soft drinks from an acid, as it comes from the factory, (ph 2.4) to an alkaline (pH 7.5). Increasing the temperature of the soft drinks from room temperature (22 degrees Celsius) to body temperatures (37 degrees Celsius) did not significantly change the spermicidal action any of the soft drinks. All soft drinks with an acid pH, except Coca-Cola, had a significantly lower percent of sperm motility than those with an alkaline pH (0-42.3% vs. 20-52.1%; p .001). In fact, Krest bitter lemon in its factory form (acid pH) completely immobilized all spermatozoa within 1 minute after the researchers diluted the semen with the soft drink. Alkaline Coca-Cola had a significantly lower percent of sperm motility than did acid Coca-Cola (35.8% vs. 46.5%; p .001). Other than Krest bitter lemon, the significant decreases in sperm motility were not enough to prevent pregnancy. These findings indicated that researchers should test Krest bitter lemon for effectiveness as a postcoital contraceptive. If indeed it proves effective, it has great potential as such a contraceptive among the poor in the densely population developed countries since it is readily available and inexpensive.

  5. Improvement of the optimum pH of Aspergillus niger xylanase towards an alkaline pH by site-directed mutagenesis.

    PubMed

    Li, Fei; Xie, Jingcong; Zhang, Xuesong; Zhao, Linguo

    2015-01-01

    In an attempt to shift the optimal pH of the xylanase B (XynB) from Aspergillus niger towards alkalinity, target mutation sites were selected by alignment between Aspergillus niger xylanase B and other xylanases that have alkalophilic pH optima that highlight charged residues in the eight-residues-longer loop in the alkalophilic xylanase. Multiple engineered XynB mutants were created by site-directed mutagenesis with substitutions Q164K and Q164K+D117N. The variant XynB-117 had the highest optimum pH (at 5.5), which corresponded to a basic 0.5 pH unit shift when compared with the wild-type enzyme. However, the optimal pH of the XynB- 164 mutation was not changed, similar to the wild type. These results suggest that the residues at positions 164 and 117 in the eight-residues-longer loop and the cleft's edge are important in determining the pH optima of XynB from Aspergillus niger.

  6. Carbon dioxide addition to microbial fuel cell cathodes maintains sustainable catholyte pH and improves anolyte pH, alkalinity, and conductivity.

    PubMed

    Fornero, Jeffrey J; Rosenbaum, Miriam; Cotta, Michael A; Angenent, Largus T

    2010-04-01

    Bioelectrochemical system (BES) pH imbalances develop due to anodic proton-generating oxidation reactions and cathodic hydroxide-ion-generating reduction reactions. Until now, workers added unsustainable buffers to reduce the pH difference between the anode and cathode because the pH imbalance contributes to BES potential losses and, therefore, power losses. Here, we report that adding carbon dioxide (CO(2)) gas to the cathode, which creates a CO(2)/bicarbonate buffered catholyte system, can diminish microbial fuel cell (MFC) pH imbalances in contrast to the CO(2)/carbonate buffered catholyte system by Torres, Lee, and Rittmann [Environ. Sci. Technol. 2008, 42, 8773]. We operated an air-cathode and liquid-cathode MFC side-by-side. For the air-cathode MFC, CO(2) addition resulted in a stable catholyte film pH of 6.61 +/- 0.12 and a 152% increase in steady-state power density. By adding CO(2) to the liquid-cathode system, we sustained a steady catholyte pH (pH = 5.94 +/- 0.02) and a low pH imbalance (DeltapH = 0.65 +/- 0.18) over a 2-week period without external salt buffer addition. By migrating bicarbonate ions from the cathode to the anode (with an anion-exchange membrane), we increased the anolyte pH (DeltapH = 0.39 +/- 0.31), total alkalinity (494 +/- 6 to 582 +/- 6 as mg CaCO(3)/L), and conductivity (1.53 +/- 0.49 to 2.16 +/- 0.03 mS/cm) relative to the feed properties. We also verified with a phosphate-buffered MFC that our reaction rates were limited mainly by the reactor configuration rather than limitations due to the bicarbonate buffer.

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

    PubMed

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

    2010-07-07

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

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

    PubMed

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

    2014-12-28

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

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

    PubMed

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

    2011-08-01

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

  11. Computational Design of a pH Stable Enzyme: Understanding Molecular Mechanism of Penicillin Acylase's Adaptation to Alkaline Conditions

    PubMed Central

    Suplatov, Dmitry; Panin, Nikolay; Kirilin, Evgeny; Shcherbakova, Tatyana; Kudryavtsev, Pavel; Švedas, Vytas

    2014-01-01

    Protein stability provides advantageous development of novel properties and can be crucial in affording tolerance to mutations that introduce functionally preferential phenotypes. Consequently, understanding the determining factors for protein stability is important for the study of structure-function relationship and design of novel protein functions. Thermal stability has been extensively studied in connection with practical application of biocatalysts. However, little work has been done to explore the mechanism of pH-dependent inactivation. In this study, bioinformatic analysis of the Ntn-hydrolase superfamily was performed to identify functionally important subfamily-specific positions in protein structures. Furthermore, the involvement of these positions in pH-induced inactivation was studied. The conformational mobility of penicillin acylase in Escherichia coli was analyzed through molecular modeling in neutral and alkaline conditions. Two functionally important subfamily-specific residues, Gluβ482 and Aspβ484, were found. Ionization of these residues at alkaline pH promoted the collapse of a buried network of stabilizing interactions that consequently disrupted the functional protein conformation. The subfamily-specific position Aspβ484 was selected as a hotspot for mutation to engineer enzyme variant tolerant to alkaline medium. The corresponding Dβ484N mutant was produced and showed 9-fold increase in stability at alkaline conditions. Bioinformatic analysis of subfamily-specific positions can be further explored to study mechanisms of protein inactivation and to design more stable variants for the engineering of homologous Ntn-hydrolases with improved catalytic properties. PMID:24959852

  12. Computational design of a pH stable enzyme: understanding molecular mechanism of penicillin acylase's adaptation to alkaline conditions.

    PubMed

    Suplatov, Dmitry; Panin, Nikolay; Kirilin, Evgeny; Shcherbakova, Tatyana; Kudryavtsev, Pavel; Svedas, Vytas

    2014-01-01

    Protein stability provides advantageous development of novel properties and can be crucial in affording tolerance to mutations that introduce functionally preferential phenotypes. Consequently, understanding the determining factors for protein stability is important for the study of structure-function relationship and design of novel protein functions. Thermal stability has been extensively studied in connection with practical application of biocatalysts. However, little work has been done to explore the mechanism of pH-dependent inactivation. In this study, bioinformatic analysis of the Ntn-hydrolase superfamily was performed to identify functionally important subfamily-specific positions in protein structures. Furthermore, the involvement of these positions in pH-induced inactivation was studied. The conformational mobility of penicillin acylase in Escherichia coli was analyzed through molecular modeling in neutral and alkaline conditions. Two functionally important subfamily-specific residues, Gluβ482 and Aspβ484, were found. Ionization of these residues at alkaline pH promoted the collapse of a buried network of stabilizing interactions that consequently disrupted the functional protein conformation. The subfamily-specific position Aspβ484 was selected as a hotspot for mutation to engineer enzyme variant tolerant to alkaline medium. The corresponding Dβ484N mutant was produced and showed 9-fold increase in stability at alkaline conditions. Bioinformatic analysis of subfamily-specific positions can be further explored to study mechanisms of protein inactivation and to design more stable variants for the engineering of homologous Ntn-hydrolases with improved catalytic properties.

  13. Excipient hydrolysis and ester formation increase pH in a parenteral solution over aging.

    PubMed

    Hirakura, Yutaka; Nakamura, Mitsuhiro; Wakasawa, Tatsuyoshi; Ban, Kazutoshi; Yokota, Shoji; Kitamura, Satoshi

    2006-11-15

    Recently, the number of drug substances that are poorly water-soluble has increased dramatically. This makes improving solubility one of the most critical tasks in pharmaceutical development today. In this study, the physicochemical stability of an injectable solution of conivaptan hydrochloride salt was investigated. Because its free form is hydrophobic, the drug substance was solubilized in a co-solvent system, 40% of which was composed of different alcohols. Since the free form is also alkaline, lactic acid was added to the co-solvent system to further improve its solubility. Remarkably, the pH of the solution was found to increase gradually over time. Considering the physicochemical nature of the drug substance, uncontrolled increases in pH would pose a potential threat of reducing solubility and forming precipitates. For this reason, a risk evaluation was performed. The evaluation revealed that the pH increase was caused by the hydrolysis of lactic acid oligomers as well as by the ester formation occurring between lactic acid and the alcohols. High concentrations of lactic acid supplied as an excipient usually contain lactic acid oligomers, which are hydrolyzed into lactic acid monomers upon dilution with water. Commercial software was used to determine the pK(a) values of the lactic acid oligomers, which were found to be lower than that of lactic acid monomers. This indicates that hydrolysis causes the pH to increase. Ester formation consumes the acid, which also causes the pH to increase. However, both hydrolysis and ester formation equilibrated by the 16-month time point when stored at 25 degrees C. This information allowed the upper limit of the pH increase to be determined molecularly, thereby ensuring product quality through the prevention of precipitate formation due to reduced solubility. Increased awareness of the importance of risk evaluation in pharmaceutical development is critical as these kinds of chemical reactions between excipients constitute

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

    NASA Astrophysics Data System (ADS)

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

    2004-12-01

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

  15. Extraction of starch from wheat flour by alkaline solution

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    DOEpatents

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

    2001-01-01

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

  18. Tendency for oxidation of annelid hemoglobin at alkaline pH and dissociated states probed by redox titration.

    PubMed

    Bispo, Jose Ailton Conceicao; Landini, Gustavo Fraga; Santos, Jose Luis Rocha; Norberto, Douglas Ricardo; Bonafe, Carlos Francisco Sampaio

    2005-08-01

    The redox titration of extracellular hemoglobin of Glossoscolex paulistus (Annelidea) was investigated in different pH conditions and after dissociation induced by pressure. Oxidation increased with increasing pH, as shown by the reduced amount of ferricyanide necessary for the oxidation of hemoglobin. This behavior was the opposite of that of vertebrate hemoglobins. The potential of half oxidation (E1/2) changed from -65.3 to +146.8 mV when the pH increased from 4.50 to 8.75. The functional properties indicated a reduction in the log P50 from 1.28 to 0.28 in this pH range. The dissociation at alkaline pH or induced by high pressure, confirmed by HPLC gel filtration, suggested that disassembly of the hemoglobin could be involved in the increased potential for oxidation. These results suggest that the high stability and prolonged lifetime common to invertebrate hemoglobins is related to their low tendency to oxidize at acidic pH, in contrast to vertebrate hemoglobins.

  19. Metabolic flux modeling of detoxification of acetic acid by Ralstonia eutropha at slightly alkaline pH levels.

    PubMed

    Yu, J; Wang, J

    2001-06-20

    Ralstonia eutropha grows on and produces polyhydroxyalkanoates (PHAs) from fermentation acids. Acetic acid, one major organic acid from acidogenesis of organic wastes, has an inhibitory effect on the bacterium at slightly alkaline pH (6 g HAc/L at pH 8). The tolerance of R. eutropha to acetate, however, was increased significantly up to 15 g/L at the slightly alkaline pH level with high cell mass concentration. A metabolic cell model with five fluxes is proposed to depict the detoxification mechanism including mass transfer and acetyl-CoA formation of acetic acid and the formation of three final metabolic products, polyhydroxybutyrate (PHB), active biomass, and CO(2). The fluxes were measured under different conditions such as cell mass concentration, acetic acid concentration, and medium composition. The experimental results indicate that the acetate detoxification by high cell mass concentration is attributed to the increased fluxes at high extracellular acetate concentrations. The fluxes could be doubled to reduce and hence detoxify the accumulated intracellular acetate anions.

  20. On the effect of alkaline pH and cofactor availability in the conformational and oligomeric state of Escherichia coli glutamate decarboxylase.

    PubMed

    Giovannercole, F; Mérigoux, C; Zamparelli, C; Verzili, D; Grassini, G; Buckle, M; Vachette, P; De Biase, D

    2017-01-05

    Escherichia coli glutamate decarboxylase (EcGad) is a homohexameric pyridoxal 5'-phosphate (PLP)-dependent enzyme. It is the structural component of the major acid resistance system that protects E. coli from strong acid stress (pH < 3), typically encountered in the mammalian gastrointestinal tract. In fact EcGad consumes one proton/catalytic cycle while yielding γ-aminobutyrate and carbon dioxide from the decarboxylation of l-glutamate. Two isoforms of Gad occur in E. coli (GadA and GadB) that are 99% identical in sequence. GadB is the most intensively investigated. Prompted by the observation that some transcriptomic and proteomic studies show EcGad to be expressed in conditions far from acidic, we investigated the structural organization of EcGadB in solution in the pH range 7.5-8.6. Small angle X-ray scattering, combined with size exclusion chromatography, and analytical ultracentrifugation analysis show that the compact and entangled EcGadB hexameric structure undergoes dissociation into dimers as pH alkalinizes. When PLP is not present, the dimeric species is the most abundant in solution, though evidence for the occurrence of a likely tetrameric species was also obtained. Trp fluorescence emission spectra as well as limited proteolysis studies suggest that PLP plays a key role in the acquisition of a folding necessary for the canonical catalytic activity.

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

    SciTech Connect

    Mah, V.; Jalilehvand, F.

    2009-05-19

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

  2. Electrochemical Recovery of Sodium Hydroxide from Alkaline Salt Solution

    SciTech Connect

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

    1996-10-01

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

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

    EPA Science Inventory

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

  4. In vitro susceptibility of oral Candida albicans strains to different pH levels and calcium hydroxide saturated aqueous solution.

    PubMed

    Weckwerth, Paulo Henrique; Carnietto, Cristiane; Weckwerth, Ana Carolina Villas Boas; Duarte, Marco Antonio Hungaro; Kuga, Milton Carlos; Vivan, Rodrigo Ricci

    2012-01-01

    Candida albicans is present in the oral cavity and in the whole digestive tract of humans and other animals, being frequently related to endodontic treatment failure. The present study determined the incidence of C. albicans in the oral cavity and the susceptibility of isolates to different pH values and saturated calcium hydroxide aqueous solution at pH 12.5. Sixty-five patients attending the Endodontic Clinic at the Sagrado Coração University participated in the study. The collected samples were cultivated in selective media for C. albicans and the isolates were tested in terms of resistance to both alkaline pH and saturated aqueous solution of calcium hydroxide. In relation to time variables, yeast viability was assessed by the Sabouraud's agar culture and fluorescein diacetate and ethidium bromide fluorescent staining method. Results from the different pHs and experimental times, including those from different techniques measuring fungal viability, were compared using the chi-square and Fisher's exact tests (α=0.05). The yeasts became completely inviable after 48 h of contact with the calcium hydroxide solution. On the other hand, when exposed to the alkaline culture broth, the yeasts were found to be viable at pHs 9.5 and 10.5 for up to 7 days. In conclusion, C. albicans can only be completely inhibited by direct contact with saturated calcium hydroxide aqueous solution after 48 h of exposure.

  5. Coordinate responses to alkaline pH stress in budding yeast

    PubMed Central

    Serra-Cardona, Albert; Canadell, David; Ariño, Joaquín

    2015-01-01

    Alkalinization of the medium represents a stress condition for the budding yeast Saccharomyces cerevisiae to which this organism responds with profound remodeling of gene expression. This is the result of the modulation of a substantial number of signaling pathways whose participation in the alkaline response has been elucidated within the last ten years. These regulatory inputs involve not only the conserved Rim101/PacC pathway, but also the calcium-activated phosphatase calcineurin, the Wsc1-Pkc1-Slt2 MAP kinase, the Snf1 and PKA kinases and oxidative stress-response pathways. The uptake of many nutrients is perturbed by alkalinization of the environment and, consequently, an impact on phosphate, iron/copper and glucose homeostatic mechanisms can also be observed. The analysis of available data highlights cases in which diverse signaling pathways are integrated in the gene promoter to shape the appropriate response pattern. Thus, the expression of different genes sharing the same signaling network can be coordinated, allowing functional coupling of their gene products. PMID:28357292

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

    PubMed

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

    2013-11-15

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

  7. Contrasting pH buffering patterns in neutral-alkaline soils along a 3600 km transect in northern China

    NASA Astrophysics Data System (ADS)

    Luo, W.; Nelson, P. N.; Li, M.-H.; Cai, J.; Zhang, Y.; Zhang, Y.; Shan, Y.; Wang, R.; Han, X.; Jiang, Y.

    2015-08-01

    Soil pH buffering capacity (pHBC) plays a crucial role in predicting acidification rates, yet its large-scale patterns and controls are poorly understood, especially for neutral-alkaline soils. Here, we evaluated the spatial patterns and drivers of pHBC along a 3600 km long transect (1900 km sub-transect with carbonate containing soils and 1700 km sub-transect with non-carbonate containing soils) across northern China. Soil pHBC was greater in the carbonate containing soils than in the non-carbonate containing soils. Acid addition decreased soil pH in the non-carbonate containing soils more markedly than in the carbonate containing soils. Within the carbonate soil sub-transect, soil pHBC was positively correlated with cation exchange capacity (CEC), carbonate content and exchangeable sodium (Na) concentration, but negatively correlated with initial pH and clay content, and not correlated with soil organic carbon (SOC) content. Within the non-carbonate sub-transect, soil pHBC was positively related to initial pH, clay content, CEC and exchangeable Na concentration, but not related to SOC content. Carbonate content was the primary determinant of pHBC in the carbonate containing soils and CEC was the main determinant of buffering capacity in the non-carbonate containing soils. Soil pHBC was positively related to aridity index and carbonate content across the carbonate containing soil sub-transect. Our results indicated that mechanisms controlling pHBC differ among neutral-alkaline soils of northern China, especially between carbonate and non-carbonate containing soils, leading to different rates, risks, and impacts of acidification. This understanding should be incorporated into the acidification risk assessment and landscape management in a changing world.

  8. Contrasting pH buffering patterns in neutral-alkaline soils along a 3600 km transect in northern China

    NASA Astrophysics Data System (ADS)

    Luo, W. T.; Nelson, P. N.; Li, M.-H.; Cai, J. P.; Zhang, Y. Y.; Zhang, Y. G.; Yang, S.; Wang, R. Z.; Wang, Z. W.; Wu, Y. N.; Han, X. G.; Jiang, Y.

    2015-12-01

    Soil pH buffering capacity (pHBC) plays a crucial role in predicting acidification rates, yet its large-scale patterns and controls are poorly understood, especially for neutral-alkaline soils. Here, we evaluated the spatial patterns and drivers of pHBC along a 3600 km long transect (1900 km sub-transect with carbonate-containing soils and 1700 km sub-transect with non-carbonate-containing soils) across northern China. Soil pHBC was greater in the carbonate-containing soils than in the non-carbonate-containing soils. Acid addition decreased soil pH in the non-carbonate-containing soils more markedly than in the carbonate-containing soils. Within the carbonate soil sub-transect, soil pHBC was positively correlated with cation exchange capacity (CEC), carbonate content and exchangeable sodium (Na) concentration, but negatively correlated with initial pH and clay content, and not correlated with soil organic carbon (SOC) content. Within the non-carbonate sub-transect, soil pHBC was positively related to initial pH, clay content, CEC and exchangeable Na concentration, but not related to SOC content. Carbonate content was the primary determinant of pHBC in the carbonate-containing soils and CEC was the main determinant of buffering capacity in the non-carbonate-containing soils. Along the transect, soil pHBC was different in regions with different aridity index. Soil pHBC was positively related to aridity index and carbonate content across the carbonate-containing soil sub-transect. Our results indicated that mechanisms controlling pHBC differ among neutral-alkaline soils of northern China, especially between carbonate- and non-carbonate-containing soils. This understanding should be incorporated into the acidification risk assessment and landscape management in a changing world.

  9. Isolation of a Sulfur-oxidizing Bacterium That can Grow under Alkaline pH, from Corroded Concrete.

    PubMed

    Maeda, T; Negishi, A; Oshima, Y; Nogami, Y; Kamimura, K; Sugio, T

    1998-01-01

    To study the early stages of concrete corrosion by bacteria, sulfur-oxidizing bacterium strain RO-1, which grows in an alkaline thiosulfate medium (pH 10.0) was isolated from corroded concreate and characterized. Strain RO-1 was a Gram negative, rod-shaped bacterium (0.5-0.6×0.9-1.5 μm). The mean G+C content of the DNA of strain RO-1 was 65.0 mol%. Optimum pH and temperature for growth were 8.0. and 30-37°C, respectively. When grown in thiosulfate medium with pH 10.0, growth rate of the strain was 48% of that observed at the optimum pH for growth. Strain RO-1 used sulfide, thiosulfate, and glucose, but not elemental sulfur or tetrathionate, as a sole energy source. Strain RO-1 grew under anaerobic conditions in pepton-NO3 (-) medium containing sodium nitrate as an electron acceptor, and had enzyme activities that oxidized sulfide, elemental sulfur, thiosulfate, sulfite, and glucose, but not tetrathionate. The bacterium had an activity to assimilate (14)CO2 into the cells when thiosulfate was used as an energy source. These results suggest that strain RO-1 is Thiobacillus versutus. Strain RO-1 exuded Ca(2+) from concrete blocks added to thiosulfate medium with pH 9.0 and the pH of the medium decreased from 9.0 to 5.5 after 22 days of cultivation. In contrast, Thiobacillus thiooxidans strain NB1-3 could not exude Ca(2+) in the same thiosulfate medium, suggesting that strain RO-1, but not T. thiooxidans NB1-3, is involved in the early stage of concrete corrosion because concrete structures just after construction contain calcium hydroxide and have a pH of 12-13.

  10. Two pore channel 2 (TPC2) inhibits autophagosomal-lysosomal fusion by alkalinizing lysosomal pH.

    PubMed

    Lu, Yingying; Hao, Bai-Xia; Graeff, Richard; Wong, Connie W M; Wu, Wu-Tian; Yue, Jianbo

    2013-08-16

    Autophagy is an evolutionarily conserved lysosomal degradation pathway, yet the underlying mechanisms remain poorly understood. Nicotinic acid adenine dinucleotide phosphate (NAADP), one of the most potent Ca(2+) mobilizing messengers, elicits Ca(2+) release from lysosomes via the two pore channel 2 (TPC2) in many cell types. Here we found that overexpression of TPC2 in HeLa or mouse embryonic stem cells inhibited autophagosomal-lysosomal fusion, thereby resulting in the accumulation of autophagosomes. Treatment of TPC2 expressing cells with a cell permeant-NAADP agonist, NAADP-AM, further induced autophagosome accumulation. On the other hand, TPC2 knockdown or treatment of cells with Ned-19, a NAADP antagonist, markedly decreased the accumulation of autophagosomes. TPC2-induced accumulation of autophagosomes was also markedly blocked by ATG5 knockdown. Interestingly, inhibiting mTOR activity failed to increase TPC2-induced autophagosome accumulation. Instead, we found that overexpression of TPC2 alkalinized lysosomal pH, and lysosomal re-acidification abolished TPC2-induced autophagosome accumulation. In addition, TPC2 overexpression had no effect on general endosomal-lysosomal degradation but prevented the recruitment of Rab-7 to autophagosomes. Taken together, our data demonstrate that TPC2/NAADP/Ca(2+) signaling alkalinizes lysosomal pH to specifically inhibit the later stage of basal autophagy progression.

  11. Cs diffusion in local Taiwan laterite with different solution concentration, pH and packing density.

    PubMed

    Wang, Tsing-Hai; Li, Ming-Hsu; Teng, Shi-Ping

    2008-09-01

    In this work we used an "in-diffusion" method to study the effects of pH, solution concentration and packing density on Cs diffusion by packing local Taiwan laterite (LTL) into modified capillary columns with 5mm diameter. These packed columns were first pre-equilibrated with synthetic groundwater (GW) for 3 weeks. The diffusion experiments were then carried out at ambient condition for 2 weeks. Our experimental results showed that the Cs diffusion profile fits Fick's second law very well in given experimental conditions, indicating the validity of modified capillary column method. Generally speaking, Cs diffusion in LTL decreases as the pH increases and as Cs concentration decreases. The apparent diffusion coefficient (D(a)) increases from 5.52 x 10(-12) (10(-7)M) to 2.18 x 10(-11) (10(-3)M)m(2)/s, while the effective diffusion coefficient (D(e)) shows slight variation as the Cs concentration changes. Both the derived D(a) and D(e) values decrease as the pH increases, implying that the diffusion mechanisms of Cs nuclide in alkaline and acid environment are different. In addition, our results show that Cs diffusion is unaffected by the given packing density, indicating the interlaminary space is not the major determinant of Cs adsorption and diffusion in LTL.

  12. The Aspergillus PacC zinc finger transcription factor mediates regulation of both acid- and alkaline-expressed genes by ambient pH.

    PubMed Central

    Tilburn, J; Sarkar, S; Widdick, D A; Espeso, E A; Orejas, M; Mungroo, J; Peñalva, M A; Arst, H N

    1995-01-01

    The pH regulation of gene expression in Aspergillus nidulans is mediated by pacC, whose 678 residue-derived protein contains three putative Cys2His2 zinc fingers. Ten pacCc mutations mimicking growth at alkaline pH remove between 100 and 214 C-terminal residues, including a highly acidic region containing an acidic glutamine repeat. Nine pacC+/- mutations mimicking acidic growth conditions remove between 299 and 505 C-terminal residues. Deletion of the entire pacC coding region mimics acidity but leads additionally to poor growth and conidiation. A PacC fusion protein binds DNA with the core consensus GCCARG. At alkaline ambient pH, PacC activates transcription of alkaline-expressed genes (including pacC itself) and represses transcription of acid-expressed genes. pacCc mutations obviate the need for pH signal transduction. Images PMID:7882981

  13. Comparison of Salivary pH, Buffering Capacity and Alkaline Phosphatase in Smokers and Healthy Non-Smokers

    PubMed Central

    Ahmadi-Motamayel, Fatemeh; Falsafi, Parisa; Goodarzi, Mohammad T.; Poorolajal, Jalal

    2016-01-01

    Objectives: Saliva contains alkaline phosphatase (ALP)—a key intracellular enzyme related to destructive processes and cellular damage—and has buffering capacity (BC) against acids due to the presence of bicarbonate and phosphate ions. Smoking may have deleterious effects on the oral environment due to pH changes which can affect ALP activity. This study aimed to evaluate the salivary pH, BC and ALP activity of male smokers and healthy non-smokers. Methods: This retrospective cohort study took place between August 2012 and December 2013. A total of 251 healthy male non-smokers and 259 male smokers from Hamadan, Iran, were selected. Unstimulated whole saliva was collected from each participant and pH and BC were determined using a pH meter. Salivary enzymes were measured by spectrophotometric assay. Results: Mean salivary pH (7.42 ± 0.48 and 7.52 ± 0.43, respectively; P = 0.018) and BC (3.41 ± 0.54 and 4.17 ± 0.71; P = 0.001) was significantly lower in smokers compared to non-smokers. Mean ALP levels were 49.58 ± 23.33 IU/L among smokers and 55.11 ± 27.85 IU/L among non-smokers (P = 0.015). Conclusion: Significantly lower pH, BC and ALP levels were observed among smokers in comparison to a healthy control group. These salivary alterations could potentially be utilised as biochemical markers for the evaluation of oral tissue function and side-effects among smokers. Further longitudinal studies are recommended to evaluate the effects of smoking on salivary components. PMID:27606111

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

    NASA Astrophysics Data System (ADS)

    Radovanovic, Milan B.; Antonijevic, Milan M.

    2016-03-01

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

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

    PubMed

    Keshk, Sherif M A S

    2015-01-22

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

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

    SciTech Connect

    Langton, C. A.

    2016-06-30

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

  17. Proteolytic Activity at Alkaline pH in Oat Leaves, Isolation of an Aminopeptidase 1

    PubMed Central

    Casano, Leonardo M.; Desimone, Marcelo; Trippi, Victorio S.

    1989-01-01

    Proteolytic activity in oat leaf extracts was measured with both azocasein and ribulose bisphosphate carboxylase (Rubisco) as substrates over a wide range of pH (3.0-9.2). With either azocasein or Rubisco activity peaks appeared at pH 4.8, 6.6, and 8.4. An aminopeptidase (AP) which hydrolyzes leucine-nitroanilide was partially purified. Purification consisted of a series of six steps which included ammonium sulfate precipitation, gel filtration, and two ionic exchange chromatographies. The enzyme was purified more than 100-fold. The apparent Km for leucine-nitroanilide is 0.08 millimolar at its pH optimum of 8.4. AP may be a cystein protease since it is inhibited by heavy metals and activated by 2-mercaptoethanol. Isolated chloroplasts were also able to hydrolyze leucine-nitroanilide at a pH optimum of 8.4, indicating that AP could be localized inside the photosynthetic organelles. PMID:16667194

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

    SciTech Connect

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

    2008-08-26

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

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

    SciTech Connect

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

    2005-11-01

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

  20. Characterization of steady-state activities of cytochrome c oxidase at alkaline pH: mimicking the effect of K-channel mutations in the bovine enzyme.

    PubMed

    Riegler, David; Shroyer, Lois; Pokalsky, Christine; Zaslavsky, Dmitry; Gennis, Robert; Prochaska, Lawrence J

    2005-01-07

    The cytochrome c oxidase activity of the bovine heart enzyme decreases substantially at alkaline pH, from 650 s(-1) at pH 7.0 to less than 10 s(-1) at pH 9.75. In contrast, the cytochrome c peroxidase activity of the enzyme shows little or no pH dependence (30-50 s(-1)) at pH values greater than 8.5. Under the conditions employed, it is demonstrated that the dramatic decrease in oxidase activity at pH 9.75 is fully reversible and not due to a major alkaline-induced conformational change in the enzyme. Furthermore, the Km values for cytochrome c interaction with the enzyme were also not significantly different at pH 7.8 and pH 9.75, suggesting that the pH dependence of the activity is not due to an altered interaction with cytochrome c at alkaline pH. However, at alkaline pH, the steady-state reduction level of the hemes increased, consistent with a slower rate of electron transfer from heme a to heme a3 at alkaline pH. Since it is well established that the rate of electron transfer from heme a to heme a3 is proton-coupled, it is reasonable to postulate that at alkaline pH, proton uptake becomes rate-limiting. The fact that this is not observed when hydrogen peroxide is used as a substrate in place of O2 suggests that the rate-limiting step is proton uptake via the K-channel associated with the reduction of the heme a3/CuB center prior to the reaction with O2. This step is not required for the reaction with H2O2, as shown previously in the examination of mutants of bacterial oxidases in which the K-channel was blocked. It is concluded that at pH values near 10, the delivery of protons via the K-channel becomes the rate-limiting step in the catalytic cycle with O2, so that the behavior of the bovine enzyme resembles that of the K-channel mutants in the bacterial enzymes.

  1. Effect of Alkaline pH on Polishing and Etching of Single and Polycrystalline Silicon

    NASA Astrophysics Data System (ADS)

    Venkatesh, R. Prasanna; Prasad, Y. Nagendra; Kwon, Tae-Young; Kang, Young-Jae; Park, Jin-Goo

    2012-07-01

    In this paper, the polishing and etching behavior of single and polycrystalline silicon were studied. Prior to chemical mechanical polishing (CMP) process, the surfaces were treated with dilute hydrofluoric acid (DHF) to remove native oxides. The surface analysis shows that the poly contains trace amount of oxygen even after DHF treatment. The static and dynamic etch rates, and removal rates were measured as a function of slurry pH. The single silicon showed a higher static etch rate than the poly. After static etch rate measurements, poly showed higher surface roughness and more hydrophilic which indicates that the surface of poly is different from single crystal silicon. The friction force between pad and substrate and pad temperature was also measured as a function of pH during polishing in order to get more understanding of polishing process. At all the pH values being investigated, poly showed lower dynamic and removal rates, higher friction force and higher temperature. This indicates that the removal of poly in CMP is predominantly by mechanical actions. Also, these results, suggest a mechanism in which the oxygen present in the poly grain boundaries strongly influences the etching and removal mechanism.

  2. Diversity and food web structure of nematode communities under high soil salinity and alkaline pH.

    PubMed

    Salamún, Peter; Kucanová, Eva; Brázová, Tímea; Miklisová, Dana; Renčo, Marek; Hanzelová, Vladimíra

    2014-10-01

    A long-term and intensive magnesium (Mg) ore processing in Slovenské Magnezitové Závody a.s. in Jelšava has resulted in a high Mg content and alkaline pH of the soil environment, noticeable mainly in the close vicinity of the smelter. Nematode communities strongly reacted to the contamination mostly by a decrease in abundance of the sensitive groups. Nematodes from c-p 1 group and bacterivores, tolerant to pollution played a significant role in establishing the dominance at all sites. With increasing distance from the pollution source, the nematode communities were more structured and complex, with an increase in proportion of sensitive c-p 4 and 5 nematodes, composed mainly of carnivores and omnivores. Various ecological indices (e.g. MI2-5, SI, H') indicated similar improvement of farther soil ecosystems.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  4. Catalytically active alkaline molten globular enzyme: Effect of pH and temperature on the structural integrity of 5-aminolevulinate synthase.

    PubMed

    Stojanovski, Bosko M; Breydo, Leonid; Hunter, Gregory A; Uversky, Vladimir N; Ferreira, Gloria C

    2014-12-01

    5-Aminolevulinate synthase (ALAS), a pyridoxal-5'phosphate (PLP)-dependent enzyme, catalyzes the first step of heme biosynthesis in mammals. Circular dichroism (CD) and fluorescence spectroscopies were used to examine the effects of pH (1.0-3.0 and 7.5-10.5) and temperature (20 and 37°C) on the structural integrity of ALAS. The secondary structure, as deduced from far-UV CD, is mostly resilient to pH and temperature changes. Partial unfolding was observed at pH2.0, but further decreasing pH resulted in acid-induced refolding of the secondary structure to nearly native levels. The tertiary structure rigidity, monitored by near-UV CD, is lost under acidic and specific alkaline conditions (pH10.5 and pH9.5/37°C), where ALAS populates a molten globule state. As the enzyme becomes less structured with increased alkalinity, the chiral environment of the internal aldimine is also modified, with a shift from a 420nm to 330nm dichroic band. Under acidic conditions, the PLP cofactor dissociates from ALAS. Reaction with 8-anilino-1-naphthalenesulfonic acid corroborates increased exposure of hydrophobic clusters in the alkaline and acidic molten globules, although the reaction is more pronounced with the latter. Furthermore, quenching the intrinsic fluorescence of ALAS with acrylamide at pH1.0 and 9.5 yielded subtly different dynamic quenching constants. The alkaline molten globule state of ALAS is catalytically active (pH9.5/37°C), although the kcat value is significantly decreased. Finally, the binding of 5-aminolevulinate restricts conformational fluctuations in the alkaline molten globule. Overall, our findings prove how the structural plasticity of ALAS contributes to reaching a functional enzyme.

  5. Effect of immersion into solutions at various pH on the color stability of composite resins with different shades

    PubMed Central

    Moon, Ji-Deok; Seon, Eun-Mi; Son, Sung-Ae; Jung, Kyoung-Hwa; Kwon, Yong-Hoon

    2015-01-01

    Objectives This study examined the color changes of a resin composite with different shades upon exposure to water with different pH. Materials and Methods Nanohybrid resin composites (Filtek Z350XT, 3M ESPE) with four different shades (A2, A3, B1, and B2) were immersed in water with three different pH (pH 3, 6, and 9) for 14 day. The CIE L*a*b* color coordinates of the specimens were evaluated before and after immersion in the solutions. The color difference (ΔE*) and the translucency parameter (TP) were calculated using the color coordinates. Results ΔE* ranged from 0.33 to 1.58, and the values were affected significantly by the pH. The specimens immersed in a pH 6 solution showed the highest ΔE* values (0.87 - 1.58). The specimens with a B1 shade showed the lowest ΔE* change compared to the other shades. TP ranged from 7.01 to 9.46 depending on the pH and resin shade. The TP difference between before and after immersion in the pH solutions was less than 1.0. Conclusions The resulting change of color of the tested specimens did not appear to be clinically problematic because the color difference was < 1.6 in the acidic, neutral, and alkaline solutions regardless of the resin shade, i.e., the color change was imperceptible. PMID:26587412

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

    NASA Astrophysics Data System (ADS)

    Aoyagi, Wataru; Omiya, Masaki

    2013-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1997-10-01

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

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

    PubMed

    Ogata, Fumihiko; Iwata, Yuka; Kawasaki, Naohito

    2014-01-01

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

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

    PubMed

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

    2013-01-01

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

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

    PubMed

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

    2011-04-01

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

  11. Application of a fluidized bed reactor charged with aragonite for control of alkalinity, pH and carbon dioxide in marine recirculating aquaculture systems

    USGS Publications Warehouse

    Paul S Wills, PhD; Pfeiffer, Timothy; Baptiste, Richard; Watten, Barnaby J.

    2016-01-01

    Control of alkalinity, dissolved carbon dioxide (dCO2), and pH are critical in marine recirculating aquaculture systems (RAS) in order to maintain health and maximize growth. A small-scale prototype aragonite sand filled fluidized bed reactor was tested under varying conditions of alkalinity and dCO2 to develop and model the response of dCO2 across the reactor. A large-scale reactor was then incorporated into an operating marine recirculating aquaculture system to observe the reactor as the system moved toward equilibrium. The relationship between alkalinity dCO2, and pH across the reactor are described by multiple regression equations. The change in dCO2 across the small-scale reactor indicated a strong likelihood that an equilibrium alkalinity would be maintained by using a fluidized bed aragonite reactor. The large-scale reactor verified this observation and established equilibrium at an alkalinity of approximately 135 mg/L as CaCO3, dCO2 of 9 mg/L, and a pH of 7.0 within 4 days that was stable during a 14 day test period. The fluidized bed aragonite reactor has the potential to simplify alkalinity and pH control, and aid in dCO2 control in RAS design and operation. Aragonite sand, purchased in bulk, is less expensive than sodium bicarbonate and could reduce overall operating production costs.

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

  13. High-resolution Imaging of pH in Alkaline Sediments and Water Based on a New Rapid Response Fluorescent Planar Optode

    NASA Astrophysics Data System (ADS)

    Han, Chao; Yao, Lei; Xu, Di; Xie, Xianchuan; Zhang, Chaosheng

    2016-05-01

    A new dual-lumophore optical sensor combined with a robust RGB referencing method was developed for two-dimensional (2D) pH imaging in alkaline sediments and water. The pH sensor film consisted of a proton-permeable polymer (PVC) in which two dyes with different pH sensitivities and emission colors: (1) chloro phenyl imino propenyl aniline (CPIPA) and (2) the coumarin dye Macrolex® fluorescence yellow 10 GN (MFY-10 GN) were entrapped. Calibration experiments revealed the typical sigmoid function and temperature dependencies. This sensor featured high sensitivity and fast response over the alkaline working ranges from pH 7.5 to pH 10.5. Cross-sensitivity towards ionic strength (IS) was found to be negligible for freshwater when IS <0.1 M. The sensor had a spatial resolution of approximately 22 μm and aresponse time of <120 s when going from pH 7.0 to 9.0. The feasibility of the sensor was demonstrated using the pH microelectrode. An example of pH image obtained in the natrual freshwater sediment and water associated with the photosynthesis of Vallisneria spiral species was also presented, suggesting that the sensor held great promise for the field applications.

  14. High-resolution Imaging of pH in Alkaline Sediments and Water Based on a New Rapid Response Fluorescent Planar Optode

    PubMed Central

    Han, Chao; Yao, Lei; Xu, Di; Xie, Xianchuan; Zhang, Chaosheng

    2016-01-01

    A new dual-lumophore optical sensor combined with a robust RGB referencing method was developed for two-dimensional (2D) pH imaging in alkaline sediments and water. The pH sensor film consisted of a proton-permeable polymer (PVC) in which two dyes with different pH sensitivities and emission colors: (1) chloro phenyl imino propenyl aniline (CPIPA) and (2) the coumarin dye Macrolex® fluorescence yellow 10 GN (MFY-10 GN) were entrapped. Calibration experiments revealed the typical sigmoid function and temperature dependencies. This sensor featured high sensitivity and fast response over the alkaline working ranges from pH 7.5 to pH 10.5. Cross-sensitivity towards ionic strength (IS) was found to be negligible for freshwater when IS <0.1 M. The sensor had a spatial resolution of approximately 22 μm and aresponse time of <120 s when going from pH 7.0 to 9.0. The feasibility of the sensor was demonstrated using the pH microelectrode. An example of pH image obtained in the natrual freshwater sediment and water associated with the photosynthesis of Vallisneria spiral species was also presented, suggesting that the sensor held great promise for the field applications. PMID:27199163

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

    SciTech Connect

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

    1999-07-01

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

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

    PubMed Central

    Muñoz-Santiburcio, Daniel; Marx, Dominik

    2016-01-01

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

  17. Roles of alkaline phosphatase and labile internal mineral in matrix vesicle-mediated calcification. Effect of selective release of membrane-bound alkaline phosphatase and treatment with isosmotic pH 6 buffer.

    PubMed

    Register, T C; McLean, F M; Low, M G; Wuthier, R E

    1986-07-15

    The roles of alkaline phosphatase and labile internal mineral in matrix vesicle-mediated mineralization have been studied by selectively releasing the enzyme from a wide variety of matrix vesicle preparations using treatment with a bacterial phosphatidylinositol-specific phospholipase C and by demineralization of the vesicles using isosmotic pH 6 buffer. Following depletion of 50-90% of the alkaline phosphatase activity or treatment with citrate buffer, the vesicles were tested for their ability to accumulate 45Ca2+ and 32Pi from a synthetic cartilage lymph. Removal of alkaline phosphatase by phospholipase C treatment caused two principal effects, depending on the matrix vesicle preparation. In rapidly mineralizing vesicle fractions which did not require organic phosphate esters (Po) to accumulate mineral ions, release of alkaline phosphatase had only a minor effect. In slowly mineralizing vesicles preparations or those dependent on Po substrates for mineral ion uptake, release of alkaline phosphatase caused significant loss of mineralizing activity. The activity of rapidly calcifying vesicles was shown to be dependent on the presence of labile internal mineral, as demonstrated by major loss in activity when the vesicles were decalcified by various treatments. Ion uptake by demineralized vesicles or those fractionated on sucrose step gradients required Po and was significantly decreased by alkaline phosphatase depletion. Uptake of Pi, however, was not coupled with hydrolysis of the Po substrate. These findings argue against a direct role for alkaline phosphatase as a porter in matrix vesicle Pi uptake, contrary to previous postulates. The results emphasize the importance of internal labile mineral in rapid uptake of mineral ions by matrix vesicles.

  18. Role of pH in metal adsorption from aqueous solutions containing chelating agents on chitosan

    SciTech Connect

    Wu, F.C.; Tseng, R.L.; Juang, R.S.

    1999-01-01

    The role of pH in adsorption of Cu(II) from aqueous solutions containing chelating agents on chitosan was emphasized. Four chelating agents including ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, and sodium gluconate were used. It was shown that the adsorption ability of Cu(II) on chitosan from its chelated solutions varied significantly with pH variations. The competition between coordination of Cu(II) with unprotonated chitosan and electrostatic interaction of the Cu(II) chelates with protonated chitosan took place because of the change in solution pH during adsorption. The maximum adsorption capacity was obtained within each optimal pH range determined from titration curves of the chelated solutions. Coordination of Cu(II) with the unprotonated chitosan was found to dominate at pH below such an optimal pH value.

  19. Electrochemical control of pH in a hydroponic nutrient solution

    NASA Technical Reports Server (NTRS)

    Schwartzkopf, S. H.

    1986-01-01

    The electrochemical pH control system described was found to provide a feasible alternative method of controlling nutrient solution pH for CELSS applications. The plants grown in nutrient solution in which the pH was controlled electrochemically showed no adverse effects. Further research into the design of a larger capacity electrode bridge for better control is indicated by the results of this experiment, and is currently under way.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  1. Determination of the equilibrium formation constants of two U(VI)-peroxide complexes at alkaline pH.

    PubMed

    Meca, S; Martínez-Torrents, A; Martí, V; Giménez, J; Casas, I; de Pablo, J

    2011-08-21

    The formation of uranyl-peroxide complexes was studied at alkaline media by using UV-Visible spectrophotometry and the STAR code. Two different complexes were found at a H(2)O(2)/U(VI) ratio lower than 2. A graphical method was used in order to obtain the formation constants of such complexes and the STAR program was used to refine the formation constants values because of its capacity to treat multiwavelength absorbance data and refining equilibrium constants. The values obtained for the two complexes identified were: UO(2)(2+) + H(2)O(2) + 4OH(-) <−> UO(2)(O(2))(OH)(2)(2-) + 2H(2)O: log β°(1,1,4) = 28.1 ± 0.1 (1). UO(2)(2+) + 2H(2)O(2) + 6OH(-) <−> UO(2)(O(2))(2)(OH)(2)(4-) + 4H(2)O: log β°(1,2,6) = 36.8 ± 0.2 (2). At hydrogen peroxide concentrations higher than 10(-5) mol dm(-3), and in the absence of carbonate, the UO(2)(O(2))(2)(OH)(2)(4-) complex is predominant in solution, indicating the significant peroxide affinity of peroxide ions for uranium and the strong complexes of uranium(VI) with peroxide.

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

    USGS Publications Warehouse

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

    1986-01-01

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

  3. Microprofiles of oxygen, redox potential, and pH, and microbial fermentation products in the highly alkaline gut of the saprophagous larva of Penthetria holosericea (Diptera: Bibionidae).

    PubMed

    Šustr, Vladimír; Stingl, Ulrich; Brune, Andreas

    2014-08-01

    The saprophagous larvae of bibionid flies harbor bacteria in their alkaline intestinal tracts, but little is known about the contribution of the gut microbiota to the digestion of their recalcitrant diet. In this study, we measured oxygen and hydrogen partial pressure, redox potential and pH in the midgut, gastric caeca and hindgut of larvae of the bibionid fly Penthetria holosericea with Clark-type O2 and H2 microsensors, platinum redox microelectrodes, and LIX-type pH microelectrodes. The center of the midgut lumen was anoxic, whereas gastric caeca and hindgut were hypoxic. However, redox potential profiles indicated oxidizing conditions throughout the gut, with lowest values in the midgut (+20 to +60mV). Hydrogen production was not detected. The midgut was extremely alkaline (pH around 11), whereas hindgut and gastric caeca were neutral to slightly alkaline. While HPLC analysis showed high concentrations of glucose in the midgut (15mM) and gastric caeca (27mM), the concentrations of microbial fermentation products such as lactate (2-4mM), acetate (<1mM) and succinate (<0.5mM) were low in all gut regions, suggesting that the contribution of microorganisms to the digestive process, particularly in the alkaline midgut, is only of minor importance. We conclude that the digestive strategy of the saprophytic larva of P. holosericea, which feeds selectively on decomposed leaves and its own microbe-rich faeces, differs fundamentally from those of detritivorous and humivorous insects, which host a highly active, fermentative microbiota in their alkaline midgut or hindgut compartments.

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

    PubMed

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

    2014-12-14

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

  5. Strategies for regulation of hemolymph pH in acidic and alkaline water by the larval mosquito Aedes aegypti (L.) (Diptera; Culicidae).

    PubMed

    Clark, Thomas M; Vieira, Marcus A L; Huegel, Kara L; Flury, Dawn; Carper, Melissa

    2007-12-01

    The responses of larval Aedes aegypti to media of pH 4, 7 and 11 provide evidence for pH regulatory strategies. Drinking rates in pH 4 media were elevated 3- to 5-fold above those observed in pH 7 or 11. Total body water was elevated during acute exposure to acidic media. During chronic exposure, total body water was decreased and Malpighian tubule mitochondrial luminosity, quantified using Mitotracker Green FM, increased. Malpighian tubule secretion rates and energy demands thus appear to increase dramatically during acid exposure. In alkaline media, drinking rates were quite low. Larvae in pH 11 media excreted net acid (0.12 nequiv H(+) g(-1) h(-1)) and the pH indicators azolitmin and bromothymol blue revealed that the rectal lumen is acidic in vivo at all ambient pH values. The anal papillae (AP) were found to be highly permeant to acid-base equivalents. Ambient pH influenced the length, and the mass-specific length, of the AP in the presence of NaCl (59.9 mmol l(-1)). In contrast, the length and mass-specific length of AP were not influenced by ambient pH in low NaCl conditions. Mitochondrial luminosity was reduced in AP of larvae reared in acidic media, and was not elevated in alkaline media, relative to that of larvae reared in neutral media. These data suggest that the AP may compromise acid-base balance in acidic media, and may also be an important site of trade-offs between H(+) homeostasis and NaCl uptake in dilute, acidic media.

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

    PubMed

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

    2017-02-01

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

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

    PubMed

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

    2017-01-01

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

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

    SciTech Connect

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

    2012-06-11

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

  9. Carbon Dioxide Addition to Microbial Fuel Cell Cathodes Maintains Sustainable Catholyte pH and Improves Anolyte pH, Alkalinity, and Conductivity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bioelectrochemical system (BES) pH imbalances develop due to anodic proton-generating oxidation reactions and cathodic hydroxide-ion-generating reduction reactions. Until now, workers added unsustainable buffers to reduce the pH difference between the anode and cathode because the pH imbalance cont...

  10. Alkaline pH Is a signal for optimal production and secretion of the heat labile toxin, LT in enterotoxigenic Escherichia coli (ETEC).

    PubMed

    Gonzales, Lucia; Ali, Zahra Bagher; Nygren, Erik; Wang, Zhiyun; Karlsson, Stefan; Zhu, Baoli; Quiding-Järbrink, Marianne; Sjöling, Åsa

    2013-01-01

    Enterotoxigenic Escherichia coli (ETEC) cause secretory diarrhea in children and travelers to endemic areas. ETEC spreads through the fecal-oral route. After ingestion, ETEC passes through the stomach and duodenum before it colonizes the lower part of the small intestine, exposing bacteria to a wide range of pH and environmental conditions. This study aimed to determine the impact of external pH and activity of the Cyclic AMP receptor protein (CRP) on the regulation of production and secretion of heat labile (LT) enterotoxin. ETEC strain E2863wt and its isogenic mutant E2863ΔCRP were grown in LBK media buffered to pH 5, 7 and 9. GM1 ELISA, cDNA and cAMP analyses were carried out on bacterial pellet and supernatant samples derived from 3 and 5 hours growth and from overnight cultures. We confirm that CRP is a repressor of LT transcription and production as has been shown before but we show for the first time that CRP is a positive regulator of LT secretion both in vitro and in vivo. LT secretion increased at neutral to alkaline pH compared to acidic pH 5 where secretion was completely inhibited. At pH 9 secretion of LT was optimal resulting in 600 percent increase of secreted LT compared to unbuffered LBK media. This effect was not due to membrane leakage since the bacteria were viable at pH 9. The results indicate that the transition to the alkaline duodenum and/or exposure to high pH close to the epithelium as well as activation of the global transcription factor CRP are signals that induce secretion of the LT toxin in ETEC.

  11. Combined effects of carbonate alkalinity and pH on survival, growth and haemocyte parameters of the Venus clam Cyclina sinensis.

    PubMed

    Lin, Tingting; Lai, Qifang; Yao, Zongli; Lu, Jianxue; Zhou, Kai; Wang, Hui

    2013-08-01

    Carbonate alkalinity (CA) and pH are considered to be two important stress factors that determine the response of aquatic animals to sudden transfers into saline-alkaline water. To evaluate the potential for aquaculture production of Venus clams (Cyclina sinensis) farmed in saline-alkaline water, the combined effects of CA (2.5 (control), 10.0, 20.0 and 40.0 meq/l) and pH (8.0 (control), 8.5, 9.0 and 9.5) on survival rate was monitored every day for 10 days. Length gain rate (LGR) and weight gain rate (WGR) were also monitored for two months, and total haemocyte count (THC), phagocytic rate (PR) and haemocyte mortality (HM) were measured for 3, 6, 12 and 24 days under the same water temperature (20 °C) and salinity (15‰) conditions. The results showed that survival rates in treatments of CA ≤ 20.0, combined with pH ≤ 9.0, were 100%. LGR and WGR in treatments of CA 2.5 & pH 8.0 (control), CA 2.5 & pH 8.5 and CA 10.0 & pH 8.0 exhibited the largest values (P > 0.05), while in other treatments, they showed a decreasing trend with an increase in either CA or pH or both (P < 0.05). Similarly, for THC, PR and HM, no significant differences were observed among the fast growth treatments during the entire experimental period (P > 0.05), however, in other treatments, they presented significant differences, especially on day 3 and 6 (P < 0.05), most notably with increases in CA or pH, but returned to control levels on day 12. In conclusion, in this study, a strong interaction between CA and pH was observed. Additionally, it was ascertained that the Venus clam C. sinensis can withstand the stress of CA 20.0 combined pH 9.0, although individuals grows slowly and may take approximately 12 days to recover to the unstressed condition.

  12. Improving the expression of recombinant proteins in E. coli BL21 (DE3) under acetate stress: an alkaline pH shift approach.

    PubMed

    Wang, Hengwei; Wang, Fengqing; Wang, Wei; Yao, Xueling; Wei, Dongzhi; Cheng, Hairong; Deng, Zixin

    2014-01-01

    Excess acetate has long been an issue for the production of recombinant proteins in E. coli cells. Recently, improvements in acetate tolerance have been achieved through the use of genetic strategies and medium supplementation with certain amino acids and pyrimidines. The aim of our study was to evaluate an alternative to improve the acetate tolerance of E. coli BL21 (DE3), a popular strain used to express recombinant proteins. In this work we reported the cultivation of BL21 (DE3) in complex media containing acetate at high concentrations. In the presence of 300 mM acetate, compared with pH 6.5, pH 7.5 improved cell growth by approximately 71%, reduced intracellular acetate by approximately 50%, and restored the expression of glutathione S-transferase (GST), green fluorescent protein (GFP) and cytochrome P450 monooxygenase (CYP). Further experiments showed that alkaline pHs up to 8.5 had little inhibition in the expression of GST, GFP and CYP. In addition, the detrimental effect of acetate on the reduction of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) by the cell membrane, an index of cellular metabolic capacity, was substantially alleviated by a shift to alkaline pH values of 7.5-8.0. Thus, we suggest an approach of cultivating E. coli BL21 (DE3) at pH 8.0 ± 0.5 to minimize the effects caused by acetate stress. The proposed strategy of an alkaline pH shift is a simple approach to solving similar bioprocessing problems in the production of biofuels and biochemicals from sugars.

  13. Fate of cadmium at the soil-solution interface: a thermodynamic study as influenced by varying pH at South 24 Parganas, West Bengal, India.

    PubMed

    Karak, Tanmoy; Paul, Ranjit Kumar; Das, Sampa; Das, Dilip K; Dutta, Amrit Kumar; Boruah, Romesh K

    2015-11-01

    A study on the sorption kinetics of Cd from soil solution to soils was conducted to assess the persistence of Cd in soil solution as it is related to the leaching, bioavailability, and potential toxicity of Cd. The kinetics of Cd sorption on two non-contaminated alkaline soils from Canning (22° 18' 48.02″ N and 88° 39' 29.0″ E) and Lakshmikantapur (22° 06' 16.61″ N and 88° 19' 08.66″ E) of South 24 Parganas, West Bengal, India, were studied using conventional batch experiment. The variable soil suspension parameters were pH (4.00, 6.00, 8.18, and 9.00), temperatures (308, 318, and 328 K) and Cd concentrations (5-100 mg L(-1)). The average rate coefficient (kavg) and half-life (t1/2) values indicate that the persistence of Cd in soil solution is influenced by both temperature and soil suspension pH. The concentration of Cd in soil solution decreases with increase of temperature; therefore, Cd sorption on the soil-solution interface is an endothermic one. Higher pH decreases the t 1/2 of Cd in soil solution, indicating that higher pH (alkaline) is not a serious concern in Cd toxicity than lower pH (acidic). Based on the energy of activation (Ea) values, Cd sorption in acidic pH (14.76±0.29 to 64.45±4.50 kJ mol(-1)) is a surface control phenomenon and in alkaline pH (9.33±0.09 to 44.60±2.01 kJ mol(-1)) is a diffusion control phenomenon The enthalpy of activation (ΔH∓) values were found to be between 7.28 and 61.73 kJ mol(-1). Additionally, higher positive energy of activation (ΔG∓) values (46.82±2.01 to 94.47±2.36 kJ mol(-1)) suggested that there is an energy barrier for product formation.

  14. Hydrolysis and volatile fatty acids accumulation of waste activated sludge enhanced by the combined use of nitrite and alkaline pH.

    PubMed

    Huang, Cheng; Liu, Congcong; Sun, Xiuyun; Sun, Yinglu; Li, Rui; Li, Jiansheng; Shen, Jinyou; Han, Weiqing; Liu, Xiaodong; Wang, Lianjun

    2015-12-01

    Volatile fatty acids (VFAs) production from anaerobic digestion of waste activated sludge (WAS) is often limited by the slow hydrolysis and/or poor substrate availability. Increased attention has been given to enhance the hydrolysis and acidification of WAS recently. This study presented an efficient and green strategy based on the combined use of nitrite pretreatment and alkaline pH to stimulate hydrolysis and VFA accumulation from WAS. Results showed that both proteins and polysaccharides increased in the presence of nitrite, indicating the enhancement of sludge solubilization and hydrolysis processes. Mechanism investigations showed that nitrite pretreatment could disintegrate the sludge particle and disperse extracellular polymeric substances (EPS). Then, anaerobic digestion tests demonstrated VFA production increased with nitrite treatment. The maximal VFA accumulation was achieved with 0.1 g N/L nitrite dosage and pH 10.0 at a sludge retention time (SRT) of 7 days, which was much higher VFA production in comparison with the blank, sole nitrite pretreatment, or sole pH 10. The potential analysis suggested that the combined nitrite pretreatment and alkaline pH is capable of enhancing WAS digestion with a great benefit for biological nutrient removal (BNR).

  15. The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media

    DOE PAGES

    John, Samuel St.; Atkinson, Robert W.; Roy, Asa; ...

    2016-01-11

    In this paper, we investigated the performance of several carbon-supported RuxPty electrocatalysts for their alkaline hydrogen oxidation and oxygen reduction performance in the presence of carbonate and compared their performance with monometallic, carbon-supported Pt. Our results indicate a strong dependence of HOR upon pH for the monometallic Pt catalysts (22 mV/pH) and a weak dependence upon pH for the Ru-containing electrocatalysts (3.7, 2.5, and 4.7 mV/pH on Ru0.2Pt0.8, Ru0.4Pt0.6, and Ru0.8Pt0.2, respectively). These results are consistent with our previous findings that illustrate a change in rds from electron transfer (on monometallic Pt) to dissociative hydrogen adsorption (on RuxPty catalysts). Analysismore » of the kinetic currents to determine the rate-determining step via Tafel slope analysis provides additional data supporting this conclusion. There is no difference in the performance at comparable pH values in the presence or absence of carbonate on monometallic Pt indicating that water/hydroxide is the primary proton acceptor for alkaline HOR in 0.1 M KOH aqueous electrolyte. Finally, we observe no pH or carbonate dependence for the ORR on monometallic Pt.« less

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

    USGS Publications Warehouse

    Zielinski, Robert A.

    1977-01-01

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

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

    SciTech Connect

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

    2008-10-11

    No thermodynamic data for Th complexes with aqueous Si are available. To obtain such data, extensive studies on ThO2(am) solubility were carried out as functions of: (1) a wide range of aqueous silica concentrations (0.0004 to 0.14 mol•L-1) at fixed pH values of about 10, 11, 12, and 13; and (2) and variable pH (ranging from 10 to 13.3) at fixed aqueous Si concentrations of about 0.006 mol•L-1 or 0.018 mol•L-1. The samples were equilibrated over long periods (ranging up to 487 days), and the data showed that steady-state concentrations were reached in < 29 days. X-ray diffraction, FTIR, and Raman analyses of the equilibrated solid phases showed that the Th solids were amorphous ThO2(am) containing some adsorbed Si. The solubility of ThO2(am) at pH values ranging from 10 to 13.3 at fixed 0.018 mol•L-1 aqueous Si concentrations decreases rapidly with an increase in pH, and increases dramatically with an increase in Si concentrations beyond about 0.003 mol•L-1 at fixed pH values > 10. The data were interpreted using both the Pitzer and SIT models, and required only the inclusion of one mixed-hydroxy-silica complex of Th [Th(OH)3(H3SiO4)32-]. Both models provided similar complexation constant values for the formation of this species. Density functional theory calculations predict complexes of this stoichiometry, having six-fold coordination of the Th cation, to be structurally stable. Predictions based on the fitted value of log10 K 0=-18.5±0.7 for the ThO2(am) solubility reaction involving Th(OH)3(H3SiO4)32-[ThO2(am)+3H4SiO4+H2O↔Th(OH)3(H3SiO4)32-+2H+], along with the thermodynamic data for aqueous Si species reported in the

  18. Effects of sodium hypochlorite and high pH buffer solution in electrokinetic soil treatment on soil chromium removal and the functional diversity of soil microbial community.

    PubMed

    Cang, Long; Zhou, Dong-Mei; Alshawabkeh, Akram N; Chen, Hai-Feng

    2007-04-02

    Effects of sodium hypochlorite (NaClO), applied as an oxidant in catholyte, and high pH buffer solution on soil Cr removal and the functional diversity of soil microbial community during enhanced electrokinetic treatments of a chromium (Cr) contaminated red soil are evaluated. Using pH control system to maintain high alkalinity of soil together with the use of NaClO increased the electrical conductivities of soil pore liquid and electroosmotic flux compared with the control (Exp-01). The pH control and NaClO improved the removal of Cr(VI) and total Cr from the soil. The highest removal percentages of soil Cr(VI) and total Cr were 96 and 72%, respectively, in Exp-04 when the pH value of the anolyte was controlled at 10 and NaClO was added in the catholyte. The alkaline soil environment and introduction of NaClO in the soil enhanced the desorption of Cr(VI) from the soil and promoted Cr(III) oxidation to mobile Cr(VI), respectively. However, the elevated pH and introduction of NaClO in the soil, which are necessary for improving the removal efficiency of soil Cr, resulted in a significantly adverse impact on the functional diversity of soil microbial community. It suggests that to assess the negative impact of extreme conditions for enhancing the extraction efficiencies of Cr on the soil properties and function is necessary.

  19. Nonlinear friction characteristics between silica surfaces in high pH solution.

    PubMed

    Taran, Elena; Kanda, Yoichi; Vakarelski, Ivan U; Higashitani, Ko

    2007-03-15

    Molecular-scale characteristics of friction forces between silica particles and silica wafers in aqueous solutions of the normal (pH 5.6) and high pH (pH 10.6) are investigated, using the lateral force measuring procedure of the atomic force microscope (AFM). Various significant differences of friction characteristics between solutions of normal and high pH's are found. In the case of solutions of normal pH, the friction force increases linearly with increasing loading force, as the Amonton's law for solid bodies indicates. However, in the case of high pH solutions, the increasing rate with the loading force is considerably reduced in the low loading region, but the value increases abruptly above a critical loading force to overcome the magnitude of friction force of normal pH above the region of very high loading. It is very interesting to know that this nonlinear force curve at high pH is independent of the atomic-scale roughness of surfaces, although the magnitude of friction is greatly influenced by the roughness in the case of normal pH. The reason why the friction at high pH is independent of the surface roughness is postulated to be due to the hairy-like layer formed on the silica surface. The existence of hairy-like layers at high pH is proven directly by the dynamic method of normal force measurements with AFM and the thickness is estimated to be at least ca. 1.3 nm.

  20. Pho4 Is Essential for Dissemination of Cryptococcus neoformans to the Host Brain by Promoting Phosphate Uptake and Growth at Alkaline pH

    PubMed Central

    Kaufman-Francis, Keren; Desmarini, Desmarini; Juillard, Pierre G.; Li, Cecilia; Stifter, Sebastian A.; Feng, Carl G.; Sorrell, Tania C.; Grau, Georges E. R.; Bahn, Yong-Sun

    2017-01-01

    ABSTRACT Phosphate acquisition by fungi is regulated by the phosphate-sensing and acquisition (PHO) signaling pathway. Cryptococcus neoformans disseminates from the lung to the brain and is the commonest cause of fungal meningitis worldwide. To investigate the contribution of PHO signaling to cryptococcal dissemination, we characterized a transcription factor knockout strain (hlh3Δ/pho4Δ) defective in phosphate acquisition. Despite little similarity with other fungal Pho4 proteins, Hlh3/Pho4 functioned like a typical phosphate-responsive transcription factor in phosphate-deprived cryptococci, accumulating in nuclei and triggering expression of genes involved in phosphate acquisition. The pho4Δ mutant strain was susceptible to a number of stresses, the effect of which, except for alkaline pH, was alleviated by phosphate supplementation. Even in the presence of phosphate, the PHO pathway was activated in wild-type cryptococci at or above physiological pH, and under these conditions, the pho4Δ mutant had a growth defect and compromised phosphate uptake. The pho4Δ mutant was hypovirulent in a mouse inhalation model, where dissemination to the brain was reduced dramatically, and markedly hypovirulent in an intravenous dissemination model. The pho4Δ mutant was not detected in blood, nor did it proliferate significantly when cultured with peripheral blood monocytes. In conclusion, dissemination of infection and the pathogenesis of meningitis are dependent on cryptococcal phosphate uptake and stress tolerance at alkaline pH, both of which are Pho4 dependent. IMPORTANCE Cryptococcal meningitis is fatal without treatment and responsible for more than 500,000 deaths annually. To be a successful pathogen, C. neoformans must obtain an adequate supply of essential nutrients, including phosphate, from various host niches. Phosphate acquisition in fungi is regulated by the PHO signaling cascade, which is activated when intracellular phosphate decreases below a critical

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

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

    PubMed

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

    2011-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1998-06-01

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

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

    PubMed

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

    2000-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

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

  6. Computer model of hydroponics nutrient solution pH control using ammonium.

    PubMed

    Pitts, M; Stutte, G

    1999-01-01

    A computer simulation of a hydroponics-based plant growth chamber using ammonium to control pH was constructed to determine the feasibility of such a system. In nitrate-based recirculating hydroponics systems, the pH will increase as plants release hydroxide ions into the nutrient solution to maintain plant charge balance. Ammonium is an attractive alternative to traditional pH controls in an ALSS, but requires careful monitoring and control to avoid overdosing the plants with ammonium. The primary advantage of using NH4+ for pH control is that it exploits the existing plant nutrient uptake charge balance mechanisms to maintain solution pH. The simulation models growth, nitrogen uptake, and pH of a l-m2 stand of wheat. Simulation results indicated that ammonium-based control of nutrient solution pH is feasible using a proportional integral controller. Use of a 1 mmol/L buffer (Ka = 1.6 x 10(-6)) in the nutrient solution is required.

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

    SciTech Connect

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

    1998-09-01

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

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

    PubMed

    Russell, Michael J

    2007-01-01

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

  9. Thermal Characterization of Solutions Containing Gold Nanoparticles at Different pH Values

    NASA Astrophysics Data System (ADS)

    Jiménez-Pérez, J. L.; Sánchez-Ramírez, J. F.; Correa-Pacheco, Z. N.; Cruz-Orea, A.; Anota, E. Chigo; Sánchez-Sinencio, F.

    2013-05-01

    The thermal lens spectrometry (TLS) technique was used to obtain the thermal diffusivity of solutions containing gold nanoparticles (15 nm average diameter) at different pH values. TLS, in a mode-mismatched dual beam configuration, provides a reliable alternative to measure, with high sensitivity, the thermal diffusivities of semitransparent materials, and low thermal diffusivities. The results show that the nanofluid thermal diffusivity increases when the pH is increased. These results will be compared with reported studies for nanofluids with variable pH. From this comparison, it can be seen that the pH values of the solutions influenced the superficial density of charges in the nanoparticles. Also, optical absorption spectra for these gold nanoparticle solutions were obtained using a spectrophotometer, and the nanoparticle size was obtained by the TEM technique. The present measurements were performed at room temperature. This study is important for some medical applications such as photothermal cancer therapy.

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

    DOE PAGES

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

    2016-06-30

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

  11. Effect of pH value of freeze-drying solution on the chromosome integrity and developmental ability of mouse spermatozoa.

    PubMed

    Kaneko, Takehito; Whittingham, David G; Yanagimachi, Ryuzo

    2003-01-01

    The nuclei of freeze-dried mouse spermatozoa are able to retain their chromosome integrity and developmental potential. To optimize the conditions of freeze-drying, we examined whether pH values of the freeze-drying solution affect the chromosome integrity and developmental potential of sperm nuclei. The sperm freeze-drying solution we used contained a high concentration (50 mM) of calcium-chelating EGTA. Sperm chromosomes were examined at the metaphase of the first mitosis after injection of freeze-dried spermatozoa into matured oocytes. The developmental potential of sperm nuclei was assessed by examining the development of fetuses in midgestation. The results showed that both sperm chromosomes and sperm developmental potential are maintained better when the freeze-drying solution was slightly alkaline (pH 8.0) rather than near neutral or acidic (pH 7.4-6.0). The data indicated that the chromosome integrity and developmental ability of mouse spermatozoa are affected by the pH value of freeze-drying solution.

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

    PubMed Central

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

    1993-01-01

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

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

    SciTech Connect

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

    1993-04-01

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

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

    PubMed

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

    2003-01-15

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

  15. Enhanced production of heterologous proteins by the filamentous fungus Trichoderma reesei via disruption of the alkaline serine protease SPW combined with a pH control strategy.

    PubMed

    Zhang, Guoxiu; Zhu, Yao; Wei, Dongzhi; Wang, Wei

    2014-01-01

    The filamentous fungus Trichoderma reesei has received attention as a host for heterologous protein production because of its high secretion capacity and eukaryotic post-translational modifications. However, the heterologous production of proteins in T. reesei is limited by its high expression of proteases. The pH control strategies have been proposed for eliminating acidic, but not alkaline, protease activity. In this study, we verified the expression of a relatively major extracellular alkaline protease (GenBank accession number: EGR49466.1, named spw in this study) from 20 candidates through real-time polymerase chain reaction. The transcriptional level of spw increased about 136 times in response to bovine serum albumin as the sole nitrogen source. Additionally, extracellular protease activity was reduced by deleting the spw gene. Therefore, using this gene expression system, we observed enhanced production and stability of the heterologous alkaline endoglucanase EGV from Humicola insolens using the Δspw strain as compared to the parental strain RUT-C30.

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

    PubMed

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

    2012-02-01

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

  17. The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media

    SciTech Connect

    John, Samuel St.; Atkinson, Robert W.; Roy, Asa; Unocic, Raymond R.; Papandrew, Alexander B.; Zawodzinski, Thomas A.

    2016-01-11

    In this paper, we investigated the performance of several carbon-supported RuxPty electrocatalysts for their alkaline hydrogen oxidation and oxygen reduction performance in the presence of carbonate and compared their performance with monometallic, carbon-supported Pt. Our results indicate a strong dependence of HOR upon pH for the monometallic Pt catalysts (22 mV/pH) and a weak dependence upon pH for the Ru-containing electrocatalysts (3.7, 2.5, and 4.7 mV/pH on Ru0.2Pt0.8, Ru0.4Pt0.6, and Ru0.8Pt0.2, respectively). These results are consistent with our previous findings that illustrate a change in rds from electron transfer (on monometallic Pt) to dissociative hydrogen adsorption (on RuxPty catalysts). Analysis of the kinetic currents to determine the rate-determining step via Tafel slope analysis provides additional data supporting this conclusion. There is no difference in the performance at comparable pH values in the presence or absence of carbonate on monometallic Pt indicating that water/hydroxide is the primary proton acceptor for alkaline HOR in 0.1 M KOH aqueous electrolyte. Finally, we observe no pH or carbonate dependence for the ORR on monometallic Pt.

  18. Influence of pH changes on chlorine-containing endodontic irrigating solutions.

    PubMed

    Rossi-Fedele, G; Guastalli, A R; Doğramacı, E J; Steier, L; De Figueiredo, J A P

    2011-09-01

    Chlorine-containing solutions are used for broad disinfection purposes. Water disinfection literature suggests that their disinfectant action depends on pH values as this will influence the available free chlorine forms. Hypochlorous acid (HOCl) has been suggested to have an antimicrobial effect around 80-100 times stronger than the hypochlorite ion. The aim of this paper was to review the influence of pH changes on the efficacy of chlorine-containing endodontic irrigating solutions. An electronic and hand search (articles published through to 2010, including 'in press' articles; English language; search terms 'root canal irrigants AND sodium hypochlorite or hypochlorous acid or superoxidized water or electrochemically activated solution'; 'antimicrobial action AND sodium hypochlorite or hypochlorous acid or superoxidized water or electrochemically activated solution'; 'tissue dissolution AND sodium hypochlorite or hypochlorous acid or superoxidized water or electrochemically activated solution'; 'smear layer AND sodium hypochlorite or hypochlorous acid or superoxidized water or electrochemically activated solution') was performed to identify publications that compared chlorine water solutions with different pH. Of 1304 publications identified, 20 were considered for inclusion in the review. The search resulted in the retrieval of articles studying sodium hypochlorite (NaOCl), superoxidized waters (SOW) and sodium dichloroisocyanurate (NaDCC). Regarding antimicrobial efficacy, the literature suggested that reducing the pH value of NaOCl to between 6 and 7.5 would lead to improved action; SOW was described as having a lower antimicrobial effect. The tissue dissolution activity NaOCl decreased when the pH reached values between 6 and 7.5; NaDCC and SOW had no clinically relevant tissue dissolution capability. Chlorine solutions of different characteristics appeared to have some cleaning efficacy although they should to be used in conjunction with chelating and

  19. Effect of some anionic polymers on pH of triethanolamine aqueous solutions.

    PubMed

    Musiał, Witold; Kubis, Aleksander

    2004-01-01

    One of the suggested approaches in the management and prophylaxis of acne involves binding of free fatty acids in the form of soap with alcoholamines. Due to a possible irritating effect of alcoholamines associated with a relatively high pH of their aqueous solutions, complexation of alcoholamines with acid polymers is advocated. Triethanolamine is one of the best recognized alcoholamines. It was conventionally neutralized with Carbopols, Eudragits, alginic acid and pectin. During neutralization of polymer dispersions with triethanolamine, variations in the course of the neutralization curve have been observed among individual macromolecular compounds. The pH of 0.1 mol/l triethanolamine solution reaches 10.51, while following a complete neutralization with anionic polymers, such as Carbopols, Eudragits, alginic acid and pectin, pH ranges from 3.88 for systems neutralized with alginic acid to 8.50 for the system neutralized with Eudragit S-100. Complexation of triethanolamine with anionic polymers decreases its pH, and it is possible to find such pH range in which pH of the preparation containing the polymer and triethanolamine will correspond to the physiological pH of the skin.

  20. Changes of the solution pH due to exposure by high-voltage electric pulses.

    PubMed

    Saulis, Gintautas; Lape, Remigijus; Praneviciūte, Rita; Mickevicius, Donatas

    2005-09-01

    The change of the pH of a NaCl solution (139-149 mM NaCl) buffered with 5-15 mM sodium phosphates (pH 7.4) during electromanipulation was studied. It has been determined that an increase in the pH value of electroporation solution of a whole chamber volume, caused by the application of electric field pulses, commonly used in cell electromanipulation procedures, can exceed 1-2 pH units. Several materials for the cathode were tested. In all cases a stainless steel anode was utilized. The aluminum cathode gave a two-fold greater DeltapH in comparison with platinum, copper or stainless steel cathodes. In addition, a substantial release of aluminum (up to 1 mg/l) from the cathode was observed. It has also been found that the shift in pH depended on the medium conductivity: DeltapH of the solution, in which sucrose was substituted for NaCl, was about 5 times less. On the basis of the results obtained here, to avoid the plausible undesirable consequences of the cathodic electrolysis processes, in particular under the conditions of strong electric treatment, it could be recommended that chambers with aluminum electrodes not be utilized and one should use strongly buffered solutions of low conductivity and alternating current (sine or square wave) bipolar electric pulses.

  1. "Biocompatible" Neutral pH Low-GDP Peritoneal Dialysis Solutions: Much Ado About Nothing?

    PubMed

    Misra, Paraish S; Nessim, Sharon J; Perl, Jeffrey

    2017-03-01

    Adverse outcomes in peritoneal dialysis (PD), including PD related infections, the loss of residual kidney function (RKF), and longitudinal, deleterious changes in peritoneal membrane function continue to limit the long-term success of PD therapy. The observation that these deleterious changes occur upon exposure to conventional glucose-based PD solutions fuels the search for a more biocompatible PD solution. The development of a novel PD solution with a neutral pH, and lower in glucose degradation products (GDPs) compared to its conventional predecessors has been labeled a "biocompatible" solution. While considerable evidence in support of these novel solutions' biocompatibility has emerged from cell culture and animal studies, the clinical benefits as compared to conventional PD solutions are less clear. Neutral pH low GDP (NpHLGDP) PD solutions appear to be effective in reducing infusion pain, but their effects on other clinical endpoints including peritoneal membrane function, preservation of RKF, PD-related infections, and technique and patient survival are less clear. The literature is limited by studies characterized by relatively few patients, short follow-up time, heterogeneity with regards to the novel PD solution type under study, and the different patient populations under study. Nonetheless, the search for a more biocompatible PD solution continues with emerging data on promising non glucose-based solutions.

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

    DOEpatents

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

    1994-01-01

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

  3. Halotolerant cyanobacterium Aphanothece halophytica contains NapA-type Na+/H+ antiporters with novel ion specificity that are involved in salt tolerance at alkaline pH.

    PubMed

    Wutipraditkul, Nuchanat; Waditee, Rungaroon; Incharoensakdi, Aran; Hibino, Takashi; Tanaka, Yoshito; Nakamura, Tatsunosuke; Shikata, Masamitsu; Takabe, Tetsuko; Takabe, Teruhiro

    2005-08-01

    Aphanothece halophytica is a halotolerant alkaliphilic cyanobacterium which can grow at NaCl concentrations up to 3.0 M and at pH values up to 11. The genome sequence revealed that the cyanobacterium Synechocystis sp. strain PCC 6803 contains five putative Na+/H+ antiporters, two of which are homologous to NhaP of Pseudomonas aeruginosa and three of which are homologous to NapA of Enterococcus hirae. The physiological and functional properties of NapA-type antiporters are largely unknown. One of NapA-type antiporters in Synechocystis sp. strain PCC 6803 has been proposed to be essential for the survival of this organism. In this study, we examined the isolation and characterization of the homologous gene in Aphanothece halophytica. Two genes encoding polypeptides of the same size, designated Ap-napA1-1 and Ap-napA1-2, were isolated. Ap-NapA1-1 exhibited a higher level of homology to the Synechocystis ortholog (Syn-NapA1) than Ap-NapA1-2 exhibited. Ap-NapA1-1, Ap-NapA1-2, and Syn-NapA1 complemented the salt-sensitive phenotypes of an Escherichia coli mutant and exhibited strongly pH-dependent Na+/H+ and Li+/H+ exchange activities (the highest activities were at alkaline pH), although the activities of Ap-NapA1-2 were significantly lower than the activities of the other polypeptides. Only one these polypeptides, Ap-NapA1-2, complemented a K+ uptake-deficient E. coli mutant and exhibited K+ uptake activity. Mutagenesis experiments suggested the importance of Glu129, Asp225, and Asp226 in the putative transmembrane segment and Glu142 in the loop region for the activity. Overexpression of Ap-NapA1-1 in the freshwater cyanobacterium Synechococcus sp. strain PCC 7942 enhanced the salt tolerance of cells, especially at alkaline pH. These findings indicate that A. halophytica has two NapA1-type antiporters which exhibit different ion specificities and play an important role in salt tolerance at alkaline pH.

  4. Oxygen permeability of soft contact lenses in different pH, osmolality and buffering solution

    PubMed Central

    Lee, Se Eun; Kim, So Ra; Park, Mijung

    2015-01-01

    AIM To determine the effect of pH, osmolality, and buffering system on the oxygen permeability (Dk) of soft contact lenses. METHODS Two hydrogel lenses (nelfilcon A and etafilcon A) and 2 silicone hydrogel lenses (lotrafilcon A and balafilcon A) were used in the study. These lenses were incubated in phosphate-buffered saline (PBS) and borate-buffered saline (BBS) solutions adjusted by 0.8 pH increments to a pH in the range of 5.8-9.0 or in hypotonic (280 mOsmol/kg), isotonic (310 mOsmol/kg) and hypertonic (380 mOsmol/kg) PBS solutions. Polarographic method was used for measuring the Dk and lenses were stacked as 4 layers to correct the boundary effect. RESULTS Dk values of all contact lenses measured in BBS solutions were more stable than those in PBS solutions. Especially the etafilcon A lens showed a relative big change compared with other types of contact lenses at the same conditions. When the osmolality of PBS solution increased from hypotonic to hypertonic, Dk of all contact lenses decreased. Variations in Dk existed depending on lens materials, etafilcon A lens was the most affected and nelfilcon A was the least affected by osmolality. CONCLUSION From the result obtained, it is revealed that Dk of contact lenses is changed by the pH, osmolality, and buffering condition of tear. Thus, Dk of contact lens can be varied by the lens wearers' physiological and/or pathological conditions. PMID:26558223

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

    DOEpatents

    Krot, Nikolai N.; Charushnikova, Iraida A.

    1997-01-01

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

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

    SciTech Connect

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

    1997-06-17

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

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

    NASA Astrophysics Data System (ADS)

    Estevez Mews, Jorge

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

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

    SciTech Connect

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

    1996-06-06

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

  9. Extracellular pH alkalinization by Cl-/HCO3- exchanger is crucial for TASK2 activation by hypotonic shock in proximal cell lines from mouse kidney.

    PubMed

    L'Hoste, S; Barriere, H; Belfodil, R; Rubera, I; Duranton, C; Tauc, M; Poujeol, C; Barhanin, J; Poujeol, P

    2007-02-01

    We have previously shown that K(+)-selective TASK2 channels and swelling-activated Cl(-) currents are involved in a regulatory volume decrease (RVD; Barriere H, Belfodil R, Rubera I, Tauc M, Lesage F, Poujeol C, Guy N, Barhanin J, Poujeol P. J Gen Physiol 122: 177-190, 2003; Belfodil R, Barriere H, Rubera I, Tauc M, Poujeol C, Bidet M, Poujeol P. Am J Physiol Renal Physiol 284: F812-F828, 2003). The aim of this study was to determine the mechanism responsible for the activation of TASK2 channels during RVD in proximal cell lines from mouse kidney. For this purpose, the patch-clamp whole-cell technique was used to test the effect of pH and the buffering capacity of external bath on Cl(-) and K(+) currents during hypotonic shock. In the presence of a high buffer concentration (30 mM HEPES), the cells did not undergo RVD and did not develop outward K(+) currents (TASK2). Interestingly, the hypotonic shock reduced the cytosolic pH (pH(i)) and increased the external pH (pH(e)) in wild-type but not in cftr (-/-) cells. The inhibitory effect of DIDS suggests that the acidification of pH(i) and the alkalinization of pH(e) induced by hypotonicity in wild-type cells could be due to an exit of HCO(3)(-). In conclusion, these results indicate that Cl(-) influx will be the driving force for HCO(3)(-) exit through the activation of the Cl(-)/HCO(3)(-) exchanger. This efflux of HCO(3)(-) then alkalinizes pH(e), which in turn activates TASK2 channels.

  10. A low-temperature-active alkaline pectate lyase from Xanthomonas campestris ACCC 10048 with high activity over a wide pH range.

    PubMed

    Yuan, Peng; Meng, Kun; Wang, Yaru; Luo, Huiying; Shi, Pengjun; Huang, Huoqing; Tu, Tao; Yang, Peilong; Yao, Bin

    2012-11-01

    Alkaline pectate lyases are favorable for the textile industry. Here, we report the gene cloning and expression of a low-temperature-active alkaline pectate lyase (PL D) from Xanthomonas campestris ACCC 10048. Deduced PL D consists of a putative 27-residue signal peptide and a catalytic domain of 320 residues belonging to family PF09492. Recombinant PL D (r-PL D) produced in Escherichia coli was purified to electrophoretic homogeneity with a single step of Ni(2+)-NTA affinity chromatography and showed an apparent molecular weight of ~38 kDa. The pH and temperature optima of r-PL D were found to be 9.0 °C and 30 °C, respectively. Compared with its microbial counterparts, r-PL D had higher activity over a wide pH range (>45 % of the maximum activity at pH 3.0-12.0) and at lower temperatures (>35 % of activity even at 0 °C). The K(m) and V(max) values of r-PL D for polygalacturonic acid were 4.9 gl(-1) and 30.1 μmolmin(-1) mg(-1), respectively. Compared with the commercial compound pectinase from Novozymes, r-PL D showed similar efficacy in reducing the intrinsic viscosity of polygalacturonic acid (35.1 % vs. 36.5 %) and in bioscouring of jute (10.25 % vs. 10.82 %). Thus, r-PL D is a valuable additive candidate for the textile industry.

  11. The effect of temperature and solution pH on the nucleation of tetragonal lysozyme crystals.

    PubMed

    Judge, R A; Jacobs, R S; Frazier, T; Snell, E H; Pusey, M L

    1999-09-01

    Part of the challenge of macromolecular crystal growth for structure determination is obtaining crystals with a volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature, and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over 1 week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions. Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable, however, was pH; crystal numbers changed by two orders of magnitude over the pH range 4.0-5.2. Crystal size also varied with solution conditions, with the largest crystals obtained at pH 5.2. Having optimized the crystallization conditions, we prepared a batch of crystals under the same initial conditions, and 50 of these crystals were analyzed by x-ray diffraction techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.

  12. The Effect of Temperature and Solution pH on the Nucleation of Tetragonal Lysozyme Crystals

    NASA Technical Reports Server (NTRS)

    Judge, Russell A.; Jacobs, Randolph S.; Frazier, Tyralynn; Snell, Edward H.; Pusey, Marc L.

    1999-01-01

    Part of the challenge of macromolecular crystal growth for structure determination is obtaining crystals with a volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature, and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over 1 week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions. Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable, however, was pH; crystal numbers changed by two orders of magnitude over the pH range 4.0-5.2. Crystal size also varied with solution conditions, with the largest crystals obtained at pH 5.2. Having optimized the crystallization conditions, we prepared a batch of crystals under the same initial conditions, and 50 of these crystals were analyzed by x-ray diffraction techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.

  13. The Effect of Temperature and Solution pH on Tetragonal Lysozyme Nucleation Kinetics

    NASA Technical Reports Server (NTRS)

    Judge, Russell A.; Jacobs, Randolph S.; Frazier, Tyralynn; Snell, Edward H.; Pusey, Marc L.

    1998-01-01

    Part of the challenge of macromolecular crystal growth for structure determination is obtaining an appropriate number of crystals with a crystal volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over one week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions, Duplicate experiments indicate the reproducibility of the technique, Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable however, was pH, where crystal numbers changed by two orders of magnitude over the pH range 4.0 to 5.2. Crystal size varied also with solution conditions, with the largest crystals being obtained at pH 5.2. Having optimized the crystallization conditions, a batch of crystals were prepared under exactly the same conditions and fifty of these crystals were analyzed by x-ray techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.

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

    NASA Astrophysics Data System (ADS)

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

    2003-06-01

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

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

    SciTech Connect

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

    2016-06-30

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

  16. Properties of edible films based on pullulan-chitosan blended film-forming solutions at different pH

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Influences of solution pH on the properties of pullulan-chitosan blended (Pul-Chi) films and the rheological properties of film-forming solutions were investigated. The extended conformation of chitosan in pH 4.0 solution increased intermolecular interactions with pullulan compared to the more compa...

  17. Automated pH Control of Nutrient Solution in a Hydroponic Plant Growth System

    NASA Technical Reports Server (NTRS)

    Smith, B.; Dogan, N.; Aglan, H.; Mortley, D.; Loretan, P.

    1998-01-01

    Over, the years, NASA has played an important role in providing to and the development of automated nutrient delivery and monitoring, systems for growing crops hydroponically for long term space missions. One example are the systems used in the Biomass Production Chamber (BPC) at Kennedy Space Center (KSC). The current KSC monitoring system is based on an engineering workstation using standard analog/digital input/output hardware and custom written software. The monitoring system uses completely separate sensors to provide a check of control sensor accuracy and has the ability to graphically display and store data form past experiment so that they are available for data analysis [Fortson, 1992]. In many cases, growing systems have not been fitted with the kind of automated control systems as used at KSC. The Center for Food and Environmental Systems for Human Exploration of Space (CFESH) located on the campus of Tuskegee University, has effectively grown sweetpotatoes and peanuts hydroponically for the past five years. However they have adjusted the pH electrical conductivity and volume of the hydroponic nutrient solution only manually at times when the solution was to be replenished or changed out according to its protocol (e.g. one-week, two-week, or two-day cycle). But the pH of the nutrient solution flowing through the channel is neither known nor controlled between the update, change out, or replenishment period. Thus, the pH of the nutrient solution is not held at an optimum level over the span of the plant's growth cycle. To solve this dilemma, an automated system for the control and data logging of pH data relative to sweetpotato production using the nutrient film technique (NFT) has been developed, This paper discusses a microprocessor-based system, which was designed to monitor, control, and record the pH of a nutrient solution used for growing sweetpotatoes using NFT.

  18. Catalysis and stability of an alkaline protease from a haloalkaliphilic bacterium under non-aqueous conditions as a function of pH, salt and temperature.

    PubMed

    Pandey, Sandeep; Rakholiya, Kalpna D; Raval, Vikram H; Singh, Satya P

    2012-09-01

    A haloalkaliphilic bacterium, isolated from Coastal Gujarat (India) was identified as Oceanobacillus sp. (GQ162111) based on 16S rRNA gene sequence. The organism grew and secreted extra cellular protease in presence of various organic solvents. At 30% (v/v) concentration of hexane, heptane, isooctane, dodecane and decane, significant growth and protease production was evident. The alkaline protease was purified in a single step on phenyl sepharose 6 FF with 28% yield. The molecular mass as judged by SDS-PAGE was 30 kDa. The temperature optimum of protease was 50°C and the enzyme retained 70% activity in 10% (v/v) isooctane. Effect of salt and pH was investigated in combination to assess the effect of isooctane. In organic solvents, the enzyme was considerably active at pH 8-11, with optimum activity at pH 10. Salt at 2 M was optimum for activity and enzyme maintained significant stability up to 18 h even at 3 M salt concentration. Patters of growth, protease production, catalysis and stability of the enzyme are presented. The study resumes significance as limited information is available on the interaction of haloalkaliphilic bacteria and their enzymes with organic solvents.

  19. Growth of Leuconostoc mesenteroides NRRL-B523 in an alkaline medium: suboptimal pH growth inhibition of a lactic acid bacterium.

    PubMed

    Wolf, Barry F; Fogler, H Scott

    2005-01-05

    Bacterial profile modification (BPM), a form of tertiary oil recovery, diverts water from the water-flooded high-permeability zone into the oil-bearing low-permeability zone. During field use, exopolymer-producing bacteria plug the high-permeability zone only in the immediate vicinity of the injection point (the near-well bore region). For effective BPM the plug must penetrate far into the formation. Slowing the specific growth rate, lengthening the lag phase, and slowing the polymerization rate are techniques that can prolong the onset of biopolymer gelation and extend the depth of the biological plug. In batch experiments, the growth of Leuconostoc mesenteroides NRRL-B523 was inhibited by the synergistic effects of high substrate loading and an alkaline pH. Exponential growth was delayed up to 190 h. It was observed that cell division was significantly retarded until the medium pH, reduced by the acid byproducts of fermentation, reached a critical value of 6.79 +/- 0.06. A mathematical model was developed to describe the relationship between specific growth rate, lag time, and medium pH.

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

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

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

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

    SciTech Connect

    Delegard, Calvin H.

    2013-05-01

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

  2. Effects of solution pH and complexing reagents on the desorption of radionuclides in soil

    SciTech Connect

    Wang, Yug-Yea; Yu, C.

    1992-05-01

    In contaminated soils, radionuclides such as uranium and/or thorium may be associated with different chemical species on soil surfaces or inside soil grains with consequent differences in leachability and mobility. Chemical species in contacting solutions can react with soil contaminants by dissolution, ion exchange, or complexation to release contaminants from the soil to the solution. It is important to understand the effect of chemical species in solution for investigating the distribution of uranium and thorium between the soil and the solution under desorption conditions. In this work, the effects of the solution pH and the complexing reagents on the desorption of uranium and thorium under saturated equilibrium conditions were investigated.

  3. Effects of solution pH and complexing reagents on the desorption of radionuclides in soil

    SciTech Connect

    Wang, Yug-Yea; Yu, C.

    1992-01-01

    In contaminated soils, radionuclides such as uranium and/or thorium may be associated with different chemical species on soil surfaces or inside soil grains with consequent differences in leachability and mobility. Chemical species in contacting solutions can react with soil contaminants by dissolution, ion exchange, or complexation to release contaminants from the soil to the solution. It is important to understand the effect of chemical species in solution for investigating the distribution of uranium and thorium between the soil and the solution under desorption conditions. In this work, the effects of the solution pH and the complexing reagents on the desorption of uranium and thorium under saturated equilibrium conditions were investigated.

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

    NASA Astrophysics Data System (ADS)

    Majari Kasmaee, L.; Gobal, F.

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

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

    SciTech Connect

    Kannan, S.; Kelly, R.G.

    1995-12-01

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

  6. Effect of shear force and solution pH on flocs breakage and re-growth formed by nano-Al(13) polymer.

    PubMed

    Xu, Weiying; Gao, Baoyu; Yue, Qinyan; Wang, Yan

    2010-03-01

    The breakage and re-growth of flocs formed by polyaluminum chloride (PAC) and the Al(13)O(4) (OH)(24)(7+) (Al(13) for short) polymer were comparatively evaluated for the coagulation of humic acid (HA). A series of jar experiments were conducted to investigate the impacts of shear rate and solution pH on flocs breakage and re-aggregation potential. Results indicated that the responses of flocs to the increasing shear force and solution pH depend on the coagulant used. The ability of flocs to resist breakage decreased with the increasing shear rate. For all levels of shear force investigated in this study, the flocs formed by Al(13) polymer were weaker than those of PAC, whereas Al(13) polymer displayed a better recoverability than PAC. The similar results were obtained when pH of solution was changed. The flocs generated in acidic conditions were stronger and more recoverable than those generated in alkaline conditions no matter which coagulant was used.

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

    NASA Astrophysics Data System (ADS)

    Chasse, Kevin Robert

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

  8. Rhesus glycoprotein and urea transporter genes in rainbow trout embryos are upregulated in response to alkaline water (pH 9.7) but not elevated water ammonia.

    PubMed

    Sashaw, Jessica; Nawata, Michele; Thompson, Sarah; Wood, Chris M; Wright, Patricia A

    2010-03-01

    Recent studies have shown that genes for the putative ammonia transporter, Rhesus glycoproteins (Rh) and the facilitated urea transporter (UT) are expressed before hatching in rainbow trout (Oncorhychus mykiss Walbaum) embryos. We tested the hypothesis that Rh and UT gene expressions are regulated in response to environmental conditions that inhibit ammonia excretion during early life stages. Eyed-up embryos (22 days post-fertilization (dpf)) were exposed to control (pH 8.3), high ammonia (1.70 mmol l(-1) NH4HCO3) and high pH (pH 9.7) conditions for 48h. With exposure to high water ammonia, ammonia excretion rates were reversed, tissue ammonia concentration was elevated by 9-fold, but there were no significant changes in mRNA expression relative to control embryos. In contrast, exposure to high water pH had a smaller impact on ammonia excretion rates and tissue ammonia concentrations, whereas mRNA levels for the Rhesus glycoprotein Rhcg2 and urea transporter (UT) were elevated by 3.5- and 5.6-fold, respectively. As well, mRNAs of the genes for H+ATPase and Na+/H+ exchanger (NHE2), associated with NH3 excretion, were also upregulated by 7.2- and 13-fold, respectively, in embryos exposed to alkaline water relative to controls. These results indicate that the Rhcg2, UT and associated transport genes are regulated in rainbow trout embryos, but in contrast to adults, there is no effect of high external ammonia at this stage of development.

  9. Hemoglobin correction for near-infrared pH determination in lysed blood solutions.

    PubMed

    Alam, M Kathleen; Franke, James E; Rohrscheib, Mark R; Nunez, David; Abate, Vincent; Maynard, John D; Kemeny, Gabor J

    2003-09-01

    The near-infrared (NIR) measurement of blood pH relies on the spectral signature of histidine residing on the hemoglobin molecule. If the amount of hemoglobin in solution varies, the size of the histidine signal can vary depending on changes in either the pH or hemoglobin concentration. Multivariate calibration models developed using the NIR spectra collected from blood at a single hemoglobin concentration are shown to predict data from different hemoglobin levels with a bias and slope. A simple, scalar path length correction of the spectral data does not correct this problem. However, global partial least-square (PLS) models built with data encompassing a range of hemoglobin concentration have a cross-validated standard error of prediction (CVSEP) similar to the CVSEP of data obtained from a single hemoglobin level. It will be shown that the prediction of pH of an unknown sample using a global PLS model requires that the unknown have a hemoglobin concentration falling within the range encompassed by the global model. An alternative method for correcting the predicted pH for hemoglobin levels is also presented. The alternative method updates the single-hemoglobin-level models with slope and intercept estimates from the pH predictions of data collected at alternate hemoglobin levels. The slope and intercept correction method gave SEP values averaging to 0.034 pH units. Since both methods require some knowledge of the hemoglobin concentration in order for a pH prediction to be made, a model for hemoglobin concentration is developed using spectral data and is used for pH correction.

  10. Characterization of photosystem I from spinach: effect of solution pH.

    PubMed

    Liu, Jianguo; Zhang, Xuefang; Wang, Meng; Liu, Jing; Cao, Meiwen; Lu, Jianren; Cui, Zhanfeng

    2012-04-01

    Our previous work has demonstrated the isolation of photosystem I (PSI) from spinach using ultrafiltration with a final purity of 84%. In order to get a higher purity of PSI and more importantly to develop a practical bioseparation process, key physiochemical properties of PSI and their dependence on operational parameters must be assessed. In this study, the effect of solution pH, one of the most important operating parameters for membrane process, on the property of PSI was examined. Following the isolation of crude PSI from spinach using n-dodecyl-beta-D: -maltoside as detergent, the isoelectric point, aggregation size, zeta potential, low-temperature fluorescence, atomic force microscopy imaging, secondary structure, and thermal stability were determined. Solution pH was found to have a significant effect on the activity, aggregation size and thermal stability of PSI. The results also suggested that the activity of PSI was related to its aggregation size.

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

    SciTech Connect

    Lassinantti Gualtieri, Magdalena

    2015-01-15

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

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

    PubMed

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

    2013-07-01

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

  13. pH dependence of friction forces between silica surfaces in solutions.

    PubMed

    Taran, Elena; Donose, Bogdan C; Vakarelski, Ivan U; Higashitani, Ko

    2006-05-01

    The pH dependence of the friction between a silica particle and a silica wafer was investigated using lateral force microscopy. Measurements were done in the range of 3.6 < or = pH < or = 10.6 and the effect of high loading force was also examined. It is found that the friction is independent of the pH of solutions and increases linearly with the applied load, when the pH is between 3.6 and 8.6. On the other hand, once the pH is above 9.0, the friction becomes extremely small and the dependence on the applied load becomes nonlinear. It is postulated that this transition is due to the development of a gel layer composed of polymer-like segments of silicilic acid anchored on the surface; at the lower applied load, this layer acts as a boundary lubricant between the surfaces, but, at the higher applied load, the entanglements of these segments and more direct contact between two solid surfaces leads to the increase of the friction. The effects found here are expected to play an important role in elucidating the basic mechanism of the planarization process of silica wafers.

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

    NASA Astrophysics Data System (ADS)

    Fattah-alhosseini, A.; Vafaeian, S.

    2016-01-01

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

  15. The effect of solution pH on the electrochemical performance of nanocrystalline metal ferrites MFe2O4 (M=Cu, Zn, and Ni) thin films

    NASA Astrophysics Data System (ADS)

    Elsayed, E. M.; Rashad, M. M.; Khalil, H. F. Y.; Ibrahim, I. A.; Hussein, M. R.; El-Sabbah, M. M. B.

    2016-04-01

    Nanocrystalline metal ferrite MFe2O4 (M=Cu, Zn, and Ni) thin films have been synthesized via electrodeposition-anodization process. Electrodeposited (M)Fe2 alloys were obtained from aqueous sulfate bath. The formed alloys were electrochemically oxidized (anodized) in aqueous (1 M KOH) solution, at room temperature, to the corresponding hydroxides. The parameters controlling the current efficiency of the electrodeposition of (M)Fe2 alloys such as the bath composition and the current density were studied and optimized. The anodized (M)Fe2 alloy films were annealed in air at 400 °C for 2 h. The results revealed the formation of three ferrite thin films were formed. The crystallite sizes of the produced films were in the range between 45 and 60 nm. The microstructure of the formed film was ferrite type dependent. The corrosion behavior of ferrite thin films in different pH solutions was investigated using open circuit potential (OCP) and potentiodynamic polarization measurements. The open circuit potential indicates that the initial potential E im of ZnFe2O4 thin films remained constant for a short time, then sharply increased in the less negative direction in acidic and alkaline medium compared with Ni and Cu ferrite films. The values of the corrosion current density I corr were higher for the ZnFe2O4 films at pH values of 1 and 12 compared with that of NiFe2O4 and CuFe2O4 which were higher only at pH value 1. The corrosion rate was very low for the three ferrite films when immersion in the neutral medium. The surface morphology recommended that Ni and Cu ferrite films were safely used in neutral and alkaline medium, whereas Zn ferrite film was only used in neutral atmospheres.

  16. Development of a selective enterococcus medium based on manganese ion deficiency, sodium azide, and alkaline pH.

    PubMed

    Efthymiou, C J; Joseph, S W

    1974-09-01

    Rogosa broth, without its salt supplement and dissolved in deionized water, was adapted for the selective isolation and enumeration of enterococci. This medium supported good growth of enterococci, but it suppressed growth of other lactic acid bacteria. The sensitivity and specificity of the medium were tested after addition of various increasing concentrations of NaN(3) against known strains of enterococci and other bacteria. Many strains of Streptococcus faecium showed low azide tolerance; optimal growth was obtained at a concentration of 0.01% NaN(3), which totally or partially inhibited unrelated species of lactic acid bacteria. The selectivity of the medium was further increased by pH adjustment to 9.6. Carbonate and Tween 80 were added to overcome partial inhibition of enterococcal growth by the new combination of selective conditions. The final medium was evaluated in agar form in isolations from human and animal feces, polluted water, meat, and dairy products. Counts were obtained after 16 to 17 h of incubation at 37 C. The isolates satisfactorily conformed to the group characteristics of enterococci.

  17. Development of a Selective Enterococcus Medium Based on Manganese Ion Deficiency, Sodium Azide, and Alkaline pH

    PubMed Central

    Efthymiou, C. J.; Joseph, S. W.

    1974-01-01

    Rogosa broth, without its salt supplement and dissolved in deionized water, was adapted for the selective isolation and enumeration of enterococci. This medium supported good growth of enterococci, but it suppressed growth of other lactic acid bacteria. The sensitivity and specificity of the medium were tested after addition of various increasing concentrations of NaN3 against known strains of enterococci and other bacteria. Many strains of Streptococcus faecium showed low azide tolerance; optimal growth was obtained at a concentration of 0.01% NaN3, which totally or partially inhibited unrelated species of lactic acid bacteria. The selectivity of the medium was further increased by pH adjustment to 9.6. Carbonate and Tween 80 were added to overcome partial inhibition of enterococcal growth by the new combination of selective conditions. The final medium was evaluated in agar form in isolations from human and animal feces, polluted water, meat, and dairy products. Counts were obtained after 16 to 17 h of incubation at 37 C. The isolates satisfactorily conformed to the group characteristics of enterococci. Images PMID:4214072

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

    PubMed

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

    2013-03-07

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

  19. Formation of neptunium(IV)-silica colloids at near-neutral and slightly alkaline pH.

    PubMed

    Husar, Richard; Weiss, Stephan; Hennig, Christoph; Hübner, René; Ikeda-Ohno, Atsushi; Zänker, Harald

    2015-01-06

    The reducing conditions in a nuclear waste repository render neptunium tetravalent. Thus, Np is often assumed to be immobile in the subsurface. However, tetravalent actinides can also become mobile if they occur as colloids. We show that Np(IV) is able to form silica-rich colloids in solutions containing silicic acid at concentrations of both the regions above and below the "mononuclear wall" of silicic acid at 2 × 10(-3) M (where silicic acid is expected to start polymerization). These Np(IV)-silica colloids have a size of only very few nanometers and can reach significantly higher concentrations than Np(IV) oxyhydroxide colloids. They can be stable in the waterborne form over longer spans of time. In the Np(IV)-silica colloids, the actinide--oxygen--actinide bonds are increasingly replaced by actinide--oxygen--silicon bonds due to structural incorporation of Si. Possible implications of the formation of such colloids for environmental scenarios are discussed.

  20. Net alkalinity and net acidity 2: Practical considerations

    USGS Publications Warehouse

    Kirby, C.S.; Cravotta, C.A.

    2005-01-01

    The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the

  1. Effects of alkalinity on ammonia removal, carbon dioxide stripping, and system pH in semi-commercial scale water recirculating aquaculture systems operated with moving bed bioreactors

    Technology Transfer Automated Retrieval System (TEKTRAN)

    When operating water recirculating systems (RAS) with high make-up water flushing rates in locations that have low alkalinity in the raw water, such as Norway, knowledge about the required RAS alkalinity concentration is important. Flushing RAS with make-up water containing low alkalinity washes out...

  2. Alkaline Cytosolic pH and High Sodium Hydrogen Exchanger 1 (NHE1) Activity in Th9 Cells.

    PubMed

    Singh, Yogesh; Zhou, Yuetao; Shi, Xiaolong; Zhang, Shaqiu; Umbach, Anja T; Salker, Madhuri S; Lang, Karl S; Lang, Florian

    2016-11-04

    CD4(+) T helper 9 (Th9) cells are a newly discovered Th cell subset that produce the pleiotropic cytokine IL-9. Th9 cells can protect against tumors and provide resistance against helminth infections. Given their pivotal role in the adaptive immune system, understanding Th9 cell development and the regulation of IL-9 production could open novel immunotherapeutic opportunities. The Na(+)/H(+) exchanger 1 (NHE1; gene name Slc9α1)) is critically important for regulating intracellular pH (pHi), cell volume, migration, and cell survival. The pHi influences cytokine secretion, activities of membrane-associated enzymes, ion transport, and other effector signaling molecules such as ATP and Ca(2+) levels. However, whether NHE1 regulates Th9 cell development or IL-9 secretion has not yet been defined. The present study explored the role of NHE1 in Th9 cell development and function. Th cell subsets were characterized by flow cytometry and pHi was measured using 2',7'-bis-(2-carboxyethyl)-5-(and-6)-carboxyfluorescein-acetoxymethyl ester (BCECF-AM) dye. NHE1 functional activity was estimated from the rate of realkalinization following an ammonium pulse. Surprisingly, in Th9 cells pHi and NHE1 activity were significantly higher than in all other Th cell subsets (Th1/Th2/Th17 and induced regulatory T cells (iTregs)). NHE1 transcript levels and protein abundance were significantly higher in Th9 cells than in other Th cell subsets. Inhibition of NHE1 by siRNA-NHE1 or with cariporide in Th9 cells down-regulated IL-9 and ATP production. NHE1 activity, Th9 cell development, and IL-9 production were further blunted by pharmacological inhibition of protein kinase Akt1/Akt2. Our findings reveal that Akt1/Akt2 control of NHE1 could be an important physiological regulator of Th9 cell differentiation, IL-9 secretion, and ATP production.

  3. Ozone oxidation of cassava starch in aqueous solution at different pH.

    PubMed

    Klein, Bruna; Vanier, Nathan Levien; Moomand, Khalid; Pinto, Vânia Zanella; Colussi, Rosana; da Rosa Zavareze, Elessandra; Dias, Alvaro Renato Guerra

    2014-07-15

    Ozone is a more powerful oxidant than common oxidising agents, such as sodium hypochlorite and hydrogen peroxide. It is considered as a safer starch modification method for both consumers and the environment. However, few studies have investigated the changes in starch properties associated with ozone treatment, particularly when applied in aqueous solution. This work aimed to evaluate the carbonyl and carboxyl contents, the X-ray diffraction patterns, the spectrum profiles of Fourier transform infrared spectroscopy, the pasting properties and the surface morphology of ozone-oxidised cassava starch during 60 min under different pH (3.5, 6.5 and 9.5) at 25°C. The pH 6.5 and 9.5 seemed to favour the cross-linking between the depolymerised starch molecules during ozonation. The pH 3.5 was more effective in reducing the peak viscosity, breakdown, setback and final viscosity of cassava starch during ozonation in aqueous solution. No differences in the granule surface morphology were observed in the ozone-treated cassava starches compared to native starch.

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

    SciTech Connect

    Worthington, R.E.; Magdics, A.

    1987-03-24

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

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

    SciTech Connect

    Worthington, R.E.; Magdics, A.

    1987-03-24

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

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

    DOE PAGES

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

    2014-12-04

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

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

    SciTech Connect

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

    2014-12-04

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

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

    SciTech Connect

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

    2006-06-13

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

  9. Escherichia coli YqjA, a Member of the Conserved DedA/Tvp38 Membrane Protein Family, Is a Putative Osmosensing Transporter Required for Growth at Alkaline pH

    PubMed Central

    Kumar, Sujeet

    2015-01-01

    ABSTRACT The ability to persist and grow under alkaline conditions is an important characteristic of many bacteria. In order to survive at alkaline pH, Escherichia coli must maintain a stable cytoplasmic pH of about 7.6. Membrane cation/proton antiporters play a major role in alkaline pH homeostasis by catalyzing active inward proton transport. The DedA/Tvp38 family is a highly conserved membrane protein family of unknown function present in most sequenced genomes. YqjA and YghB are members of the E. coli DedA family with 62% amino acid identity and partially redundant functions. We have shown that E. coli with ΔyqjA and ΔyghB mutations cannot properly maintain the proton motive force (PMF) and is compromised in PMF-dependent drug efflux and other PMF-dependent functions. Furthermore, the functions of YqjA and YghB are dependent upon membrane-embedded acidic amino acids, a hallmark of several families of proton-dependent transporters. Here, we show that the ΔyqjA mutant (but not ΔyghB) cannot grow under alkaline conditions (ranging from pH 8.5 to 9.5), unlike the parent E. coli. Overexpression of yqjA restores growth at alkaline pH, but only when more than ∼100 mM sodium or potassium is present in the growth medium. Increasing the osmotic pressure by the addition of sucrose enhances the ability of YqjA to support growth under alkaline conditions in the presence of low salt concentrations, consistent with YqjA functioning as an osmosensor. We suggest that YqjA possesses proton-dependent transport activity that is stimulated by osmolarity and that it plays a significant role in the survival of E. coli at alkaline pH. IMPORTANCE The ability to survive under alkaline conditions is important for many species of bacteria. Escherichia coli can grow at pH 5.5 to 9.5 while maintaining a constant cytoplasmic pH of about 7.6. Under alkaline conditions, bacteria rely upon proton-dependent transporters to maintain a constant cytoplasmic pH. The DedA/Tvp38 protein family

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

    PubMed

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

    2015-06-15

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

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

    PubMed

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

    2015-06-17

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

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

    SciTech Connect

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

    1995-04-01

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

  13. Study on the Crack Propagation Behavior of ×80 Pipeline Steel Under AC Application in High pH Solution

    NASA Astrophysics Data System (ADS)

    Zhu, M.; Ou, G. F.; Jin, H. Z.; Du, C. W.; Li, X. G.; Liu, Z. Y.

    2015-06-01

    The crack propagation behavior of pipeline steels with or without AC application was studied in high pH solution using the crack propagation experiment (cyclic load). The results show that there is a significant difference in the crack propagation behavior of steels with or without AC interference. The crack growth rate (CGR) of steel under superimposed AC is considerably greater than that without AC. AC could cause an obvious effect on the crack propagation behavior, and enhance the CGR. The crack propagation behavior of steel under AC application in high pH solution is analogous to that in near-neutral pH solution.

  14. Sorption of chlorophenols on microporous minerals: mechanism and influence of metal cations, solution pH, and humic acid.

    PubMed

    Yang, Hui; Hu, Yuanan; Cheng, Hefa

    2016-10-01

    Sorption of 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) on a range of dealuminated zeolites were investigated to understand the mechanism of their sorption on microporous minerals, while the influence of common metal cations, solution pH, and humic acid was also studied. Sorption of chlorophenols was found to increase with the hydrophobicity of the sorbates and that of the microporous minerals, indicating the important role of hydrophobic interactions, while sorption was also stronger in the micropores of narrower sizes because of greater enhancement of the dispersion interactions. The presence of metal cations could enhance chlorophenol sorption due to the additional electrostatic attraction between metal cations exchanged into the mineral micropores and the chlorophenolates, and this effect was apparent on the mineral sorbent with a high density of surface cations (2.62 sites/nm(2)) in its micropores. Under circum-neutral or acidic conditions, neutral chlorophenol molecules adsorbed into the hydrophobic micropores through displacing the "loosely bound" water molecules, while their sorption was negligible under moderately alkaline conditions due to electrostatic repulsion between the negatively charged zeolite framework and anionic chlorophenolates. The influence of humic acid on sorption of chlorophenols on dealuminated Y zeolites suggests that its molecules did not block the micropores but created a secondary sorption sites by forming a "coating layer" on the external surface of the zeolites. These mechanistic insights could help better understand the interactions of ionizable chlorophenols and metal cations in mineral micropores and guide the selection and design of reusable microporous mineral sorbents for sorptive removal of chlorophenols from aqueous stream.

  15. High-resolution kinetics of transferrin acidification in BALB/c 3T3 cells: exposure to pH 6 followed by temperature-sensitive alkalinization during recycling.

    PubMed

    Sipe, D M; Murphy, R F

    1987-10-01

    The kinetics of acidification of diferric human transferrin in BALB/c mouse 3T3 cells were determined by flow cytometry using a modification of the fluorescein-rhodamine fluorescence ratio technique. For cells labeled at 0 degrees C and warmed to 37 degrees C, the minimum pH observed was 6.1 +/- 0.2, occurring 5 min after warmup. This step was followed by a slower alkalinization to the pH of the external medium, occurring with a half-time of 5 min. Warmup to 24 degrees C or 17 degrees C resulted in slowing of the time of onset of acidification such that the minimum pH was 6.3 +/- 0.2, attained 15 and 25 min after warmup, respectively; the alkalinization step was completely blocked. The limited acidification observed for transferrin corresponds to the initial phase of acidification normally observed for other (nonrecycled) ligands. Since transferrin is not further acidified, the results confirm the existence of two phases of acidification during endocytosis. Measurements of transferrin dissociation at neutral pH after exposure to mildly acidic pH support the conclusion that the transferrin cycle may be completed without exposure of transferrin to a pH below 6. The mildly acidic pH of the endocytic compartments involved in recycling may play a role in regulating enzymatic processing of endocytosed material.

  16. Framework stability of nanocrystalline NaY in aqueous solution at varying pH.

    PubMed

    Petushkov, Anton; Freeman, Jasmine; Larsen, Sarah C

    2010-05-04

    Nanocrystalline zeolites are emerging as important materials for a variety of potential applications in industry and medicine. Reducing the particle size to less than 100 nm results in advantages for nanocrystalline zeolites relative to micrometer-sized zeolite crystals, such as very large total and external specific surface areas and reduced diffusion path lengths. Understanding the physical and chemical properties of zeolite nanocrystals is imperative for further development and application of nanocrystalline zeolites. In this study, the framework stability of nanocrystalline NaY zeolite with a crystal size of 66 nm and Si/Al = 1.74 was investigated at pH 7.4, 4, 2, and 1. The solids and solutions were analyzed using several different analytical techniques. The relative crystallinity and crystal size and morphology of the solids were examined by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The aluminum content, Si/Al, and coordination were monitored by inductively coupled plasma/optical emission spectroscopy (ICP/OES), X-ray photoelectron spectroscopy (XPS), and aluminum-27 solid-state magic-angle spinning NMR. As the acidity of the medium increased, the framework stability of nanocrystalline NaY decreased. Treatment of the zeolite samples at pH 1 resulted in complete degradation of the zeolite framework after 1 h. An increase in Si/Al was also observed, suggesting the selective removal of aluminum at low pH.

  17. Unusual Salt and pH Induced Changes in Polyethylenimine Solutions

    PubMed Central

    Millard, Paul; Basu, Saswati; Horkay, Ferenc; Chandran, Preethi L

    2016-01-01

    Linear PEI is a cationic polymer commonly used for complexing DNA into nanoparticles for cell-transfection and gene-therapy applications. The polymer has closely-spaced amines with weak-base protonation capacity, and a hydrophobic backbone that is kept unaggregated by intra-chain repulsion. As a result, in solution PEI exhibits multiple buffering mechanisms, and polyelectrolyte states that shift between aggregated and free forms. We studied the interplay between the aggregation and protonation behavior of 2.5 kDa linear PEI by pH probing, vapor pressure osmometry, dynamic light scattering, and ninhydrin assay. Our results indicate that: At neutral pH, the PEI chains are associated and the addition of NaCl initially reduces and then increases the extent of association. The aggregate form is uncollapsed and co-exists with the free chains. PEI buffering occurs due to continuous or discontinuous charging between stalled states. Ninhydrin assay tracks the number of unprotonated amines in PEI. The size of PEI-DNA complexes is not significantly affected by the free vs. aggregated state of the PEI polymer. Despite its simple chemical structure, linear PEI displays intricate solution dynamics, which can be harnessed for environment-sensitive biomaterials and for overcoming current challenges with DNA delivery. PMID:27685846

  18. Effect of pH upon electroreduction of cadmium(II) ions in aqueous solutions containing polyethylenimine

    SciTech Connect

    Turbanov, K.Yu.; Ermakov, S.S.; Krasikov, B.S.

    1994-02-10

    The effect of the pH of the solution upon electroreduction of cadmium(II) complexes with polyethylenimine has been studied by methods of differential impulse and tast polarography and square-wave and cyclic voltammetry in the region of pH from 4 to 12. A scheme is proposed for the electrode process involving the Cd(II) complexes with polyethylenimine in the studied pH range.

  19. pH dependence of uranyl retention in a quartz/solution system: an XPS study.

    PubMed

    Froideval, A; Del Nero, M; Barillon, R; Hommet, J; Mignot, G

    2003-10-15

    We have investigated the pH dependence of U(VI) retention in quartz/10(-4) M uranyl solution systems, under conditions favoring formation of polynuclear aqueous species and of colloids of amorphous schoepite as U(VI) solubility-limiting phases. X-ray photoelectron spectroscopy was used to gain insights into the coordination environments of sorbed/precipitated uranyl ions in the centrifuged quartz samples. The U4f XPS spectra made it possible to identify unambiguously the presence of two uranyl components. A high binding energy component, whose relative proportion increases with pH, exhibits the U4f lines characteristic of a reference synthetic metaschoepite. Such a high binding energy component is interpreted as a component having a U(VI) oxide hydrate character, either as polynuclear surface oligomers and/or as amorphous schoepite-like (surface) precipitates. Its pH dependence suggests that a binding of polynuclear species at quartz surfaces and/or a formation of amorphous schoepite-like (surface) precipitates is favored when the proportion of aqueous polynuclear species increases. A second surface component exhibits binding energies for the U4f core levels at values significantly lower (DeltaE(b)=1.2 eV) than for metaschoepite, evidencing uranyl ions in a distinct coordination environment. Such a low binding energy component may be attributed to monomeric uranyl surface complexes on the basis of published EXAFS data. Such a hypothesis is supported by a major contribution of the low binding energy component to the U4f XPS spectra of reference samples for uranyl sorbed on quartz from very acidic 10(-3) M uranyl solutions where UO(2)(2+) ions predominate.

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

    SciTech Connect

    Hyder, M.L.

    1997-03-17

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

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

    PubMed

    Mahmud-Ali, Amalid; Bechtold, Thomas

    2015-02-13

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

  2. Tracing of γ-radiation-induced electrical conductivity and pH change of hexamethylenetetramine aqueous solutions and its applications.

    PubMed

    Sife-Eldeen, Kh A

    2013-04-01

    The interest in studying γ-radiation effects on hexamethylenetetramine (HMTA) is due to its importance in nuclear fuel technology. The current study indicates that γ-radiation induces electrical conductivity (RIC) and pH changes in HMTA aqueous solutions. The effects of HMTA concentration, absorbed radiation dose, absorbed dose rate and storage time on RIC and pH changes were studied. HMTA aqueous solutions could be considered as a promising γ-radiation dosimeter, in both technical and medical fields.

  3. Hexavalent chromium reduction with scrap iron in continuous-flow system Part 1: effect of feed solution pH.

    PubMed

    Gheju, M; Iovi, A; Balcu, I

    2008-05-01

    The reduction of hexavalent chromium by scrap iron was investigated in continuous system, using long-term column experiments, for aqueous Cr(VI) solutions having low buffering capacities, over the pH range of 2.00-7.30. The results showed that the initial pH of Cr(VI) solution significantly affects the reduction capacity of scrap iron. The highest reduction capacity was determined to be 19.2 mg Cr(VI)/g scrap iron, at pH 2.50, and decreased with increasing the initial pH of Cr(VI) solution. A considerable decrease in scrap iron reduction capacity (25%) was also observed at pH 2.00, as compared to pH 2.50, due to the increased contribution of H(+) ions to the corrosion of scrap iron, which leads to a rapid decrease in time of the scrap iron volume. Over the pH range of 2.50-7.30, hexavalent chromium concentration increases slowly in time after its breakthrough in column effluent, until a steady-state concentration was observed; similarly, over the same pH range, the amount of solubilized Cr(III) in treated column effluent decreases in time, until a steady-state concentration was observed. The steady-state concentration in column effluent decreased for Cr(VI) and increased for Cr(III) with decreasing the initial pH of Cr(VI) solution. No steady-state Cr(VI) or Cr(III) concentrations in column effluent were observed at pH 2.00. Over the entire studied pH range, the amount of Fe(total) in treated solution increases as the initial pH of column influent is decreased; the results show also a continuously decrease in time of Fe(total) concentration, for a constant initial pH, due to a decrease in time of iron corrosion rate. Cr(III) concentration in column effluent also continuously decreased in time, for a constant initial pH, over the pH range of 2.50-7.30. This represents an advantage, because the amount of precipitant agent used to remove Fe(total) and Cr(III) from the column effluent will also decrease in time. The optimum pH for Cr(VI) reduction with scrap iron in

  4. The effects of surface chemistry of mesoporous silica materials and solution pH on kinetics of molsidomine adsorption

    SciTech Connect

    Dolinina, E.S.; Parfenyuk, E.V.

    2014-01-15

    Adsorption kinetics of molsidomine on mesoporous silica material (UMS), the phenyl- (PhMS) and mercaptopropyl-functionalized (MMS) derivatives from solution with different pH and 298 K was studied. The adsorption kinetics was found to follow the pseudo-second-order kinetic model for all studied silica materials and pH. Effects of surface functional groups and pH on adsorption efficiency and kinetic adsorption parameters were investigated. At all studied pH, the highest molsidomine amount is adsorbed on PhMS due to π–π interactions and hydrogen bonding between surface groups of PhMS and molsidomine molecules. An increase of pH results in a decrease of the amounts of adsorbed molsidomine onto the silica materials. Furthermore, the highest adsorption rate kinetically evaluated using a pseudo-second-order model, is observed onto UMS and it strongly depends on pH. The mechanism of the adsorption process was determined from the intraparticle diffusion and Boyd kinetic film–diffusion models. The results showed that the molsidomine adsorption on the silica materials is controlled by film diffusion. Effect of pH on the diffusion parameters is discussed. - Graphical abstract: The kinetic study showed that the k{sub 2} value, the rate constant of pseudo-second order kinetic model, is the highest for molsidomine adsorption on UMS and strongly depends on pH because it is determined by availability and accessibility of the reaction sites of the adsorbents molsidomine binding. Display Omitted - Highlights: • The adsorption capacities of UMS, PhMS and MMS were dependent on the pH. • At all studied pH, the highest molsidomine amount is adsorbed on PhMS. • The highest adsorption rate, k{sub 2}, is observed onto UMS and strongly depends on pH. • Film diffusion was the likely rate-limiting step in the adsorption process.

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

    PubMed Central

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  7. Snow leopard (Panthera uncia) spermatozoa are sensitive to alkaline pH, but motility in vitro is not influenced by protein or energy supplements.

    PubMed

    Roth, T L; Swanson, W F; Collins, D; Burton, M; Garell, D M; Wildt, D E

    1996-01-01

    To better understand the biology of snow leopard spermatozoa and to facilitate developing assisted reproduction, a series of studies was conducted to: 1) identify the component(s) of complex culture media responsible for the detrimental effect on sperm survival in vitro, 2) optimize medium for supporting sperm viability, and 3) evaluate sperm capacitation in vitro. Constituents of complex media were added systematically to phosphate-buffered saline (PBS) to isolate the factor(s) influencing snow leopard sperm motility in vitro. Sperm capacitation was also assessed following incubation in PBS with bovine serum albumin (BSA), fetal calf serum (FCS), or heparin. For maintaining sperm motility, there was no benefit (P > or = 0.05) to supplementing PBS with low (5%) or high (20%) concentrations of snow leopard serum (SLS) versus FCS or BSA. Likewise, adding supplemental energy substrates (pyruvate, glucose, lactate, or glutamine) did not enhance or hinder (P > or = 0.05) sperm motility. However, motility rapidly decreased (P < 0.05) with the addition of NaHCO3 to PBS or Ham's F10 nutrient mixture. Surprisingly, Ham's F10 with no buffering component or with both NaHCO3 and N-Z-hydroxyethylpiperazine-N'-2-ethanesulfonic acid (HEPES) maintained sperm motility at levels similar (P > or = 0.05) to PBS. Although sperm motility in all treatments decreased with time, there was a strong inverse relationship (P < 0.01; r = 0.90) between motility and sample pH at 6 hours. Spermatozoa incubated in PBS containing FCS, BSA, or heparin did not undergo the acrosome reaction when exposed to calcium ionophore. In summary, alkaline pH has a profound detrimental effect on snow leopard sperm motility, and capacitation does not occur under conditions that normally promote this event in other felid species. These results clearly demonstrate a high degree of interspecific variation among felids in fundamental sperm function, and they provide evidence for the necessity of basic research when

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  9. Effect of pH of spray solution on the electrical properties of cadmium oxide thin films

    NASA Astrophysics Data System (ADS)

    Hodlur, R. M.; Gunnagol, Raghu M.; Rabinal, M. K.

    2015-06-01

    Highly conducting transparent cadmium oxide thin films were prepared by conventional spray pyrolysis technique on glass at 375 °C substrate temperature. The pH of the spray solution was varied by adding ammonia/hydrochloric acid in the spray solution. The XRD pattern showed cubic phase. A lowest resistivity of 9.9 × 10-4 Ω cm (with carrier concentration (n) = 5.1 × 1020 cm-3, mobility (µ)=12.4 cm2/Vs) is observed for pH ˜12. The resistivity is tuned almost by three orders of magnitude by controlling the bath pH with optical transmittance more than 70 %. Thus, without any doping, the electrical conductivity of CdO films could be easily tuned by simply varying the pH of spray solution without compromising the transparency and keeping the other deposition parameters fixed.

  10. Effect of pH of spray solution on the electrical properties of cadmium oxide thin films

    SciTech Connect

    Hodlur, R. M.; Gunnagol, Raghu M.; Rabinal, M. K.

    2015-06-24

    Highly conducting transparent cadmium oxide thin films were prepared by conventional spray pyrolysis technique on glass at 375 °C substrate temperature. The pH of the spray solution was varied by adding ammonia/hydrochloric acid in the spray solution. The XRD pattern showed cubic phase. A lowest resistivity of 9.9 × 10{sup −4} Ω cm (with carrier concentration (n) = 5.1 × 10{sup 20} cm{sup −3}, mobility (µ)=12.4 cm{sup 2}/Vs) is observed for pH ∼12. The resistivity is tuned almost by three orders of magnitude by controlling the bath pH with optical transmittance more than 70 %. Thus, without any doping, the electrical conductivity of CdO films could be easily tuned by simply varying the pH of spray solution without compromising the transparency and keeping the other deposition parameters fixed.

  11. Coadsorption of ciprofloxacin and Cu(II) on montmorillonite and kaolinite as affected by solution pH.

    PubMed

    Pei, Zhiguo; Shan, Xiao-Quan; Kong, Jingjing; Wen, Bei; Owens, Gary

    2010-02-01

    The coadsorption of ciprofloxacin (Cip) and Cu(II) on montmorillonite and kaolinite was studied between pH 4.0 and 9.5. At pH < 5.0, Cu(2+), Cip(+) and [Cu(II)(Cip(+/-))](2+) were the main species in solution. Between pH 5.0-7.0 [Cu(II)(Cip(+/-))](2+) was the dominant complex species. Above pH 8.0 [Cu(II)(Cip(-))(2)](0) precipitated. The presence of Cu(II) exerted no effect on the Cip sorption onto montmorillonite at low pH, whereas it increased Cip sorption on montmorillonite at pH > 6.0 due to the stronger affinity of Cip-Cu(II) complexes compared to sole Cip(-) or Cip(+/-), or Cip sorption via a Cu(II) bridge increased. In contrast, Cip increased Cu(II) adsorption on montmorillonite at pH < 7.0, whereas it decreased the adsorption of Cu(II) on kaolinite at pH 6.0-8.0. Cip was sorbed onto the kaolinite surface via interaction of carboxyl groups over the entire pH range. At pH 4.0-4.7, Cip(+) sorption onto kaolinite's positively charged surface was more favorable than sorption of Cip-Cu(II) complexes. Batch experiments and FTIR analyses indicated that the coordination between Cip(+/-), Cip(-) and Cu(II) were most likely present on kaolinite surface at pH 7.0. At pH > 8.0, Cu(OH)(2) (s) and [Cu(II)(Cip(-))(2)](0) precipitated out of solution or on the montmorillonite or kaolinite surface, which was not considered evidence for either the sorption of Cip or the adsorption of Cu(II).

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    SciTech Connect

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

    2007-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Tian, Hongjing; Guo, Qingjie; Xu, Dongyan

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

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

    DOE PAGES

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

    2015-03-13

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

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

    SciTech Connect

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

    2015-03-13

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

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

    PubMed

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

    2011-04-18

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

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

    PubMed

    Jhuang, Ya-Yi; Cheng, Wen-Tung

    2016-01-01

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

  1. Solute-solvent friction kernels and solution properties of methyl oxazoline-phenyl oxazoline (MeOx-PhOx) copolymers in binary ethanol-water mixtures.

    PubMed

    Das, Ashok K; Hong, Po-Da

    2011-07-07

    Solvent mixtures often alter the solubility of polymeric substances. Statistical copolymers made from 2-methyl-2-oxazoline (MeOx) and 2-phenyl-2-oxazoline (PhOx) are known for their varying solubilities in pure ethanol, pure water and in binary mixtures of ethanol-water. Constrained Molecular Dynamics (MD) simulations have been carried out with an aim to explain the varying solubilities of the statistical MeOx-PhOx copolymers. The solute-solvent dynamic friction kernels calculated through constrained MD simulations corroborate the solubility pattern in these copolymers. The solvation characteristics have been analyzed in terms of the solute-solvent radial distribution functions (RDFs). The ethanol-soluble MeOx-PhOx copolymers exhibit characteristic solute-composition dependence in the dynamic solute-solvent friction kernels, indicating the strength of the solute-solvent correlations. The aggressive solvation by the ethanol molecules in the binary solvent mixtures has been brought out by the O(solute)-H(ethanol) RDFs which exhibit a characteristic dependence on the ethanol content in the solvent composition. The corresponding O(solute)-H(water) RDFs are devoid of any such composition dependence. For all the MeOx-PhOx copolymers, the O-site solvation is strongly dominated by the water molecules and the N-sites are solvated equally by both ethanol and water molecules.

  2. Rapid Assessment of the Influence of Solution pH, Anion Concentration and Temperature on the Dissolution of Alloy 22

    SciTech Connect

    Gray, J J; Hayes, J R; Gdowski, G E; Viani, B E; Orme, C A

    2005-05-19

    We introduce an acid titration technique for the rapid characterization of the influence of solution pH, anion (such as chloride) concentration and temperature on the dissolution of metals. We demonstrate the technique with the characterization of the dissolution of alloy 22 (Ni-22Cr-13Mo-3W-3Fe) exposed to chloride-containing hydrochloric, sulfuric and nitric acid environments as a function of pH (from pH 5 to pH -1) and temperature (25-90 C). A combination of electrochemical techniques (electrochemical impedance spectroscopy and linear polarization resistance) and atomic force microscopy are used to characterize the influence of the various solutions on the dissolution of alloy 22. In solutions containing hydrochloric and sulfuric acids, a critical temperature exists for passive film breakdown on alloy 22 for all environments tested. Below the critical temperature, corrosion rates are less than 1 {micro}m/year. Above the critical temperature, the effect of temperature on dissolution rates is a function of both the pH and chloride content of the solution. In nitric acid containing solutions, the presence of nitrates promotes a stable passive oxide film that inhibits dissolution in all environments tested.

  3. Reactive solute transport in streams. 2. Simulation of a pH modification experiment

    USGS Publications Warehouse

    Runkel, R.L.; McKnight, Diane M.; Bencala, K.E.; Chapra, S.C.

    1996-01-01

    We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pK(sp) from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pK(sp) from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and p H profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH- dependent processes within the context of hydrologic transport.

  4. A universal indicator dye pH assay for crystallization solutions and other high-throughput applications.

    PubMed

    Newman, Janet; Sayle, Roger A; Fazio, Vincent J

    2012-08-01

    In protein crystallization, as well as in many other fields, it is known that the pH at which experiments are performed is often the key factor in the success or failure of the trials. With the trend towards plate-based high-throughput experimental techniques, measuring the pH values of solutions one by one becomes prohibitively time- and reagent-expensive. As part of an HT crystallization facility, a colour-based pH assay that is rapid, uses very little reagent and is suitable for 96-well or higher density plates has been developed.

  5. A renaissance of soaps? - How to make clear and stable solutions at neutral pH and room temperature.

    PubMed

    Wolfrum, Stefan; Marcus, Julien; Touraud, Didier; Kunz, Werner

    2016-10-01

    Soaps are the oldest and perhaps most natural surfactants. However, they lost much of their importance since "technical surfactants", usually based on sulfates or sulfonates, have been developed over the last fifty years. Indeed, soaps are pH- and salt-sensitive and they are irritant, especially to the eyes. In food emulsions, although authorized, they have a bad taste, and long-chain saturated soaps have a high Krafft temperature. We believe that most or perhaps all of these problems can be solved with modern formulation approaches. We start this paper with a short overview of our present knowledge of soaps and soap formulations. Then we focus on the problem of the lacking soap solubility at neutral pH values. For example, it is well known that with the food emulsifier sodium oleate (NaOl), clear and stable aqueous solutions can only be obtained at pH values higher than 10. A decrease in the pH value leads to turbid and unstable solutions. This effect is not compatible with the formulation of aqueous stable and drinkable formulations with neutral or even acidic pH values. However, the pH value/phase behavior of aqueous soap solutions can be altered by the addition of other surfactants. Such a surfactant can be Rebaudioside A (RebA), a steviol glycoside from the plant Stevia rebaudiana which is used as a natural food sweetener. In a recent paper, we showed the influence of RebA on the apKa value of sodium oleate in a beverage microemulsion and on its clearing temperature. In the present paper, we report on the effect of the edible bio-surfactant RebA, on the macroscopic and microscopic phase behavior of simple aqueous sodium oleate solutions at varying pH values. The macroscopic phase behavior is investigated by visual observation and turbidity measurements. The microscopic phase behavior is analyzed by acid-base titration curves, phase-contrast and electron microscopy. It turned out that even at neutral pH, aqueous NaOl/RebA solutions can be completely clear and

  6. Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

    USGS Publications Warehouse

    Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

    1996-01-01

    Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

  7. Enzymatic characterization of peptidic materials isolated from aqueous solutions of ammonium cyanide (pH 9) and hydrocyanic acid (pH 6) exposed to ionizing radiation.

    PubMed

    Niketic, V; Draganić, Z; Nesković, S; Draganić, I

    1982-01-01

    The enzymatic digestion of some radiolytically produced peptidic materials was examined. The substrates were compounds isolated from 0.1 molar solutions of NH4CN (pH 9) and HCN (pH 6), after their exposure to gamma rays from a 60Co source (15-20 Mrad doses). Commercial proteolytic enzymes pronase and aminopeptidase M were used. The examined materials were of composite nature and proteolytic action was systematically observed after their subsequent purification. In some fractions the effect was found to be positive with up to 30% of peptide bonds cleaved with respect to the amino acid content. These findings support our previous conclusions on the free radical induced formation of peptidic backbones without the intervention of amino acids. Some side effects were also noted which might be of interest in observations on enzymatic cleavage of other composite peptidic materials of abiotic origin.

  8. Outside the pH box: Boron isotopes in synthetic calcite precipitated under varying solution chemistry

    NASA Astrophysics Data System (ADS)

    Farmer, J. R.; Uchikawa, J.; Penman, D. E.; Hoenisch, B.; Zeebe, R. E.

    2015-12-01

    Boron isotopic measurements (δ11B) in marine carbonates are a powerful tool for reconstructing past ocean carbon chemistry and the carbon cycle. Boron systematics in marine carbonates are rooted in the equilibrium dissociation of dissolved boron in seawater, but existing evidence from biogenic carbonates (corals, planktic and benthic foraminifers) suggests somewhat variable controls on boron concentration and δ11B. Synthetic precipitation experiments provide an opportunity to study boron systematics without biological interference, and recent studies (e.g., Uchikawa et al., 2015, GCA v150, 171-191) suggest that boron incorporation (measured as B/Ca ratios) into synthetic carbonates varies both with the elemental composition of experimental seawater and precipitation rate. Here we extend the geochemical characterization of synthetic calcite by investigating the influences of changing solution chemistry (pH, [Ca2+], [DIC] and [B]) and precipitation rate on their boron isotopic composition. Our results will be evaluated in the context of carbonate precipitation rates, modes of boron incorporation, and changing seawater chemistry through geologic time.

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

    PubMed

    Leriche, V; Briandet, R; Carpentier, B

    2003-01-01

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

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

    PubMed

    Dunbar, W E; Schilt, A A

    1972-09-01

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

  11. [Aluminum dissolution and changes of pH in soil solution during sorption of copper by aggregates of paddy soil].

    PubMed

    Xu, Hai-Bo; Zhao, Dao-Yuan; Qin, Chao; Li, Yu-Jiao; Dong, Chang-Xun

    2014-01-01

    Size fractions of soil aggregates in Lake Tai region were collected by the low-energy ultrasonic dispersion and the freeze-desiccation methods. The dissolution of aluminum and changes of pH in soil solution during sorption of Cu2+ and changes of the dissolution of aluminum at different pH in the solution of Cu2+ by aggregates were studied by the equilibrium sorption method. The results showed that in the process of Cu2+ sorption by aggregates, the aluminum was dissoluted and the pH decreased. The elution amount of aluminum and the decrease of pH changed with the sorption of Cu2+, both increasing with the increase of Cu2+ sorption. Under the same conditions, the dissolution of aluminum and the decrease of pH were in the order of coarse silt fraction > silt fraction > sand fraction > clay fraction, which was negatively correlated with the amount of iron oxide, aluminum and organic matter. It suggested that iron oxide, aluminum and organic matters had inhibitory and buffering effect on the aluminum dissolution and the decrease of pH during the sorption of Cu2+.

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

    NASA Astrophysics Data System (ADS)

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

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

  13. Effect of pH and coexisting anions on removal of phosphate from aqueous solutions by inorganic-based mesostructures.

    PubMed

    Choi, Jae-Woo; Choi, Yong-Soo; Hong, Seok-Won; Kim, Dong-Ju; Lee, Sang-Hyup

    2012-07-01

    This study investigated the effect of pH and the presence of coexisting (competitive) anions on the removal of phosphate by titanium mesostructures synthesized using do- or hexadecyltrimethylammonium bromide. To address these research objectives, experiments were conducted (1) under controlled initial pH values (2 to 10); and (2) through injection of nitrate, fluoride, chloride, or sulfate anions into a phosphate solution. Based on the experimental results, an initial of pH of 2 was found to be optimal for use of titanium mesostructures. The presence of fluoride anions in solution significantly decreased the removal efficiency of phosphate removal (3.56% at 3.95 mg/g). However, the addition of nitrate, chloride, and sulfate anions did not affect phosphate removal.

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

    PubMed

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

    2006-04-21

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

  15. Deletions of endocytic components VPS28 and VPS32 affect growth at alkaline pH and virulence through both RIM101-dependent and RIM101-independent pathways in Candida albicans.

    PubMed

    Cornet, Muriel; Bidard, Frédérique; Schwarz, Patrick; Da Costa, Grégory; Blanchin-Roland, Sylvie; Dromer, Françoise; Gaillardin, Claude

    2005-12-01

    Ambient pH signaling involves a cascade of conserved Rim or Pal products in ascomycetous yeasts or filamentous fungi, respectively. Recent evidences in the fungi Aspergillus nidulans, Saccharomyces cerevisiae, Yarrowia lipolytica, and Candida albicans suggested that components of endosomal sorting complexes required for transport (ESCRT) involved in endocytic trafficking were needed for signal transduction along the Rim pathway. In this study, we confirm these findings with C. albicans and show that Vps28p (ESCRT-I) and Vps32p/Snf7p (ESCRT-III) are required for the transcriptional regulation of known targets of the Rim pathway, such as the PHR1 and PHR2 genes encoding cell surface proteins, which are expressed at alkaline and acidic pH, respectively. We additionally show that deletion of these two VPS genes, particularly VPS32, has a more drastic effect than a RIM101 deletion on growth at alkaline pH and that this effect is only partially suppressed by expression of a constitutively active form of Rim101p. Finally, in an in vivo mouse model, both vps null mutants were significantly less virulent than a rim101 mutant, suggesting that VPS28 and VPS32 gene products affect virulence both through Rim-dependent and Rim-independent pathways.

  16. Effect of pH on the Electrophoretic Mobility of Spores of Bacillus anthracis and Its Surrogates in Aqueous Solutions

    EPA Science Inventory

    Electrophoretic mobility (EPM) of endospores of Bacillus anthracis and surrogates were measured in aqueous solution across a broad pH range and several ionic strengths. EPM values trended around phylogenetic clustering based on the 16S rRNA gene. Measurements reported here prov...

  17. [Effects of pH and coexisting cations on ammonia adsorption from aqueous solution by strawberry stem powder].

    PubMed

    Liu, Hai-wei; Liu, Yun; Wang, Hai-yun; Dong, Yuan-hua

    2010-08-01

    Batch equilibrium experiments were carried out to study ammonia adsorptions from aqueous solution by strawberry (Fragaia ananassa Duchesne) stem powder. The effects of pH, coexisting cations, initial ammonia concentration and temperature were investigated as well. The results showed that the equilibrium data fitted well to the Langmuir model and Freundlich model, and the maximum adsorption capacities were 3.05, 4.24 and 4.79 mg x g(-1) at 15, 25 and 35 degrees C respectively. The increase of temperature was favorable to ammonia adsorption. The optimal pH of ammonia adsorption was in the range of 4-8. The NH4+ content decreased at higher pH and the negative charges decreased at lower pH, resulting in the decrease of ammonia adsorption at both higher and lower pH. The pH changes after adsorption buffered both effects. K+, Na+, Ca2+ and Mg2+ had no effect on ammonia adsorption by strawberry stem, but Zn2+ and Al3+ decreased the adsorption for their hydrolyzation. The ammonia adsorption by strawberry stem powder could be applied in a large pH range and could not be affected by usual metal cations in wastewater, therefore the strawberry stem powder not only could be a suitable ammonia adsorbent, but also had advantages comparing with most mineral materials.

  18. Net alkalinity and net acidity 1: Theoretical considerations

    USGS Publications Warehouse

    Kirby, C.S.; Cravotta, C.A.

    2005-01-01

    Net acidity and net alkalinity are widely used, poorly defined, and commonly misunderstood parameters for the characterization of mine drainage. The authors explain theoretical expressions of 3 types of alkalinity (caustic, phenolphthalein, and total) and acidity (mineral, CO2, and total). Except for rarely-invoked negative alkalinity, theoretically defined total alkalinity is closely analogous to measured alkalinity and presents few practical interpretation problems. Theoretically defined "CO 2-acidity" is closely related to most standard titration methods with an endpoint pH of 8.3 used for determining acidity in mine drainage, but it is unfortunately named because CO2 is intentionally driven off during titration of mine-drainage samples. Using the proton condition/mass- action approach and employing graphs to illustrate speciation with changes in pH, the authors explore the concept of principal components and how to assign acidity contributions to aqueous species commonly present in mine drainage. Acidity is defined in mine drainage based on aqueous speciation at the sample pH and on the capacity of these species to undergo hydrolysis to pH 8.3. Application of this definition shows that the computed acidity in mg L -1 as CaCO3 (based on pH and analytical concentrations of dissolved FeII, FeIII, Mn, and Al in mg L -1):aciditycalculated=50{1000(10-pH)+[2(FeII)+3(FeIII)]/56+2(Mn)/ 55+3(Al)/27}underestimates contributions from HSO4- and H+, but overestimates the acidity due to Fe3+ and Al3+. However, these errors tend to approximately cancel each other. It is demonstrated that "net alkalinity" is a valid mathematical construction based on theoretical definitions of alkalinity and acidity. Further, it is shown that, for most mine-drainage solutions, a useful net alkalinity value can be derived from: (1) alkalinity and acidity values based on aqueous speciation, (2) measured alkalinity minus calculated acidity, or (3) taking the negative of the value obtained in a

  19. Fractal structure and the dynamics of aggregation of synthetic melanin in low pH aqueous solutions

    SciTech Connect

    Huang, J.S.; Sung, J.; Eisner, M.; Moss, S.C.; Gallas, J.

    1989-01-01

    We have used static and dynamic light scattering to study the dynamics of aggregation of synthetic melanin, an amorphous biopolymeric substance, in low pH aqueous solution. We have found that, depending on the final pH value of the solutions, there existed two regimes of the aggregation kinetics, one corresponding to diffusion limited aggregation (DLA), and the other corresponding to reaction limited aggregation (RLA). The precipitates formed in these two regimes can be characterized by fractal structures. We have found fractal dimensions of d/sub f/ = 1.8 for the DLA clusters and d/sub f/ = 2.2 for the RLA clusters. These results agree well with the proposed limits of the fractal dimensions of the gold aggregates formed in aqueous solutions by Weitz et al.

  20. The fractal structure and the dynamics of aggregation of synthetic melanin in low pH aqueous solutions

    NASA Astrophysics Data System (ADS)

    Huang, J. S.; Sung, J.; Eisner, M.; Moss, S. C.; Gallas, J.

    1989-01-01

    We have used static and dynamic light scattering to study the dynamics of aggregation of synthetic melanin, an amorphous biopolymeric substance, in low pH aqueous solution. We have found that, depending on the final pH value of the solutions, there existed two regimes of the aggregation kinetics, one corresponding to diffusion limited aggregation (DLA), and the other corresponding to reaction limited aggregation (RLA). The precipitates formed in these two regimes can be characterized by fractal structures. We have found fractal dimensions of df =1.8 for the DLA clusters and df =2.2 for the RLA clusters. These results agree well with the proposed limits of the fractal dimensions of the gold aggregates formed in aqueous solutions by Weitz et al.

  1. Effects of solution pH and complexing reagents on uranium and thorium desorption under saturated equilibrium conditions

    SciTech Connect

    Wang, Yug-Yea; Yu, C.

    1992-08-01

    Three contaminated bulk surface soils were used for investigating the effect of solution pH and complexing reagents on uranium and thorium desorption. At a low solution pH, the major chemical species of uranium and thorium, uranyl UO{sub 2}{sup +2}, thorium dihydroxide Th(OH){sub 2}{sup +2}, and thorium hydroxide Th(OH){sup +3}, tend to form complexes with acetates in the solution phase, which increases the fractions of uranium and thorium desorbed into this phase. At a high solution pH, important uranium and thorium species such as uranyl tricarbonate complex UO{sub 2}(CO){sub 3}{sub 3}{sup {minus}4} and thorium tetrahydroxide complex Th(OH){sub 4} tend to resist complexation with acetates. The presence of complexing reagents in solution can release radionuclides such as uranium and/or thorium from the soil to the solution by forming soluble complexes. Sodium bicarbonate (NaHCO{sub 3}) and diethylenetriaminepentaacetic acid (DTPA) are strong complex formers that released 38% to 62% of total uranium activity and 78% to 86% of total thorium activity, respectively, from the soil samples investigated. Solutions of 0.1 molar sodium nitrate (NaNO{sub 3}) and 0.1 molar sodium sulfate (Na{sub 2}SO{sub 4}) were not effective complex formers with uranium and thorium under the experimental conditions. Fractions of uranium and thorium desorbed by 0.15g/200ml humic acid ranged from 4.62% to 6.17% and 1.59% to 7.09%, respectively. This work demonstrates the importance of a knowledge of solution chemistry in investigating the desorption of radionuclides.

  2. Effects of solution pH and complexing reagents on uranium and thorium desorption under saturated equilibrium conditions

    SciTech Connect

    Wang, Yug-Yea; Yu, C.

    1992-01-01

    Three contaminated bulk surface soils were used for investigating the effect of solution pH and complexing reagents on uranium and thorium desorption. At a low solution pH, the major chemical species of uranium and thorium, uranyl UO{sub 2}{sup +2}, thorium dihydroxide Th(OH){sub 2}{sup +2}, and thorium hydroxide Th(OH){sup +3}, tend to form complexes with acetates in the solution phase, which increases the fractions of uranium and thorium desorbed into this phase. At a high solution pH, important uranium and thorium species such as uranyl tricarbonate complex UO{sub 2}(CO){sub 3}{sub 3}{sup {minus}4} and thorium tetrahydroxide complex Th(OH){sub 4} tend to resist complexation with acetates. The presence of complexing reagents in solution can release radionuclides such as uranium and/or thorium from the soil to the solution by forming soluble complexes. Sodium bicarbonate (NaHCO{sub 3}) and diethylenetriaminepentaacetic acid (DTPA) are strong complex formers that released 38% to 62% of total uranium activity and 78% to 86% of total thorium activity, respectively, from the soil samples investigated. Solutions of 0.1 molar sodium nitrate (NaNO{sub 3}) and 0.1 molar sodium sulfate (Na{sub 2}SO{sub 4}) were not effective complex formers with uranium and thorium under the experimental conditions. Fractions of uranium and thorium desorbed by 0.15g/200ml humic acid ranged from 4.62% to 6.17% and 1.59% to 7.09%, respectively. This work demonstrates the importance of a knowledge of solution chemistry in investigating the desorption of radionuclides.

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

    PubMed

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

    2011-01-01

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

  4. Low-temperature solution processing of palladium/palladium oxide films and their pH sensing performance.

    PubMed

    Qin, Yiheng; Alam, Arif U; Pan, Si; Howlader, Matiar M R; Ghosh, Raja; Selvaganapathy, P Ravi; Wu, Yiliang; Deen, M Jamal

    2016-01-01

    Highly sensitive, easy-to-fabricate, and low-cost pH sensors with small dimensions are required to monitor human bodily fluids, drinking water quality and chemical/biological processes. In this study, a low-temperature, solution-based process is developed to prepare palladium/palladium oxide (Pd/PdO) thin films for pH sensing. A precursor solution for Pd is spin coated onto pre-cleaned glass substrates and annealed at low temperature to generate Pd and PdO. The percentages of PdO at the surface and in the bulk of the electrodes are correlated to their sensing performance, which was studied by using the X-ray photoelectron spectroscope. Large amounts of PdO introduced by prolonged annealing improve the electrode's sensitivity and long-term stability. Atomic force microscopy study showed that the low-temperature annealing results in a smooth electrode surface, which contributes to a fast response. Nano-voids at the electrode surfaces were observed by scanning electron microscope, indicating a reason for the long-term degradation of the pH sensitivity. Using the optimized annealing parameters of 200°C for 48 h, a linear pH response with sensitivity of 64.71±0.56 mV/pH is obtained for pH between 2 and 12. These electrodes show a response time shorter than 18 s, hysteresis less than 8 mV and stability over 60 days. High reproducibility in the sensing performance is achieved. This low-temperature solution-processed sensing electrode shows the potential for the development of pH sensing systems on flexible substrates over a large area at low cost without using vacuum equipment.

  5. COUPLING THE ALKALINE-SURFACTANT-POLYMER TECHNOLOGY AND THE GELATION TECHNOLOGY TO MAXIMIZE OIL PRODUCTION

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson

    2004-10-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or more efficient areal sweep efficiency for those with high permeability contrast ''thief zones''. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or those with thief zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. A prior fluid-fluid report discussed interaction of different gel chemical compositions and alkaline-surfactant-polymer solutions. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in the fluid-fluid analyses. Aluminum-polyacrylamide, flowing gels are not stable to alkaline-surfactant-polymer solutions of either pH 10.5 or 12.9. Chromium acetate-polyacrylamide flowing and rigid flowing gels are stable to subsequent alkaline-surfactant-polymer solution injection. Rigid flowing chromium acetate-polyacrylamide gels maintained permeability reduction better than flowing chromium acetate-polyacrylamide gels. Silicate-polyacrylamide gels are not stable with subsequent injection of either a pH 10.5 or a 12.9 alkaline-surfactant-polymer solution. Neither aluminum citrate-polyacrylamide nor silicate-polyacrylamide gel systems produced significant incremental oil in linear corefloods. Both flowing and rigid flowing chromium acetate-polyacrylamide gels produced incremental oil with the rigid flowing gel producing the greatest amount. Higher oil recovery could have been due to higher differential pressures across cores. None of the gels tested

  6. Continuous bioproduction of short-chain fatty acids from sludge enhanced by the combined use of surfactant and alkaline pH.

    PubMed

    Chen, Yinguang; Liu, Kun; Su, Yinglong; Zheng, Xiong; Wang, Qin

    2013-07-01

    This work reported the enhancement of continuous SCFA production from sludge by the combined use of surfactant (sodium dodecylbenzene sulfonate (SDBS)) and pH 10 (i.e., SDBS & pH 10). The maximal SCFA production (2056 mg COD/L) was achieved under the SDBS & pH 10 condition at a sludge retention time (SRT) of 12d, which was much higher than that of the blank, sole SDBS, or pH 10. The mechanisms investigation showed that the combined strategy had greater sludge solubilization, higher protein hydrolysis, and lower activity of methanogens. Fluorescence in situ hybridization analysis revealed that the abundance of bacteria was increased, whereas that of archaea was decreased by SDBS & pH 10. The excitation emission matrix fluorescence spectroscopy assay further suggested that SBDS caused protein structure change, which benefited protein hydrolysis.

  7. The formation of stable pH gradients with weak monovalent buffers for isoelectric focusing in free solution

    NASA Technical Reports Server (NTRS)

    Mosher, Richard A.; Thormann, Wolfgang; Graham, Aly; Bier, Milan

    1985-01-01

    Two methods which utilize simple buffers for the generation of stable pH gradients (useful for preparative isoelectric focusing) are compared and contrasted. The first employs preformed gradients comprised of two simple buffers in density-stabilized free solution. The second method utilizes neutral membranes to isolate electrolyte reservoirs of constant composition from the separation column. It is shown by computer simulation that steady-state gradients can be formed at any pH range with any number of components in such a system.

  8. The biocompatibility of neutral pH, low-GDP peritoneal dialysis solutions: benefit at bench, bedside, or both?

    PubMed

    Perl, Jeffrey; Nessim, Sharon J; Bargman, Joanne M

    2011-04-01

    For patients on peritoneal dialysis (PD), the development of peritonitis, the decline of residual kidney function, and the loss of peritoneal membrane function are central events that affect both patient and technique survival. The use of glucose as the osmotic agent in conventional PD solutions may increase the susceptibility to each of these events. However, its use may also be associated with systemic metabolic perturbations and, in turn, an increase in cardiovascular morbidity. Both in vitro and in vivo evidence suggest that both the local peritoneal and systemic toxicity induced by the use of glucose may be in part mediated by the presence of glucose degradation products (GDPs) coupled with the hyperosmolarity, reduced pH, and use of lactate as the buffer in conventional PD solutions. Therefore, the use of neutral pH, low-GDP (NpHL(GDP)), bicarbonate-buffered PD solutions may represent a promising strategy to attenuate some of these adverse effects. However, the impact of these novel solutions on clinical outcomes remains largely unknown. In this review, we will highlight evidence regarding the biocompatibility of NpHL(GDP) PD solutions, review the utility of current biomarkers in the evaluation of biocompatibility, and discuss the clinical outcome data with these solutions.

  9. Coupling the Alkaline-Surfactant-Polymer Technology and The Gelation Technology to Maximize Oil Production

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson; Phil Dowling; David Stewart; Bill Jones

    2005-12-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or reservoirs with different sand lenses with high permeability contrast. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more crude oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or reservoirs with high permeability contrast zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. Fluid-fluid interaction with different gel chemical compositions and alkaline-surfactant-polymer solution with pH values ranging from 9.2 to 12.9 have been tested. Aluminum-polyacrylamide gels are not stable to alkaline-surfactant-polymer solutions at any pH. Chromium-polyacrylamide gels with polymer to chromium ion ratios of 25 or greater were stable to alkaline-surfactant-polymer solutions if solution pH was 10.6 or less. When the polymer to chromium ion was 15 or less, chromium-polyacrylamide gels were stable to alkaline-surfactant-polymer solutions with pH values up to 12.9. Chromium-xanthan gum gels were stable to alkaline-surfactant-polymer solutions with pH values of 12.9 at the polymer to chromium ion ratios tested. Silicate-polyacrylamide, resorcinol-formaldehyde, and sulfomethylated resorcinol-formaldehyde gels were also stable to alkaline-surfactant-polymer solutions with pH values ranging from 9.2 to 12.9. Iron-polyacrylamide gels were immediately destroyed when contacted with any of the alkaline-surfactant-polymer solutions with pH values ranging from 9.2 to 12.9. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in

  10. Efficient bacterial inactivation in aqueous solution by low-temperature atmospheric pressure plasma application with a reduction of the solution pH

    NASA Astrophysics Data System (ADS)

    Kitano, Katsuhisa; Ikawa, Satoshi; Tani, Atsushi; Ohnishi, Naofumi; Hamaguchi, Satoshi

    2009-10-01

    With some medical applications in mind, bacterial inactivation experiments in aqueous solution have been performed with the use of low-temperature atmospheric pressure plasmas. We have successfully found that efficient bactericidal activity can be achieved if the solution is sufficiently acidic. It is interesting to note that there is a critical pH value of about 4.7 for the bactericidal effects, below which the bacteria are efficiently inactivated and above which the bacteria are hardly affected by the plasma application. When the plasmas were exposed to E. coli suspensions at pH 5.2, 4.7, 4.2 and 3.7, D values were found to be 1.92, 0.96, 0.59, and 0.21 min., respectively, under our experimental conditions. It has been also found experimentally that the presence of superoxide anion radicals O2^-in the solution is essential for bacterial inactivation by the plasma application. The critical pH value may be associated with pKa of the dissociation equilibrium between O2^-and hydroperoxy radicals HOO,hich is known to be approximately 4.8. The formation of radicals in solution by such plasma has been confirmed from ESR (Electron Spin Resonance) with spin trapping agents. The ambient gas has been found to influence the radical formation in liquid significantly.

  11. Capillary zone electrophoresis in non-aqueous solutions: pH of the background electrolyte.

    PubMed

    Porras, Simo P; Kenndler, Ernst

    2004-05-28

    Although the establishment of a pH scale and the determination of the pH in water is not problematic, it is not a straightforward task in non-aqueous solvents. As capillary zone electrophoresis (CZE) in organic solvents has gained increasing interest, it seems to be valuable to re-discuss the concept of the pH in such media, especially pointing to those aspects, which make pH measurement uncertain in non-aqueous solvents. In this review, the relevant aspects when dealing with primary standard (PS) and secondary standard (SS) as recommended by the International Union of Pure and Applied Chemistry (IUPAC), and the usage of the operational pH are discussed with special emphasis to non-aqueous solvents. Here, different liquid junction potentials, incomplete dissociation of the electrolytes (especially in solvents with low or moderate relative permittivity) and the occurrence of homo- and heteroconjugation must be taken into account. Problems arising in capillary zone electrophoresis practice are addressed, e.g. when the background electrolyte (BGE) consists of organic solvents, but the measuring electrode (normally the glass electrode) is calibrated with aqueous buffers, and the liquid junction potentials between the solvents do not cancel each other. The alternative concept of establishing a certain pH is described, using mixtures of reference acids or bases with known pKa in the organic solvent, and their respective salts, at a certain concentration ratio, relying to the Henderson-Hasselbalch equation. Special discussion is directed to those organic solvents most common in capillary zone electrophoresis, methanol (MeOH) and acetonitrile (ACN), but other solvents are included as well. The potential significance of small amounts of water present in the organic solvent on changes in pKa values, and thus on the pH of the buffering components is pointed out.

  12. Use of the fluorescence of rhodamine B for the pH sensing of a glycine solution

    NASA Astrophysics Data System (ADS)

    Zhang, Weiwei; Shi, Kaixing; Shi, Jiulin; He, Xingdao

    2016-10-01

    The fluorescence of rhodamine B can be strongly affected by its environmental pH value. By directly introducing the dye into various glycine solution, the fluorescence was used to monitor the pH value in the range of 5.9 6.7. Two newly developed techniques for broadband analysis, the barycenter technique and the self-referenced intensity ratio technique, were employed to retrieve the pH sensing functions. While compared with traditional techniques, e.g. the peak shift monitoring, both the two new techniques presented finer precision. The obtained sensing functions may find their applications in the test of biochemical samples, body tissue fluid, water quality, etc.

  13. Effects of pH changes of stock normal saline solution on 5 percent red cell suspension.

    PubMed

    Martin, Gregorio L; Caraan, P J M; Chua, Jared Jenrik S; Crescini, Jules Albert L; Diokno, Joseph Martin C; Javier, Christopher Bernard D; Reyes, Kristina Barbara O; Soliven, Rianne Y

    2014-01-01

    The red cell suspension (RCS) is a universally used indicator system to demonstrate antigen and antibody reactions in vitro.Saline solutions that are used in its preparation are preferred to be fresh to avoid changes in pH that may affect the results. Thus,buffered saline such as phosphate-buffered saline (PBS) is the ideal diluent because its pH is maintained for a certain period. However,normal saline solution (NSS) is more commonly used because it is inexpensive and easy to make. pH changes in the saline solutions and the RCSs were monitored for 1 week. Macroscopic examination of changes in degree of redness of RCS was also observed. Red blood cell (RBC) indices of the ethylenediaminetetraacetic acid(EDT A)-anticoagulated blood used in the preparation of the RCS were measured in the performance of an automated complete blood count. Qualitative examination of the crenation of RBCs was done on the prepared blood smears and graded by three registered medical technologists. Percentage crenation was then determined using an improved Neubauer counting chamber. Three trials were performed, and results were averaged. Statistical analysis showed hat there were significant differences in the average pH of PBS and NSS and the average pH of RCS-PBS and RCS-NSS over 1 week. RBC indices measured in EDTA-anticoagulated donor blood showed no significant difference. Macroscopic examination of changes in degree of redness of the RCS showed that color darkened over 1 week but only by a small degree. Qualitative and quantitative examination of crenation of RBCs in RCS-PBS and RCS-NSS both showed no significant differences over 1 week. The experimental group (RCS-NSS) continuously showed a higher grade of crenation than the control group (RCS-PBS). Crenation of RBCs still manifests microscopically despite the lack of a significant relationship between the pH of the saline solutions and the degree and percentage of crenation. Crenation, therefore,cannot be attributed to pH alone but

  14. Comparative contributions of solution geochemistry, microbial metabolism and aquatic photosynthesis to the development of high pH in ephemeral wetlands in South East Australia.

    PubMed

    Reid, R J; Mosley, L M

    2016-01-15

    The development of alkaline conditions in lakes and wetlands is common but the process of alkalinisation is not well elaborated. In this study we investigated causes of the seasonal alkalinisation of ephemeral wetlands in the South East of South Australia where pH values above 10 are frequently observed. This research combined field observations, geochemical analysis of wetland sediment and surface water, with mesocosm studies under controlled conditions. The results revealed a complex interplay between a number of different processes. A primary cause was attributed to sequestration of CO2 from the water column by plant photosynthesis, coupled with slow diffusion of CO2 from the air which led to its depletion in the water. Abundant plant growth also modified the water chemistry via uptake of nutrient elements, in particular calcium and magnesium and increased carbonate alkalinity in the water. Assessment of field results and geochemical modeling showed that low Ca/(HCO3(-) and CO3(-2)) ratios in the water, coupled with carbonate mineral (calcite, Mg substituted calcite, dolomite) precipitation and evapoconcentration, create a high alkalinity and pH (>9) baseline in many wetlands. The high baseline pH is then further increased by CO2 depletion due to photosynthesis. We could find no evidence that reduction of sulfate to sulfides by sulfur-reducing bacteria significantly contributed to the very high pH conditions.

  15. pH effect on structural character of uracil in aqueous solution studied by single-shot CARS

    NASA Astrophysics Data System (ADS)

    Qin, Wenhong; Zhao, Dong; Guo, Chu

    1991-10-01

    A preliminary study is reported on the structure of uracil, a base residue of nucleic acid, in aqueous solutions of different pH values by coherent anti-Stokes Raman scattering (CARS). The results obtained reveal that Raman lines associated with the stretching and bending vibration modes of the uracil ring around 1000 and 1240 cm -1 are sensitive to the pH of the solutions. All thes findings, however, are difficult to observe by laser resonance Raman spectroscopy, which is used widely in practice at present. In addition, we conclude that CARS measurement seems to be a powerful tool capable of offering structural specificity associated with molecular vibrational frequencies of base residues of nucleic acids and their interactions with the surrounding media.

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

    SciTech Connect

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

    1993-10-01

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

  17. Kinetic and thermodynamic study of the behaviour of diphenylcarbazide in aqueous solution with pH.

    PubMed

    Salinas-Hernández, P; Rojas-Hernández, A; Ramírez-Silva, M T

    2003-09-01

    In order to find out about the chemical behaviour of the diphenylcarbazide (DPCI) in water, kinetic and thermodynamic studies were carried out using UV-Vis spectrophotometry within the 0-12 pH range. The kinetic parameters and acidity constant were then determined, and the results show that a pseudo first order reaction rate was observed during hydroxilation, while the reaction rate was also observed to increase with the pH. The acidity constant obtained with the aid of SQUAD was pK(a)=10.718+/-0.027.

  18. Effects of pH on Water-Solubilization of Carbon Nanotube Using Microplasma in Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Imasaka, Kiminobu; Kato, Yuki; Khaled, Usama; Suehiro, Junya

    2009-06-01

    The authors have previously proposed a novel technique for the preparation of water-soluble carbon nanotubes (CNTs) using microplasma generated by a pulsed streamer discharge in water. This paper describes effects of pH values on water-solubility of single-walled CNT (SWCNT) treated by the microplasma. The SWCNT treated under basic conditions showed two times higher solubility compared to that treated under neutral condition, whereas the SWCNT solubility considerably decreased under acidic conditions. Based on optical emission measurements of microplasma showed that radical formation was not pH sensitive. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis showed that the microplasma treated SWCNT was functionalized with -COO- groups with little pH dependence. In contrary, clear pH dependence was observed for zeta potential of the microplasma-treated SWCNT. The lowest zeta potential was -46 mV, which was obtained with basic solution adjusted by NH3 (pH ≈9). The SWCNT treated under basic conditions was more negatively charged due to suppressed protonation of -COO- groups. As a result, the electrostatic repulsion force between SWCNTs could overcome van der Waals force improving their solubility and dispersibility in water.

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

    SciTech Connect

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

    1997-09-01

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

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

    PubMed

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

    2015-11-01

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

  1. Dynamics of pH modification of an acidic protein bait used for tropical fruit flies (Diptera: Tephritidae).

    PubMed

    Heath, Robert R; Vazquez, Aime; Schnell, Elena Q; Villareal, Janett; Kendra, Paul E; Epsky, Nancy D

    2009-12-01

    Several species of Anastrepha and Bactrocera fruit flies (Diptera: Tephritidae) are captured in traps baited with the protein bait NuLure combined with borax (sodium tetraborate decahydrate) in an aqueous solution, typically 9% NuLure (vol:vol) with 3% borax (wt:vol). NuLure is an acid hydrolysate of corn and has an acidic pH. Addition of borax makes the solution more alkaline, and increase in alkalinity results in increase of ammonia release from the bait solution. This is a very dynamic system, with resultant pH affected by factors such as the amount of borax added, the pH of the water used for preparation, the age of the bait solution, and the development of microbial growth. Problems with borax include amount needed to increase alkalinity of NuLure solutions, which creates difficulties in disposing of spent bait in fruit fly trapping programs. Therefore, research was conducted to evaluate NaOH as an alternative method to increase alkalinity of NuLure solutions. Laboratory experiments compared effect of NaOH versus borax for pH modification on changes in pH and ammonia content of NuLure solutions over time. Although NuLure/NaOH solutions could be adjusted to a more alkaline pH than NuLure/borax solutions, borax plays a critical role in pH stability over time. However, the pH of NuLure/NaOH is stabilized when propylene glycol (10% vol:vol) was used to prepare the bait solution. The use of NaOH can provide an alternative to the use of borax to increase bait solution alkalinity.

  2. Protoplasmic pH modifies water and solute transfer in beta vulgaris root vacuoles.

    PubMed

    Amodeo, G; Sutka, M; Dorr, R; Parisi, M

    2002-06-01

    Volume changes were studied in Beta vulgaris storage root vacuoles, using video microscopy, when exposed to hypotonic conditions. The osmotic gradient was either step-applied or progressively imposed in perfusion experiments. Preincubation at low pH (6.6) or with HgCl2 strongly reduced the vacuoles' water permeability, measured in step experiments. Furthermore, the volumetric response depended on the rate with which the aniso-osmotic condition was established. In perfusion experiments a "plateau value" (osmotic equilibrium or steady-state volume value) was observed, which was significantly lower than the theoretically expected one. Furthermore, if vacuoles were preincubated in presence of HgCl2 or at low pH and then the hypo-osmotic challenge was applied in perfusion experiments, a still lower "plateau value" was observed. This reduction was concentration-dependent and completely reversible. In these conditions, when HgCl2 concentration was 300 mM or medium pH was 6.6, the volume change was abolished. In other experiments, when urea iso-osmotically replaced mannitol, a reversible, pH-dependent volumetric response was observed. These results can be interpreted accepting that 1) mercury-sensitive water channels, present in the studied structure, were blocked by low pH during the hypo-osmotic challenge; 2) modification of water permeability prevents excessive swelling during the osmotic shock; 3) the effectiveness of this last mechanism depended on the osmotic challenge rate; and 4) additionally, urea reflection coefficients were also modified by reduced medium pH.

  3. COUPLING THE ALKALINE-SURFACTANT-POLYMER TECHNOLOGY AND THE GELATION TECHNOLOGY TO MAXIMIZE OIL PRODUCTION

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson; David Stewart; Bill Jones

    2005-04-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or more efficient areal sweep efficiency for those with high permeability contrast ''thief zones''. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or those with thief zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. A prior fluid-fluid report discussed interaction of different gel chemical compositions and alkaline-surfactant-polymer solutions. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in the fluid-fluid analyses. Aluminum-polyacrylamide, flowing gels are not stable to alkaline-surfactant-polymer solutions of either pH 10.5 or 12.9. Chromium acetate-polyacrylamide flowing and rigid flowing gels are stable to subsequent alkaline-surfactant-polymer solution injection. Rigid flowing chromium acetate-polyacrylamide gels maintained permeability reduction better than flowing chromium acetate-polyacrylamide gels. Silicate-polyacrylamide gels are not stable with subsequent injection of either a pH 10.5 or a 12.9 alkaline-surfactant-polymer solution. Chromium acetate-xanthan gum rigid gels are not stable to subsequent alkaline-surfactant-polymer solution injection. Resorcinol-formaldehyde gels were stable to subsequent alkaline-surfactant-polymer solution injection. When evaluated in a dual core configuration, injected fluid flows into the core with the greatest effective permeability to the injected fluid. The same gel stability trends to subsequent

  4. Evaluating the role of metal ions in the bathochromic and hyperchromic responses of cyanidin derivatives in acidic and alkaline pH.

    PubMed

    Sigurdson, G T; Robbins, R J; Collins, T M; Giusti, M M

    2016-10-01

    In many food products, colorants derived from natural sources are increasingly popular due to consumer demand. Anthocyanins are one class of versatile and abundant naturally occurring chromophores that produce different hues in nature, especially with metal ions and other copigments assisting. The effects of chelation of metal ions (Mg(2+), Al(3+), Cr(3+), Fe(3+), and Ga(3+)) in factorial excesses to anthocyanin concentration (0-500×) on the spectral characteristics (380-700nm) of cyanidin and acylated cyanidin derivatives were evaluated to better understand the color evolution of anthocyanin-metal chelates in pH 3-8. In all pH, anthocyanins exhibited bathochromic and hyperchromic shifts. Largest bathochromic shifts most often occurred in pH 6; while largest hyperchromic shifts occurred in pH 5. Divalent Mg(2+) showed no observable effect on anthocyanin color while trivalent metal ions caused bathochromic shifts and hue changes. Generally, bathochromic shifts on anthocyanins were greatest with more electron rich metal ions (Fe(3+)≈Ga(3+)>Al(3+)>Cr(3+)).

  5. Effect of pH and temperature on stability and kinetics of novel extracellular serine alkaline protease (70 kDa).

    PubMed

    Bhunia, Biswanath; Basak, Bikram; Mandal, Tamal; Bhattacharya, Pinaki; Dey, Apurba

    2013-03-01

    A novel extracellular serine protease (70 kDa by SDS-PAGE) was purified and characterized. This enzyme retained more than 93% of its initial activity after preincubation for 30 min at 37 °C in the presence of 25% (v/v) tested organic solvents and showed feather degradation activity. The purified enzyme was deactivated at various combinations of pH and temperature to examine the interactive effect of them on enzyme activity. The deactivation process was modeled as first-order kinetics and the deactivation rate constant (k(d)) was found to be minimum at pH 9 and 37 °C. The kinetic analysis of enzyme over a range of pH values indicated two pK values at 6.21 and at 10.92. The lower pK value was likely due to the catalytic histidine in the free enzyme and higher pK value likely reflected deprotonation of the proline moiety of the substrate but ionization of the active site serine is another possibility. Inhibition kinetic showed that enzyme is serine protease because enzyme was competitively inhibited by antipain and aprotinin as these compounds are known to be competitive inhibitors of serine protease. The organic solvent, thermal and pH tolerances of enzyme suggested that it may have potential for use as a biocatalyst in industry.

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

    SciTech Connect

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

    2015-01-15

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

  7. Kinetics of hyaluronan hydrolysis in acidic solution at various pH values.

    PubMed

    Tømmeraas, Kristoffer; Melander, Claes

    2008-06-01

    Hyaluronic acid (HA) was hydrolyzed using varying temperatures (40, 60, and 80 degrees C) and acid concentrations (0.0010, 0.010, 0.10, 0.50, 1.0, and 2.0 M HCl). The degradation process was monitored by determination of weight average molecular weight ( M w) by size-exclusion chromatography with online multiangle laser light scattering, refractive index, and intrinsic viscosity detectors (SEC-MALLS-RI-visc) on samples taken out continuously during the hydrolysis. SEC-MALLS-RI-visc showed that the degradation gave narrow molecular weight distributions with polydispersity indexes ( M w/ M n) of 1.3-1.7. Kinetic plots of 1/ M w versus time gave linear plots showing that acid hydrolysis of HA is a random process and that it follows a first order kinetics. For hydrolysis in HCl at 60 and 80 degrees C, it was shown that the kinetic rate constant ( k h) for the degradation depended linearly on the acid concentration. Further, the dependence of temperature on the hydrolysis in 0.1 M HCl was found to give a linear Arrhenius plot (ln k h vs 1/ T), with an activation energy ( E a) of 137 kJ/mol and Arrhenius constant ( A) of 7.86 x 10 (15) h (-1). (1)H NMR spectroscopy was used to characterize the product of extensive hydrolysis (48 h at 60 degrees C in 0.1 M HCl). No indication of de- N-acetylation of the N-acetyl glucosamine (GlcNAc) units or other byproducts were seen. Additionally, a low molecular weight HA was hydrolyzed in 0.1 M DCl for 4 h at 80 degrees C. It was shown that it was primarily the beta-(1-->4)-linkage between GlcNAc and glucuronic acid (GlcA) that was cleaved during hydrolysis at pH < p K a,GlcA. The dependence of the hydrolysis rate constant was further studied as a function of pH between -0.3 and 5. The degradation was found to be random (linear kinetic plots) over the entire pH range studied. Further, the kinetic rate constant was found to depend linearly on pH in the region -0.3 to 3. Above this pH (around the p K a of HA), the kinetic constant

  8. Experimental study of the bending elasticity of charged lipid bilayers in aqueous solutions with pH5

    NASA Astrophysics Data System (ADS)

    Mitkova, D.; Stoyanova-Ivanova, A.; Ermakov, Yu A.; Vitkova, V.

    2012-12-01

    Exposure to high concentrations of contaminations due to air polluting gases, vapours and aerosols and possibly altering the normal pH in the body could lead to undesirable changes in the properties of biological cells. Here, we study experimentally the mechanical properties of synthetic phospholipid bilayers containing increasing molar fractions (up to 0.15) of charged lipid (synthetic phosphatidylserine) in aqueous solutions with controlled ionic strength and at pH 5, which is slightly lower than the physiological values of pH. Our observations in phase contrast and fluorescence testified to the coexistence of two phases in membranes for temperatures below 29°C. Micro-sized inhomogeneities in vesicle membranes were systematically observed at temperatures lower than 29°C and for molar fractions of phosphatidylserine in the bilayer higher than 0.1. For the quantitative determination of the membrane bending rigidity, we applied thermal fluctuation analysis of the shape of quasispherical lipid vesicles. As far as the liquid-crystalline state of the bilayer is a necessary condition for the application of the experimental method, only vesicles satisfying this requirement were processed for determination of their membrane bending rigidity. The value obtained for the bending modulus of bilayers with 0.15 molar content of charged lipid is about two times higher than the bending modulus of uncharged membranes in the same bathing solution. These findings are in qualitative agreement with our previous results for the bending rigidity of charged bilayers, measured by vesicle micromanipulation.

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

    SciTech Connect

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

    1992-01-01

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

  10. Effect of pH Value on the Electrochemical and Stress Corrosion Cracking Behavior of X70 Pipeline Steel in the Dilute Bicarbonate Solutions

    NASA Astrophysics Data System (ADS)

    Cui, Z. Y.; Liu, Z. Y.; Wang, L. W.; Ma, H. C.; Du, C. W.; Li, X. G.; Wang, X.

    2015-11-01

    In this work, effects of pH value on the electrochemical and stress corrosion cracking (SCC) behavior of X70 pipeline steel in the dilute bicarbonate solutions were investigated using electrochemical measurements, slow strain rate tensile tests and surface analysis techniques. Decrease of the solution pH from 6.8 to 6.0 promotes the anodic dissolution and cathodic reduction simultaneously. Further decrease of the pH value mainly accelerates the cathodic reduction of X70 pipeline steel. As a result, when the solution pH decreases form 6.8 to 5.5, SCC susceptibility decreases because of the enhancement of the anodic dissolution. When the solution pH decreases from 5.5 to 4.0, SCC susceptibility increases gradually because of the acceleration of cathodic reactions.

  11. Radiation crosslinking of carboxymethylcellulose of various degree of substitution at high concentration in aqueous solutions of natural pH

    NASA Astrophysics Data System (ADS)

    Wach, Radoslaw A.; Mitomo, Hiroshi; Nagasawa, Naotsugu; Yoshii, Fumio

    2003-12-01

    Carboxymethylcellulose (CMC) hydrogel formed by ionizing radiation at highly concentrated aqueous solutions was found to undergo swelling depending on the pH of the swelling media. Swelling increases at neutral and basic pH due to ionization of carboxymethyl groups on side chains. The presence of charges develops repulsive forces between polymer chains of the network causing its expansion. Hydrogel in relaxed state as well as dried gel reveals good mechanical properties. It was considered that intermolecular crosslinking reactions occur by a radical route. Radicals placed on anhydroglucose repeating unit as well as on side chains were distinguished from ESR spectra of CMC. A stable doublet signal with 2.0 mT splitting constant belongs to a radical placed on the α-carbon atom of the substituent group, R-O- rad CH-COO -. It was assumed that this species participates in intermolecular crosslinking.

  12. Effects of solutions treated with oxygen radicals in neutral pH region on inactivation of microorganism

    NASA Astrophysics Data System (ADS)

    Kobayashi, Tsuyoshi; Hashizume, Hiroshi; Ohta, Takayuki; Ishikawa, Kenji; Hori, Masaru; Ito, Masafumi

    2015-09-01

    The inactivation of microorganisms using nonequilbrium atmospheric pressure plasmas has been attracted much attention due to the low temperature processing and high speed treatment. In this study, we have inactivated E. coli suspended in solutions with neutral pH using an atmospheric-pressure oxygen radical source which can selectively supply electrically neutral oxygen radicals. E. coli cells were suspended with deionized distilled water (DDW) (pH = 6.8) or phosphate buffered saline (PBS) (pH = 7.4) or Citrate-Na buffer (pH = 6.5). The treated samples were diluted and spread on nutrient agar (Nutrient Broth). They were cultured at 37° C. The inactivation effects of oxygen radicals on those cells in solutions were evaluated by colony-counting method. O2 diluted by Ar gas were employed as a working gas for the radical source. The total gas flow rate and the gas mixture ratio of O2/(Ar + O2) were set at 5 slm and 0.6%, respectively. The distance between the radical exit and the suspension surface were set at 10 mm. As a result, the D values for DDW(pH = 6.8), PBS(pH = 7.4) and Citrate-Na buffer(pH = 6.5) were estimated to be 1.4 min, 0.9 min and 16.8 min respectively. The inactivation rates in DDW, PBS were significantly different from that in Citrate-Na buffer. This work was partly supported by JSPS KAKENHI Grant Number 26286072 and project for promoting Research Center in Meijo University.

  13. Effect of pH on the survival of Listeria innocua in calcium ascorbate solutions and on quality of fresh-cut apples.

    PubMed

    Karaibrahimoglu, Yildiz; Fan, Xuetong; Sapers, Gerald M; Sokorai, Kimberly

    2004-04-01

    Fresh-cut apple slices were dipped in calcium ascorbate (CaA) solution at pH values ranging from 2.5 to 7.0 to inhibit browning. After treatment, the cut apples were stored at 4 and 10 degrees C for up to 21 days. Color and texture of the apples were determined on days 1, 14, and 21. In a separate experiement, the pH of CaA solution was adjusted with acetic acid to six different pH levels, and the solution was inoculated with Listeria innocua. The survival of the bacterium and the stability of CaA were determined at 0, 20, and 96 h. The cut apples maintained fresh quality when the pH of the CaA solution was above 4.5, but slight discoloration of apple slices dipped in pH 4.5 solution was observed after 14 days at 10 degrees C. At pH 5.0, the CaA dip maintained the quality of the apples at both temperatures for at least 21 days. The L. innocua population was reduced by 4 to 5 log CFU/ml at pH 4.5 after 96 h. At pH 5, the bacterial population in the CaA solution was reduced by approximately 2 log CFU/ml during the same period. The CaA solution was stable at pH 5 for at least 96 h. Reduction of the pH to between 4.5 and 5.0 might reduce the risk of foodborne illness due to consumption of fresh-cut apples treated with a CaA solution contaminated with Listeria.

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

    PubMed

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

    2016-04-01

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

  15. The Effect of Crystallizing and Non-crystallizing Cosolutes on Succinate Buffer Crystallization and the Consequent pH Shift in Frozen Solutions

    SciTech Connect

    Sundaramurthi, Prakash; Suryanarayanan, Raj

    2011-09-06

    To effectively inhibit succinate buffer crystallization and the consequent pH changes in frozen solutions. Using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD), the crystallization behavior of succinate buffer in the presence of either (i) a crystallizing (glycine, mannitol, trehalose) or (ii) a non-crystallizing cosolute (sucrose) was evaluated. Aqueous succinate buffer solutions, 50 or 200 mM, at pH values 4.0 or 6.0 were cooled from room temperature to -25 C at 0.5 C/min. The pH of the solution was measured as a function of temperature using a probe designed to function at low temperatures. The final lyophiles prepared from these solutions were characterized using synchrotron radiation. When the succinic acid solution buffered to pH 4.0, in the absence of a cosolute, was cooled, there was a pronounced shift in the freeze-concentrate pH. Glycine and mannitol, which have a tendency to crystallize in frozen solutions, remained amorphous when the initial pH was 6.0. Under this condition, they also inhibited buffer crystallization and prevented pH change. At pH 4.0 (50 mM initial concentration), glycine and mannitol crystallized and did not prevent pH change in frozen solutions. While sucrose, a non-crystallizing cosolute, did not completely prevent buffer crystallization, the extent of crystallization was reduced. Sucrose decomposition, based on XRD peaks attributable to {beta}-D-glucose, was observed in frozen buffer solutions with an initial pH of 4.0. Trehalose completely inhibited crystallization of the buffer components when the initial pH was 6.0 but not at pH 4.0. At the lower pH, the crystallization of both trehalose dihydrate and buffer components was evident. When retained amorphous, sucrose and trehalose effectively inhibited succinate buffer component crystallization and the consequent pH shift. However, when trehalose crystallized or sucrose degraded to yield a crystalline decomposition product, crystallization of buffer was

  16. Solar light (hv) and H2O2/hv photo-disinfection of natural alkaline water (pH 8.6) in a compound parabolic collector at different day periods in Sahelian region.

    PubMed

    Ndounla, J; Pulgarin, C

    2015-11-01

    The photo-disinfection of natural alkaline surface water (pH 8.6 ± 0.3) for drinking purposes was carried out under solar radiation treatments. The enteric bacteria studied were the wild total coliforms/Escherichia coli (10(4) CFU/ml) and Salmonella spp. (10(4) CFU/ml) naturally present in the water. The photo-disinfection of a 25-l water sample was carried out in a solar compound parabolic collector (CPC) in the absence and in the presence of hydrogen peroxide (H2O2). The addition of H2O2 (10 mg/L) to the sample water was sufficient to enhance the photo-disinfection and ensure an irreversible lethal action on the wild enteric bacteria contents of the sample. The inactivation kinetic of the system was significantly enhanced compared to the one carried out without H2O2 addition. The effect of the solar radiation parameters on the efficiency of the photo-disinfection were assessed. The pH has increased during the treatment in all the photo-disinfection processes (hv and H2O2/hv). The Salmonella spp strain has shown the best effective inactivate time in alkaline water than the one recorded under acidic or near-neutral conditions. The evolution of some physico-chemical parameters of the water (turbidity, NO2(-), NO3(-), NH4(+), HPO4(2-), and bicarbonate (HCO3(-))) was monitored during the treatment. Finally, the possible mechanistic process involved during the enteric bacteria inactivation was suggested.

  17. Coupling the Alkaline-Surfactant-Polymer Technology and the Gelation Technology to Maximize Oil Production

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson; Phil Dowling; David Stewart; Bill Jones

    2005-12-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or reservoirs with different sand lenses with high permeability contrast. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more crude oil than waterflooding froin swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or reservoirs with high permeability contrast zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. Fluid-fluid interaction with different gel chemical compositions and alkaline-surfactant-polymer solution with pH values ranging from 9.2 to 12.9 have been tested. Aluminum-polyacrylamide gels are not stable to alkaline-surfactant-polymer solutions at any pH. Chromium-polyacrylamide gels with polymer to chromium ion ratios of 25 or greater were stable to alkaline-surfactant-polymer solutions if solution pH was 10.6 or less. When the polymer to chromium ion was 15 or less, chromium-polyacrylamide gels were stable to alkaline-surfactant-polymer solutions with pH values up to 12.9. Chromium-xanthan gum gels were stable to alkaline-surfactant-polymer solutions with pH values of 12.9 at the polymer to chromium ion ratios tested. Silicate-polyacrylamide, resorcinol-formaldehyde, and sulfomethylated resorcinol-formaldehyde gels were also stable to alkaline-surfactant-polymer solutions with pH values ranging from 9.2 to 12.9. Iron-polyacrylamide gels were immediately destroyed when contacted with any of the alkaline-surfactant-polymer solutions with pH values ranging from 9.2 to 12.9. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in

  18. Evaluation of effects of pH and ionic strength on colloidal stability of IgG solutions by PEG-induced liquid-liquid phase separation.

    PubMed

    Thompson, Ronald W; Latypov, Ramil F; Wang, Ying; Lomakin, Aleksey; Meyer, Julie A; Vunnum, Suresh; Benedek, George B

    2016-11-14

    Colloidal stability of IgG antibody solutions is important for pharmaceutical and medicinal applications. Solution pH and ionic strength are two key factors that affect the colloidal stability of protein solutions. In this work, we use a method based on the PEG-induced liquid-liquid phase separation to examine the effects of pH and ionic strength on the colloidal stability of IgG solutions. We found that at high ionic strength (≥0.25M), the colloidal stability of most of our IgGs is insensitive to pH, and at low ionic strength (≤0.15M), all IgG solutions are much more stable at pH 5 than at pH 7. In addition, the PEG-induced depletion force is less efficient in causing phase separation at pH 5 than at pH 7. In contrast to the native inter-protein interaction of IgGs, the effect of depletion force on phase separation of the antibody solutions is insensitive to ionic strength. Our results suggest that the long-range electrostatic inter-protein repulsion at low ionic strength stabilizes the IgG solutions at low pH. At high ionic strength, the short-range electrostatic interactions do not make a significant contribution to the colloidal stability for most IgGs with a few exceptions. The weaker effect of depletion force at lower pH indicates a reduction of protein concentration in the condensed phase. This work advances our basic understanding of the colloidal stability of IgG solutions and also introduces a practical approach to measuring protein colloidal stability under various solution conditions.

  19. Evaluation of effects of pH and ionic strength on colloidal stability of IgG solutions by PEG-induced liquid-liquid phase separation

    NASA Astrophysics Data System (ADS)

    Thompson, Ronald W.; Latypov, Ramil F.; Wang, Ying; Lomakin, Aleksey; Meyer, Julie A.; Vunnum, Suresh; Benedek, George B.

    2016-11-01

    Colloidal stability of IgG antibody solutions is important for pharmaceutical and medicinal applications. Solution pH and ionic strength are two key factors that affect the colloidal stability of protein solutions. In this work, we use a method based on the PEG-induced liquid-liquid phase separation to examine the effects of pH and ionic strength on the colloidal stability of IgG solutions. We found that at high ionic strength (≥0.25M), the colloidal stability of most of our IgGs is insensitive to pH, and at low ionic strength (≤0.15M), all IgG solutions are much more stable at pH 5 than at pH 7. In addition, the PEG-induced depletion force is less efficient in causing phase separation at pH 5 than at pH 7. In contrast to the native inter-protein interaction of IgGs, the effect of depletion force on phase separation of the antibody solutions is insensitive to ionic strength. Our results suggest that the long-range electrostatic inter-protein repulsion at low ionic strength stabilizes the IgG solutions at low pH. At high ionic strength, the short-range electrostatic interactions do not make a significant contribution to the colloidal stability for most IgGs with a few exceptions. The weaker effect of depletion force at lower pH indicates a reduction of protein concentration in the condensed phase. This work advances our basic understanding of the colloidal stability of IgG solutions and also introduces a practical approach to measuring protein colloidal stability under various solution conditions.

  20. A smart DNA tetrahedron that isothermally assembles or dissociates in response to the solution pH value changes.

    PubMed

    Liu, Zhiyu; Li, Yingmei; Tian, Cheng; Mao, Chengde

    2013-06-10

    This communication reports a DNA tetrahedron whose self-assembly is triggered by an acidic environment. The key element is the formation/dissociation of a short, cytosine (C)-containing, DNA triplex. As the solution pH value oscillates between 5.0 and 8.0, the DNA triplex will form and dissociate that, in turn, leads to assembly or disassembly of the DNA tetrahedron, which has been demonstrated by native polyacrylamide gel electrophoresis (PAGE). We believe that such environment-responsive behavior will be important for potential applications of DNA nanocages such as on-demand drug release.

  1. Isolated secretion granules from parotid glands of chronically stimulated rats possess an alkaline internal pH and inward-directed H/sup +/ pump activity

    SciTech Connect

    Arvan, P.; Castle, J.D.

    1986-10-01

    Secretion granules have been isolated from the parotid glands of rats that have been chronically stimulated with the ..beta..-adrenergic agonist, isoproterenol. These granules are of interest because they package a quantitatively different set of secretory proteins in comparison with granules from the normal gland. Polypeptides enriched in proline, glycine, and glutamine, which are known to have pI's >10, replace ..cap alpha..-amylase (pI's = 6.8) as the principal content species. The internal pH of granules from the treated rats changes from 7.8 in a potassium sulfate medium to 6.9 in a choline chloride medium. The increased pH over that of normal parotid granules (approx.6.8) appears to protect the change in composition of the secretory contents. Whereas normal mature parotide granules have practically negligible levels of H/sup +/ pumping ATPase activity, the isolated granules from isoproterenol-treated rats undergo a time-dependent internal acidification that requires the presence of ATP and is abolished by an H/sup +/ ionophore. Additionally, an inside-positive granule transmembrane potential develops after ATP addition that depends upon ATP hydrolysis. Two independent methods have been used that exclude the possibility that contaminating organelles are the source of the H/sup +/-ATPase activity. Together these data provide clear evidence for the presence of an H/sup +/ pump in the membranes of parotid granules from chronically stimulated rats. However, despite the presence of H/sup +/-pump activity, fluorescence microscopy with the weak base, acridine orange, reveals that the intragranular pH in live cells is greater than that of the cytoplasm.

  2. Formation of apatitic calcium phosphates in a Na-K-phosphate solution of pH 7.4.

    PubMed

    Tas, A C; Aldinger, F

    2005-02-01

    Poorly crystalline, apatitic calcium phosphate powders have been synthesized by slowly adding a Na- and K-containing reference phosphate solution with a pH value of 7.4 to an aqueous calcium nitrate solution at 37 degrees C. Nano-particulated apatitic powders obtained were shown to contain small amounts of Na and K, which render them more similar in chemical composition to that of the bone mineral. Precipitated and dried powders were found to exhibit self-hardening cement properties when kneaded in a mortar with a sodium citrate- and sodium phosphate-containing starter solution. The same phosphate solution used in powder synthesis was found to be able to partially convert natural, white and translucent marble pieces of calcite (CaCO3) into calcium-deficient hydroxyapatite upon aging the samples in that solution for 3 days at 60 degrees C. Sample characterization was performed by using scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, inductively-coupled plasma atomic emission spectroscopy, and simultaneous thermogravimetry and differential thermal analysis.

  3. Graphene transistors are insensitive to pH changes in solution.

    PubMed

    Fu, Wangyang; Nef, Cornelia; Knopfmacher, Oren; Tarasov, Alexey; Weiss, Markus; Calame, Michel; Schönenberger, Christian

    2011-09-14

    We observe very small gate-voltage shifts in the transfer characteristic of as-prepared graphene field-effect transistors (GFETs) when the pH of the buffer is changed. This observation is in strong contrast to Si-based ion-sensitive FETs. The low gate-shift of a GFET can be further reduced if the graphene surface is covered with a hydrophobic fluorobenzene layer. If a thin Al-oxide layer is applied instead, the opposite happens. This suggests that clean graphene does not sense the chemical potential of protons. A GFET can therefore be used as a reference electrode in an aqueous electrolyte. Our finding sheds light on the large variety of pH-induced gate shifts that have been published for GFETs in the recent literature.

  4. A fully vectorized numerical solution of the incompressible Navier-Stokes equations. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Patel, N.

    1983-01-01

    A vectorizable algorithm is presented for the implicit finite difference solution of the incompressible Navier-Stokes equations in general curvilinear coordinates. The unsteady Reynolds averaged Navier-Stokes equations solved are in two dimension and non-conservative primitive variable form. A two-layer algebraic eddy viscosity turbulence model is used to incorporate the effects of turbulence. Two momentum equations and a Poisson pressure equation, which is obtained by taking the divergence of the momentum equations and satisfying the continuity equation, are solved simultaneously at each time step. An elliptic grid generation approach is used to generate a boundary conforming coordinate system about an airfoil. The governing equations are expressed in terms of the curvilinear coordinates and are solved on a uniform rectangular computational domain. A checkerboard SOR, which can effectively utilize the computer architectural concept of vector processing, is used for iterative solution of the governing equations.

  5. Effect of ph on the Electrodeposition of Cu(In, Al)Se2 from Aqueous Solution in Presence of Citric Acid as Complexing Agent

    NASA Astrophysics Data System (ADS)

    Ganjkhanlou, Yadolah; Ebadzadeh, Touradj; Kazemzad, Mahmood; Maghsoudipour, Amir; Kianpour-Rad, Mansoor

    2015-05-01

    Effect of pH on the one-step electrodeposition of Cu(In, Al)Se2 chalcopyrite layer in the presence of citric acid has been investigated by applying different electrochemical and characterization techniques. It has been observed that at pH of 1.5, nanocrystalline phase of chalcopyrite and small amount of binary phase of Cu2Se with overall composition of Cu0.91In0.32Al0.39Se2 have been deposited. On the other hand, at pH of 4, the film composition changed to Cu1.9In0.05Al0.21Se2 and an additional binary phase of copper selenide (CuSe) has also been formed. Morphological investigation illustrated that smooth and compact layer with fine spherical particles having the size of 20 nm has been obtained at pH of 1.5 whereas mixture of planar and spherical particles with size of 450-550 nm have been formed at pH of 4. In alkaline environment (pH 9), the deposition current has been noticeably decreased and no deposition occurred due to the formation of a stable complex of citric acid with metal ions. The mechanism of citric acid interaction with metal ions at different pH has also been studied by cyclic voltammetry measurement.

  6. Effect of Stress on Corrosion at Crack Tip on Pipeline Steel in a Near-Neutral pH Solution

    NASA Astrophysics Data System (ADS)

    Yang, Yao; Cheng, Y. Frank

    2016-11-01

    In this work, the local corrosion at crack tip on an API 5L X46 pipeline steel specimens was investigated under various applied loads in a near-neutral pH solution. Electrochemical measurements, including potentiodynamic polarization and electrochemical impedance spectroscopy, combined with micro-electrochemical technique and surface characterization, were conducted to investigate the effect of stress on local anodic solution of the steel at the crack tip. The stress corrosion cracking of the steel was dominated by an anodic dissolution mechanism, while the effect of hydrogen was negligible. The applied load (stress) increased the corrosion rate at the crack tip, contributing to crack propagation. The deposit of corrosion products at the crack tip could protect somewhat from further corrosion. At sufficiently large applied loads such as 740 N in the work, it was possible to generate separated cathode and anode, further accelerating the crack growth.

  7. Solubility Measurements of Crystalline Cu2O in Aqueous Solution as a Function of Temperature and pH

    SciTech Connect

    Palmer, Donald

    2011-01-01

    The equilibrium solubility of crystalline cuprous oxide, cuprite, was measured in liquid water and steam using two flow-through reactors and a conventional batch autoclave. These measurements were carried out from 20 to 400 C. Different batches of pretreated cuprite were thoroughly characterized prior to and following each set of experiments. Metallic copper beads were added to the inlet end of the reactors and to the solid charge in the autoclave to preserve the Cu(I) oxidation state, although one series of experiments produced some results which were only compatible with CuO(cr) as the solubility limiting phase. Comparison of the solubility data for Cu2O(cr) in aqueous solution with those from the only available high-temperature dataset (Var yash, Geochem. Int. 26:80 90, 1989) showed that in near-neutral solutions the new data are lower by about four orders of magnitude at 350 C. Moreover, the dominant species in solution at temperatures 100 C were found to be only Cu+ and Cu(OH) 2 with Cu(OH)0 occurring over a narrow pH range at 75 C rather than the reverse trend reported previously. Solubility equations were developed as a function of temperature and pH, based on these new results, which showed increased solubility with temperature in acidic and basic solutions. The solubility of Cu2O(cr) in steam decreased slightly with temperature and as expected increased with increasing pressure to supercritical conditions where limited, compatible data were available in the literature. The solubility at subcritical conditions was on the order of one to several parts per billion, ppb. A simple empirical fit was derived for the solubility in steam as a function of temperature and pressure.

  8. Anaerobic methanethiol degradation and methanogenic community analysis in an alkaline (pH 10) biological process for liquefied petroleum gas desulfurization.

    PubMed

    van Leerdam, Robin C; Bonilla-Salinas, Monica; de Bok, Frank A M; Bruning, H; Lens, Piet N L; Stams, Alfons J M; Janssen, Albert J H

    2008-11-01

    Anaerobic methanethiol (MT) degradation by mesophilic (30 degrees C) alkaliphilic (pH 10) communities was studied in a lab-scale Upflow Anaerobic Sludge Bed (UASB) reactor inoculated with a mixture of sediments from the Wadden Sea (The Netherlands), Soap Lake (Central Washington), and Russian soda lakes. MT degradation started after 32 days of incubation. During the first 252 days, complete degradation was achieved till a volumetric loading rate of 7.5 mmol MT/L/day, and sulfide, methane, and carbon dioxide were the main reaction products. Temporary inhibition of MT degradation occurred after MT peak loads and in the presence of dimethyl disulfide (DMDS), which is the autooxidation product of MT. From day 252 onwards, methanol was dosed to the reactor as co-substrate at a loading rate of 3-6 mmol/L/day to stimulate growth of methylotrophic methanogens. Methanol was completely degraded and also a complete MT degradation was achieved till a volumetric loading rate of 13 mmol MT/L/day (0.77 mmol MT/gVSS/day). However, from day 354 till the end of the experimental run (day 365), acetate was formed and MT was not completely degraded anymore, indicating that methanol-degrading homoacetogenic bacteria had partially outcompeted the methanogenic MT-degrading archea. The archeal community in the reactor sludge was analyzed by DGGE and sequencing of 16S rRNA genes. The methanogenic archea responsible for the degradation of MT in the reactor were related to Methanolobus oregonensis. A pure culture, named strain SODA, was obtained by serial dilutions in medium containing both trimethyl amine and dimethyl sulfide (DMS). Strain SODA degraded MT, DMS, trimethyl amine, and methanol. Flow sheet simulations revealed that for sufficient MT removal from liquefied petroleum gas, the extraction and biological degradation process should be operated above pH 9.

  9. Low Alloy X100 Pipeline Steel Corrosion and Passivation Behavior in Bicarbonate-Based Solutions of pH 6.7 to 8.9 with Groundwater Anions: An Electrochemical Study

    NASA Astrophysics Data System (ADS)

    Gadala, Ibrahim M.; Alfantazi, Akram

    2015-07-01

    This research investigates the fundamental corrosion and passivation processes occurring on API-X100 pipeline steels before, during, and after passive layer formation in bicarbonate-based simulated soil solutions of pH 6.7 to 8.9. Free corrosion potentials decrease exponentially with bicarbonate (and pH), owing to increased water and bicarbonate reduction in more alkaline conditions and the coupled iron oxidation reaction. Active corrosion rates at potentials slightly above open circuit potential increase with bicarbonate, until a concentration of 1.68 g L-1 sodium bicarbonate (plus dilute amounts of chlorides/sulfate) at which first signs of film formation appear. Thereon, increased bicarbonate concentration generally decreases current densities and resists ferrous-oxide product formations due to improved iron carbonate formation conditions precipitating more durable passive layers. Potentiodynamic polarization in the anodic regime reveals varying electrochemical processes involving interactions between hydroxide, carbonate, and oxide complexes with ferrous, with diverse pH and potential dependencies. The products of corrosion reactions were investigated by scanning electron microscopy, X-ray diffraction, and/or X-ray photoelectron spectroscopy.

  10. Modeling the effect of environmental solution pH on the mechanical characteristics of glucose-sensitive hydrogels.

    PubMed

    Luo, Rongmo; Li, Hua; Lam, Khin Yong

    2009-02-01

    Many environmental conditions can influence the mechanical characteristics of the glucose-sensitive hydrogels. In this paper, a multi-effect-coupling glucose-stimulus (MECglu) model is developed to study the influence of environmental solution pH on the swelling behavior of soft smart hydrogels responding to change in surrounding blood glucose concentration. In order to characterize the chemo-electro-mechanical behaviors of the hydrogels, the model is composed of the Nernst-Planck type of diffusion-reaction partial differential equations for mobile species with consideration of the enzyme reaction catalyzed by the glucose oxidase and the catalase, the Poisson equation for electric potential, and the nonlinear equilibrium equation for mechanical large deformation of the glucose-sensitive hydrogel. In the MECglu model, the formulation of the fixed charge groups bound onto the corsslinked polymeric network is associated with the change of the ambient solution pH. Using these nonlinear coupled partial differential equations, we demonstrate that the computational mechanical deformation by the MECglu model consists well with the experimental observations published in the range of practical physiological glucose concentration from 0 to 16.5 mM (300 mg/ml). The simulations are also carried out for analysis of the influences of physiological pH on the distributive profiles of reacting and diffusive species concentrations and the electric potential as well as the mechanical deformation of the glucose-sensitive hydrogels. The simulations by the model can efficiently support the design and optimization of the insulin delivery system based on the glucose-sensitive hydrogels with the immobilized glucose oxidase and catalase.

  11. Sorption of vanadium (V) onto natural soil colloids under various solution pH and ionic strength conditions.

    PubMed

    Luo, Xiuhua; Yu, Lin; Wang, Changzhao; Yin, Xianqiang; Mosa, Ahmed; Lv, Jialong; Sun, Huimin

    2017-02-01

    Batch sorption kinetics and isothermal characteristics of V(V) were investigated on three natural soil colloids (manual loessial soil colloid (MSC), aeolian sandy soil colloid (ASC), and cultivated loessial soil colloid (CSC)) under various solution pH and ionic strength (IS) conditions. Colloids were characterized by atomic force microscopy (AFM), X-ray diffraction (XRD), and fourier transform infrared spectroscopy (FTIR). AFM micrographs showed CSC with an aggregated shape with larger particle diameter as compared with ASC and MSC. XRD spectra revealed the presence of different minerals in natural soil colloids including biotite, kaolinite, calcite and quartz, which might contribute to sorption process. The sorption ability decreased with increase of colloidal particle size. The sorption was mainly attributed to complexation by active carboxylate and alcohol groups of colloidal components. Sorption kinetics and isotherms of V(V) onto natural soil colloids were best fitted with Pseudo-second-order and Freundlich models. Langmuir model indicated that sorption capacity of MSC and ASC was comparable (285.7 and 238.1 mg g(-1)); however, CSC exhibited the lowest sorption capacity (41.5 mg g(-1)) due to its larger particle diameter and aggregated shape. The maximum V(V) sorption capacity reached plateau values at a solution pH ranged between 5.0 and 9.0 for MSC and ASC, and 6.0-8.0 for CSC. Sorption capacity of V(V) onto natural soil colloids decreased with increasing IS. Based on result of this study we can conclude that sorption of V(V) onto natural soil colloids is pH- and IS-dependent. These findings provide insights on the remediation of vanadium-contaminated soils.

  12. Effect of alkalinity on nitrite accumulation in treatment of coal chemical industry wastewater using moving bed biofilm reactor.

    PubMed

    Hou, Baolin; Han, Hongjun; Jia, Shengyong; Zhuang, Haifeng; Zhao, Qian; Xu, Peng

    2014-05-01

    Nitrogen removal via nitrite (the nitrite pathway) is more suitable for carbon-limited industrial wastewater. Partial nitrification to nitrite is the primary step to achieve nitrogen removal via nitrite. The effect of alkalinity on nitrite accumulation in a continuous process was investigated by progressively increasing the alkalinity dosage ratio (amount of alkalinity to ammonia ratio, mol/mol). There is a close relationship among alkalinity, pH and the state of matter present in aqueous solution. When alkalinity was insufficient (compared to the theoretical alkalinity amount), ammonia removal efficiency increased first and then decreased at each alkalinity dosage ratio, with an abrupt removal efficiency peak. Generally, ammonia removal efficiency rose with increasing alkalinity dosage ratio. Ammonia removal efficiency reached to 88% from 23% when alkalinity addition was sufficient. Nitrite accumulation could be achieved by inhibiting nitrite oxidizing bacteria (NOB) by free ammonia (FA) in the early period and free nitrous acid in the later period of nitrification when alkalinity was not adequate. Only FA worked to inhibit the activity of NOB when alkalinity addition was sufficient.

  13. Solution pH change in non-uniform alternating current electric fields at frequencies above the electrode charging frequency

    PubMed Central

    An, Ran; Massa, Katherine

    2014-01-01

    AC Faradaic reactions have been reported as a mechanism inducing non-ideal phenomena such as flow reversal and cell deformation in electrokinetic microfluidic systems. Prior published work described experiments in parallel electrode arrays below the electrode charging frequency (fc), the frequency for electrical double layer charging at the electrode. However, 2D spatially non-uniform AC electric fields are required for applications such as in plane AC electroosmosis, AC electrothermal pumps, and dielectrophoresis. Many microscale experimental applications utilize AC frequencies around or above fc. In this work, a pH sensitive fluorescein sodium salt dye was used to detect [H+] as an indicator of Faradaic reactions in aqueous solutions within non-uniform AC electric fields. Comparison experiments with (a) parallel (2D uniform fields) electrodes and (b) organic media were employed to deduce the electrode charging mechanism at 5 kHz (1.5fc). Time dependency analysis illustrated that Faradaic reactions exist above the theoretically predicted electrode charging frequency. Spatial analysis showed [H+] varied spatially due to electric field non-uniformities and local pH changed at length scales greater than 50 μm away from the electrode surface. Thus, non-uniform AC fields yielded spatially varied pH gradients as a direct consequence of ion path length differences while uniform fields did not yield pH gradients; the latter is consistent with prior published data. Frequency dependence was examined from 5 kHz to 12 kHz at 5.5 Vpp potential, and voltage dependency was explored from 3.5 to 7.5 Vpp at 5 kHz. Results suggest that Faradaic reactions can still proceed within electrochemical systems in the absence of well-established electrical double layers. This work also illustrates that in microfluidic systems, spatial medium variations must be considered as a function of experiment time, initial medium conditions, electric signal potential, frequency, and spatial

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

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

    SciTech Connect

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

    1995-12-31

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

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

    PubMed

    Jiang, Ping; Liu, Qian; Sun, Xuping

    2014-11-21

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

  17. Maltose-conjugated chitosans induce macroscopic gelation of pectin solutions at neutral pH.

    PubMed

    Giacomazza, D; Sabatino, M A; Catena, A; Leone, M; San Biagio, P L; Dispenza, C

    2014-12-19

    Injectable polymer scaffolds are particularly attractive for guided tissue growth and drug/cell delivery with minimally invasive intervention. In the present work, "all-polymeric" gelling systems based on pectins and water-soluble maltose-conjugated chitosans (CM) have been developed. Maltose-conjugated chitosan has been synthesized at three different molar ratios, as evaluated by FITR analysis and fluorimetric titration. A thorough rheological characterization of the blends and their parent solutions has been performed. Macroscopic gelation has been achieved by mixing the high esterification degree pectins with CM at higher maltose grafted to chitosan contents. Gels form in a few minutes and reach their full strength in less than two hours. These features encourage their further development as scaffold for tissue engineering.

  18. Silica precipitation in acidic solutions: mechanism, pH effect, and salt effect.

    PubMed

    Gorrepati, Elizabeth A; Wongthahan, Pattanapong; Raha, Sasanka; Fogler, H Scott

    2010-07-06

    This study is the first to show that silica precipitation under very acidic conditions ([HCl] = 2-8 M) proceeds through two distinct steps. First, the monomeric form of silica is quickly depleted from solution as it polymerizes to form primary particles approximately 5 nm in diameter. Second, the primary particles formed then flocculate. A modified Smoluchowski equation that incorporates a geometric population balance accurately describes the exponential growth of silica flocs. Variation of the HCl concentration between 2 and 8 M further showed that polymerization to form primary particles and subsequent particle flocculation become exponentially faster with increasing acid concentration. The effect of salt was also studied by adding 1 M chloride salts to the solutions; it was found that salts accelerated both particle formation and growth rates in the order: AlCl(3) > CaCl(2) > MgCl(2) > NaCl > CsCl > no salt. It was also found that ionic strength, over cation identity, determines silica polymerization and particle flocculation rates. This research reveals that precipitation of silica products from acid dissolution of minerals can be studied apart from the mineral dissolution process. Thus, silica product precipitation from mineral acidization follows a two-step process--formation of 5 nm primary particles followed by particle flocculation--which becomes exponentially faster with increasing HCl concentration and with salts accelerating the process in the above order. This result has implications for any study of acid dissolution of aluminosilicate or silicate material. In particular, the findings are applicable to the process of acidizing oil-containing rock formations, a common practice of the petroleum industry where silica dissolution products encounter a low-pH, salty environment within the oil well.

  19. Priming effect of abscisic acid on alkaline stress tolerance in rice (Oryza sativa L.) seedlings.

    PubMed

    Wei, Li-Xing; Lv, Bing-Sheng; Wang, Ming-Ming; Ma, Hong-Yuan; Yang, Hao-Yu; Liu, Xiao-Long; Jiang, Chang-Jie; Liang, Zheng-Wei

    2015-05-01

    Saline-alkaline stress is characterized by high salinity and high alkalinity (high pH); alkaline stress has been shown to be the primary factor inhibiting rice seedling growth. In this study, we investigated the potential priming effect of abscisic acid (ABA) on tolerance of rice seedlings to alkaline stress simulated by Na2CO3. Seedlings were pretreated with ABA at concentrations of 0 (control), 10, and 50 μM by root-drench for 24 h and then transferred to a Na2CO3 solution that did not contain ABA. Compared to control treatment, pretreatment with ABA substantially improved the survival rate of rice seedlings and increased biomass accumulation after 7 days under the alkaline condition. ABA application at 10 μM also alleviated the inhibitory effects of alkaline stress on the total root length and root surface area. Physiologically, ABA increased relative water content (RWC) and decreased cell membrane injury degree (MI) and Na(+)/K(+) ratios. In contrast, fluridone (an ABA biosynthesis inhibitor) decreased the RWC and increased MI in shoots under the alkaline conditions. These data suggest that ABA has a potent priming effect on the adaptive response to alkaline stress in rice and may be useful for improving rice growth in saline-alkaline paddy fields.

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

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

    PubMed

    Uzer, Ayşem; Erçağ, Erol; Apak, Reşat

    2008-01-30

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

  2. The alkalinizing effects of metabolizable bases in the healthy calf.

    PubMed Central

    Naylor, J M; Forsyth, G W

    1986-01-01

    The alkalinizing effect of citrate, acetate, propionate, gluconate, L and DL-lactate were compared in healthy neonatal calves. The calves were infused for a 3.5 hour period with 150 mmol/L solutions of the sodium salts of the various bases. Blood pH, base excess, and metabolite concentrations were measured and the responses compared with sodium bicarbonate and sodium chloride infusion. D-gluconate and D-lactate had poor alkalinizing abilities and accumulated in blood during infusion suggesting that they are poorly metabolized by the calf. Acetate, L-lactate and propionate had alkalinizing effects similar to bicarbonate, although those of acetate had a slightly better alkalinizing effect than L-lactate. Acetate was more effectively metabolized because blood acetate concentrations were lower than L-lactate concentrations. There was a tendency for a small improvement in metabolism of acetate and lactate with age. Sodium citrate infusion produced signs of hypocalcemia, presumably because it removed ionized calcium from the circulation. D-gluconate, D-lactate and citrate are unsuitable for use as alkalinizing agents in intravenous fluids. Propionate, acetate and L-lactate are all good alkalinizing agents in healthy calves but will not be as effective in situations where tissue metabolism is impaired. PMID:3024796

  3. The Potential of Soft Soil Improvement Through a Coupled Technique Between Electro Kinetic and Alkaline Activation of Soft Soil

    NASA Astrophysics Data System (ADS)

    Ahmed, G. E.; Ismail, H. B.; Huat, B. K.; Afshin, A.; Azhar, A. T. S.

    2016-07-01

    Soil stabilization techniques have been in development for decades with different rates of success. Alkaline activation of soft soil is one of those techniques that has proved to deliver some of the best shear strength values with minor drawbacks in comparison with conventional soil stabilization methods. However, environmental considerations have not been taken into account, as major mineral glassy phase activators are poisoning alkaline solutions, such as sodium-, potassium-hydroxide, and sodium-, potassium-silicate, which poses serious hazards to man and environment. This paper addresses the ways of discarding the involvement of the aforementioned alkaline solutions in soft soil stabilization by investigating the potential of a coupled electro kinetic alkaline activation technique for soft soil strengthening, through which the provision of alkaline pH is governed by electro kinetic potential. Uncertainties in regard to the dissolution of aluminosilicate as well as the dominance of acidic front are challenges that need to be overcome.

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

    PubMed

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

    2009-12-15

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

  5. Morphology and structure of electrospun mats from regenerated silk fibroin aqueous solutions with adjusting pH.

    PubMed

    Zhu, Jingxin; Shao, Huili; Hu, Xuechao

    2007-10-01

    In this paper, regenerated silk fibroin (SF) aqueous solutions were adjusted to a pH of 6.9 by mimicing the condition in the posterior division of silkworm's gland and rheological behavior of solutions was investigated. The electrospinning technique was used to prepare fibers, and non-woven mats of regenerated B. mori silk fibroin were successfully obtained. The effects of electrospinning parameters on the morphology and diameter of regenerated silk fibers were investigated by orthogonal design. Statistical analysis showed that voltage, the concentration of regenerated SF solutions and the distance between tip and collection plate were the most dominant parameters to fiber morphology, diameter and diameter distribution, respectively. An optimal electrospinning condition was obtained in producing uniform cylindrical fibers with an average diameter of 1300nm. It was as follows: the concentration 30%, voltage 40kV, distance 20cm. The structure of electrospun mats was characterized by Raman spectroscopy (RS), wide-angle X-ray diffraction (WAXD) and modulated differential scanning calorimetry (MDSC). It was found that electrospun mats were predominantly random coil/silk I structure, and the transition to silk II (beta-sheet) rich structure should be further explored.

  6. Metal/Metal Oxide Differential Electrode pH Sensors

    NASA Technical Reports Server (NTRS)

    West, William; Buehler, Martin; Keymeulen, Didier

    2007-01-01

    Solid-state electrochemical sensors for measuring the degrees of acidity or alkalinity (in terms of pH values) of liquid solutions are being developed. These sensors are intended to supplant older electrochemical pH sensors that include glass electrode structures and reference solutions. The older sensors are fragile and subject to drift. The present developmental solid-state sensors are more rugged and are expected to be usable in harsh environments. The present sensors are based on a differential-electrode measurement principle. Each sensor includes two electrodes, made of different materials, in equilibrium with the solution of interest.

  7. Investigation of the adsorption mechanism of a peptide in reversed phase liquid chromatography, from pH controlled and uncontrolled solutions

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2009-01-01

    The single-component equilibrium adsorption of the tripeptide Leucyl-Leucyl-Leucine (LLL) on a high-efficiency Jupiter Proteo column (C{sub 12}) was investigated experimentally and modeled theoretically. The experimental equilibrium isotherms of LLL for adsorption on a C{sub 12} packing material from an aqueous solution of methanol (48%) and trifluoroacetic acid (0.1%) were measured by frontal analysis (FA). The FA measurements were done with two solutions, one in which the pH was controlled, the other in which it was not. Two solutions of LLL in the mobile phase were prepared (4.3 and 5.4 g/L) and their pH measured (2.94 and 2.88), respectively. The first solution was titrated with TFA to match the pH of the mobile phase (2.03), so its pH was controlled. The pH of the other solution was left uncontrolled. In both cases the isotherms could be modeled by a bi-Langmuir equation, a choice consistent with the bimodal affinity energy distribution (AED) obtained for LLL. The isotherm parameters derived from the inverse method (IM) of isotherm determination under controlled pH conditions (by fitting calculated profiles to experimental breakthrough profiles) are in a good agreement with those derived from the FA data. Under uncontrolled pH conditions, the application of IM suggests the coexistence of two different adsorption mechanisms. According to the isotherm parameters found by these three methods (FA, AED and IM), the C{sub 12}-bonded silica can adsorb around 500 and 70 g/L of LLL under controlled and uncontrolled pH conditions, respectively. The adsorption of LLL on the C{sub 12} material strongly depends on the pH of the mobile phase and on the quantity of TFA added, which plays the role of an ion-pairing agent.

  8. FT-Raman study of cinchonine aqueous solutions with varying pH; 2D correlation method

    NASA Astrophysics Data System (ADS)

    Wesetucha-Birczyńska, Aleksandra

    1999-05-01

    Cinchonine (C 19H 22N 2O) is one of the Cinchona tree alkaloids. It consists of two moieties, a quinoline ring and quinuclidine linked by a hydroxymethylene bridge. Each one of these parts contains nitrogen atoms, which are proton acceptor and cause that cinchonine can be treated as a weak base. For the first time the protonation effect was evidenced in the RR spectra of cinchonine while interacting with DNA (A. Wesetucha-Birczyńska and K. Nakamoto, J. Raman Spectrosc. 27 (1996) 915). In the current study 2D correlation method was applied to analyze the FT-Raman spectra of cin aqueous solutions with varying pH, which was regarded as external perturbation in the 1300-1700 cm -1 range, which is quinuclidine and quinoline ring stretching vibration region. These monitored fluctuations transformed into 2D spectra allows to analyze these vibrations and differentiate them.

  9. Anomalous pH dependent stability behavior of surfactant-free nonpolar oil drops in aqueous electrolyte solutions.

    PubMed

    Clasohm, Lucy Y; Vakarelski, Ivan U; Dagastine, Raymond R; Chan, Derek Y C; Stevens, Geoffrey W; Grieser, Franz

    2007-08-28

    Recent advances in atomic force microscopy (AFM) force measurement techniques have allowed the direct measurement and theoretical interpretation of the interaction between a liquid droplet and a solid surface or between two liquid droplets. In this study, we investigated the interaction across an aqueous thin film between fluorocarbon (perfluoropentane) droplets, hydrocarbon (tetradecane) droplets, and a droplet and a flat mica surface in the absence of stabilizers. It was found that even at a relatively elevated electrolyte concentration of 0.1 M NaNO3, depending on the solution pH, interactions between two identical droplets or a droplet and a mica surface could be repulsive. A simple theoretical analysis of the magnitude and range of these interactive forces suggests that the DLVO theory cannot explain the observed behavior. The measured force behavior is discussed in the context of ion adsorption, and the arising charging effects, at the bare oil-water interface.

  10. Carbide precipitates in solution-quenched PH13-8 Mo stainless steel: A small-angle neutron scattering investigation

    NASA Astrophysics Data System (ADS)

    Sen, D.; Patra, A. K.; Mazumder, S.; Mittra, J.; Dey, G. K.; de, P. K.

    2004-08-01

    This paper deals with the small-angle neutron scattering (SANS) investigation on solution-quenched PH13-8 Mo stainless steel. From the nature of the variation of the functionality of the profiles for varying specimen thickness and also from the transmission electron microscopy (TEM), it has been established that the small-angle scattering signal predominantly originates from the block-like metallic carbide precipitates in the specimen. The contribution due to double Bragg reflection is not significant in the present case. The single scattering profile has been extracted from the experimental profiles corresponding to different values of specimen thickness. In order to avoid complexity and non-uniqueness of the multi-parameter minimization for randomly oriented polydisperse block-like precipitate model, the data have been analyzed assuming randomly oriented polydisperse cylindrical particle model with a locked aspect ratio.

  11. Significant improvement in photoluminescence of ZnSe(S) alloyed quantum dots prepared in high pH solution.

    PubMed

    Zan, Feng; Ren, Jicun

    2010-01-01

    In this paper, we described a simple approach for aqueous synthesis of highly luminescent ZnSe(S) alloyed quantum dots (QDs) in the presence of 3-mercaptopropionic acid as stabilizers using zinc chloride and NaHSe as precursors. The synthesis conditions were systematically investigated. We observed that the pH value of the Zn precursor solution had significant influence on the optical properties and the structure of the as-prepared ZnSe(S) QDs. The optimal pH value and molar ratio of Zn(2+) to HSe(-) were 12.0 and 25 : 1 respectively. Under the optimal conditions, we prepared highly photoluminescent ZnSe(S) QDs at up to 31% quantum yield (compared with Rhodamine 6G). The characterization of HRTEM and XRD showed that the ZnSe(S) QDs had good monodispersity and nice crystal structure. The fluorescence life time spectra demonstrated that ZnSe(S) QDs had a long lifetime in contrast to fluorescent dyes. Compared with the currently used organometallic approach, our method was 'green', the reaction condition was mild and the as-prepared ZnSe(S) QDs were water-soluble. More importantly, our method was low cost, and was very suitable for large-scale synthesis of highly luminescent ZnSe(S) QDs for the future applications.

  12. On modeling of chemical stimulation of an enhanced geothermal system using a high pH solution with chelating agent

    SciTech Connect

    Xu, T.; Rose, P.; Fayer, S.; Pruess, K.

    2009-05-01

    Dissolution of silica and calcite in the presence of a chelating agent (NTA) at a high pH was successfully demonstrated in laboratory experiments using a high-temperature flow reactor. (Note that the term 'silica' used here includes amorphous silica, quartz, and silicate glass bead). The mineral dissolution and associated porosity enhancement in the experiments were reproduced by reactive transport modeling using TOUGHREACT. The chemical stimulation method was applied by numerical modeling to a field geothermal injection well system to investigate its effectiveness. Parameters applicable to the quartz monzodiorite unit at the Enhanced Geothermal Systems (EGS) site at Desert Peak (Nevada) were used. Results indicate that the injection of a high pH chelating solution results in dissolution of both calcite and plagioclase, while avoiding precipitation of calcite at high temperature conditions. Consequently reservoir porosity and permeability can be enhanced especially near the injection well. Injection at a lower temperature of 120 C (over 160 C in the base-case) results in a porosity increase that is smaller close to the injection point, but extends to a larger radial distance. A slower kinetic rate results in less aggressive mineral dissolution close to the injection point and larger extent along the flow path, which is favorable for chemical stimulation.

  13. Alkaline buffers release EDRF from bovine cultured aortic endothelial cells.

    PubMed Central

    Mitchell, J. A.; de Nucci, G.; Warner, T. D.; Vane, J. R.

    1991-01-01

    1. Release of endothelium-derived relaxing factor (EDRF) and prostacyclin (PGI2) from bovine cultured aortic endothelial cells (EC) was measured by bioassay and radioimmunoassay, respectively. 2. Bradykinin (BK, 3-30 pmol), adenosine diphosphate (ADP, 2-6 nmol) or the sodium ionophore monensin (40-100 nmol) injected through a column of EC released EDRF. L-Arginine free base (FB; 10-20 mumol) or D-arginine FB (10-20 mumol) injected through the column of EC released similar amounts of EDRF and also caused an increase in pH of the Krebs solution perfusing the EC from 7.5-8.0 to 8.6-9.5. Sodium carbonate (Na2CO3) an alkaline buffer which caused the same changes in the pH of the Krebs solution also induced the same release of EDRF. The hydrochloride salts of L- or D-arginine did not cause either release of EDRF when injected through the column of EC or increases in the pH of the Krebs solution. 3. Inhibitors of either diacylglycerol lipase (RHC 80267) or kinase (R59022) inhibited the release of EDRF induced by BK or ADP but potentiated the release induced by L-arginine FB, monensin (40-100 nmol) or alkaline buffer (Na2CO3). R59022 and RHC 80267 infused through the EC increased the basal release of EDRF. 4. When calcium chloride was omitted from the Krebs solution the release of EDRF induced by alkaline buffer (Na2CO3; pH 8.6-9.5) or L-arginine FB (10-20 mumol) was selectively inhibited when compared to that induced by BK (3-30 pmol) or ADP (2-6 nmol). This inhibition was reversed when calcium (2.5 mM) was restored. 5. NG-monomethyl-L-arginine (NMMA; 30 microM) inhibited release of EDRF induced by BK (10-30 pmol) or alkaline buffers (Na2CO3 or D-arginine FB; pH 8.6-9.5). This inhibition was partially reversed by L- but not D-arginine FB or HCl (30-100 microM). 6. Prostacyclin was released when BK (10 pmol), ADP (2 nmol) or arachidonic acid (30 nmol) were injected through the column of EC. However, monensin (40 nmol) or alkaline buffers (pH 8.6-9.5) did not release

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

    PubMed

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

    2013-03-25

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

  15. Desorption of 137Cs from Brachythecium mildeanum moss using acid solutions with pH 4.60-6.50

    NASA Astrophysics Data System (ADS)

    Čučulović, Ana; Veselinović, Dragan

    2015-12-01

    The desorption of 137Cs from the moss Brachythecium mildeanum (Schimp.) was performed using the following solutions: H2SO4 ( I), HNO3 ( II), H2SO4 + HNO3 ( III) with pH values of 4.60, 5.15, and 5.75, respectively, as well as distilled water (D) with pH 6.50. After five successive desorptions, each lasting 24 h, 20.5-37.6% 137Cs was desorbed from the moss using these solutions, while 30.7% of the starting content was desorbed using distilled water. The first desorption removed the highest percent of the original content of 137Cs in the moss (11.3-18.4%). This was determined by measuring 137Cs activity. If the current results are compared with those obtained earlier it may be concluded that 137Cs desorption from mosses is not species-dependent. The obtained results indicate the necessity of investigating the influence of acid rain, or rather, of H+ ions, on desorption of other ions from biological systems, i.e., the role of H+ ions in spreading other polluting compounds and thus producing secondary environmental pollution. From the results of this study it follows that acid rain will lead, through H+ ion action, to a similar increasing pollution of fallout waters with other ionic compounds which may not be present in the water before the contact with the plants and thus enable the pollution spreading. In the investigated system, the replacement of H+ ions from acid rains by more dangerous radioactive ions occured, increasing the concentration of the radioactive ions in the water, which demonstrates that the same process takes place in fallout water.

  16. Cloud-point temperatures for lysozyme in electrolyte solutions: effect of salt type, salt concentration and pH.

    PubMed

    Grigsby, J J; Blanch, H W; Prausnitz, J M

    2001-07-24

    Liquid-liquid phase-separation data were obtained for aqueous saline solutions of hen egg-white lysozyme at a fixed protein concentration (87 g/l). The cloud-point temperature (CPT) was measured as a function of salt type and salt concentration to 3 M, at pH 4.0 and 7.0. Salts used included those from mono and divalent cations and anions. For the monovalent cations studied, as salt concentration increases, the CPT increases. For divalent cations, as salt concentration rises, a maximum in the CPT is observed and attributed to ion binding to the protein surface and subsequent water structuring. Trends for sulfate salts were dramatically different from those for other salts because sulfate ion is strongly hydrated and excluded from the lysozyme surface. For anions at fixed salt concentration, the CPT decreases with rising anion kosmotropic character. Comparison of CPTs for pH 4.0 and 7.0 revealed two trends. At low ionic strength for a given salt, differences in CPT can be explained in terms of repulsive electrostatic interactions between protein molecules, while at higher ionic strength, differences can be attributed to hydration forces. A model is proposed for the correlation and prediction of the CPT as a function of salt type and salt concentration. NaCl was chosen as a reference salt, and CPT deviations from that of NaCl were attributed to hydration forces. The Random Phase Approximation, in conjunction with a square-well potential, was used to calculate the strength of protein-protein interactions as a function of solution conditions for all salts studied.

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

    PubMed

    Stuhlpfarrer, Philipp; Luidold, Stefan; Antrekowitsch, Helmut

    2016-04-15

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

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

    USGS Publications Warehouse

    Zielinski, Robert A.

    1979-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  20. Adsorption equilibria between liposome membrane formed of phosphatidylcholine and aqueous sodium chloride solution as a function of pH.

    PubMed

    Kotyńska, J; Figaszewski, Z A

    2005-12-30

    The effect has been studied of the adsorption of ions (H(+), Na(+), OH(-), Cl(-)) which are present in solution upon the electric charge of the liposome membrane formed of phosphatidylcholine (PC). The surface charge density of the membrane was determined as a function of pH and electrolyte concentration from electrophoretic mobility measurements. The measurements were carried out by the laser-Doppler microelectrophoresis method. A four-equilibria model has been proposed to describe the phenomena occurring on the membrane surface. The equilibria in which the adsorption of other ions on the liposome membrane surface was involved were assumed to exist beside the equilibria in which the H(+) and OH(-) ions were engaged. The idea was confirmed by mathematical calculations. Association constants of the liposome membrane surface with ions of solution (K(AH), K(ANa), K(BOH), K(BCl)) were determined. The proposed model has been proved to be correct by comparing the resulting theoretic charge variation curves of the lecithin membrane with the experimental data.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  2. Early development of Al, Ca, and Na compositional gradients in labradorite leached in pH 2 HCl solutions

    NASA Astrophysics Data System (ADS)

    Nesbitt, H. W.; Skinner, W. M.

    2001-03-01

    Labradorite reacted with HCl solution (pH = 2.0) develops leached layers extending to about 500 Å depth after 12 h leaching, and to 1500 Å depth after 143 h leaching. Accurate Al, Ca, and Na compositional depth profiles were measured using x-ray photoelectron spectroscopy (XPS), with compositional accuracy of about 10% and depth resolution of about 50 Å. XPS analyses of pristine K-feldspar and labradorite surfaces yield Ca, Al, Si, and O analyses within about 5% of electron microprobe results. Alkali element analyses are inaccurate due to preferential sputtering or mobility induced by fracture. The accurate compositional depth profiles yield well constrained diffusion coefficients and moving boundary velocities for Ca and Al. Na, Ca, and Al compositional gradients change character after about 2 days of leaching, from a convex upward hyperboloid to a sigmoid shape. Thereafter, the feldspar diffusion front is clearly separated from the surface (where silica dissolution occurs), with the diffusion front migrating into the feldspar at about 4 × 10 -11 cm/s. Al diffuses down the compositional gradient at about 2.5 × 10 -17 cm 2/s and Ca diffuses almost twice as fast (4.0 × 10 -17 cm 2/s). The solution-solid interface and active leaching zone are separated (after 2 days) by a Si-rich zone virtually devoid of Na, Ca, and Al. Diffusion rates through this Si-rich overlayer may be very rapid and approach rates observed in aqueous solutions. Diffusive release of Ca and Al from labradorite cannot be modelled accurately with mathematical solutions where diffusion through homogeneous media is assumed. During leaching, Ca and Al apparently diffuse by "jumping" to, and residing on, previously vacated structural sites of the feldspar. The probability of Ca and Al migrating towards solution consequently is greater than their probability of migrating towards pristine plagioclase, primarily because there are many more "vacant" sites in the leached zone than in pristine

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

    PubMed Central

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

    2017-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  5. An evaluation of MES (2(N-Morpholino)ethanesulfonic acid) and Amberlite IRC-50 as pH buffers for nutrient solution studies

    NASA Technical Reports Server (NTRS)

    Bugbee, B. G.; Salisbury, F. B.

    1985-01-01

    All buffering agents used to stabilize pH in hydroponic research have disadvantages. Inorganic buffers are absorbed and may become phytotoxic. Solid carbonate salts temporarily mitigate decreasing pH but provide almost no protection against increasing pH, and they alter nutrient absorption. Exchange resins are more effective, but we find that they remove magnesium and manganese from solution. We have tested 2(N-Morpholino)ethanesulfonic acid (MES) as a buffering agent at concentrations of 1 and 10 mol m-3 (1 and 10 mM) with beans, corn, lettuce, tomatoes, and wheat. MES appears to be biologically inert and does not interact significantly with other solution ions. Relative growth rates among controls and MES treatments were nearly identical for each species during the trial period. The pH was stabilized by 1 mol m-3 MES. This buffer warrants further consideration in nutrient research.

  6. Peripheral administration of low pH solutions causes activation and sensitisation of convergent dorsal horn neurones in the anaesthetised rat.

    PubMed

    Carpenter, K J; Nandi, M; Dickenson, A H

    2001-02-09

    This is the first study to examine the effects of peripheral administration of acid on the activity of dorsal horn neurones in vivo. Extracellular recordings from convergent neurones revealed increases in neuronal activity evoked by administration of low pH solutions into the peripheral receptive field. Threshold for activity ranged from pH 5.85 to 2.5. The magnitude of responses increased with decreasing pH; maximum effects were achieved with pH 2.5 (648+/-181 action potentials/60 s, as compared to control-evoked activity of 86.3+/-29 action potentials/60 s). Activity lasted for up to 60 s, likely to represent the time for which the solutions were able to surmount the buffering capacity of the intact hindpaw. Significant sensitisation of the neurones to both innocuous (von Frey filament 9 g) and noxious (30 g) mechanical punctate stimuli was also observed.

  7. An evaluation of MES (2(N-Morpholino)ethanesulfonic acid) and Amberlite IRC-50 as pH buffers for nutrient solution studies.

    PubMed

    Bugbee, B G; Salisbury, F B

    1985-01-01

    All buffering agents used to stabilize pH in hydroponic research have disadvantages. Inorganic buffers are absorbed and may become phytotoxic. Solid carbonate salts temporarily mitigate decreasing pH but provide almost no protection against increasing pH, and they alter nutrient absorption. Exchange resins are more effective, but we find that they remove magnesium and manganese from solution. We have tested 2(N-Morpholino)ethanesulfonic acid (MES) as a buffering agent at concentrations of 1 and 10 mol m-3 (1 and 10 mM) with beans, corn, lettuce, tomatoes, and wheat. MES appears to be biologically inert and does not interact significantly with other solution ions. Relative growth rates among controls and MES treatments were nearly identical for each species during the trial period. The pH was stabilized by 1 mol m-3 MES. This buffer warrants further consideration in nutrient research.

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2011-05-01

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

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

    PubMed

    Huang, Tsung-Yuan; Lin, Wann-Yin

    2011-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

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

    PubMed

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

    2015-03-13

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

  15. Polyhydroxyflavones as extractants. Communication 7. Solvent extraction of europrium complexes with morin from alkaline media

    SciTech Connect

    Blank, A.B.

    1985-09-01

    This paper studies the analytical application of europium (III)-morin complex which is formed in alkaline medium and has an intense color. The extent of europium extraction was determined by adding to the extract a morin solution in isoamyl alcohol in a 50-100-fold excess with respect to europium. The dependence of the optical density of the extracts on the ph in the system europium (III)-morin-water-organic solvent for different excesses of the reagent is shown: this indicates formation of two extractable complexes, one being dominant in the pH range 4-7, the other at pH greater than or equal to 8.5. The extraction of the europium (III)-morin complex from alkaline solution is used for direct extraction-photometric determination of europium(III) in compounds of elements having amphoteric properties or forming amines (Zns, Mo0/sub 3/).

  16. Experimental studies on the toxicity of lithographic developer solution.

    PubMed

    Saito, T; Takeichi, S

    1995-01-01

    The purpose of this study was to determine whether the toxicity of a lithographic developer solution which contains hydroquinone is caused by hydroquinone or the alkaline lithographic developer solution. Male Wistar rats were divided into seven groups. In four groups, rats were dosed orally with 3% hydroquinone or 3% hydroquinone in 3% lithographic developer solution. Hydroquinone levels were measured after one and 24 hours. In two groups, rats were dosed orally with 6% hydroquinone or 6% hydroquinone in lithographic developer solution. In the seventh group, rats received the alkaline solution only. Hydroquinone measurement was made using gas chromatography-mass spectrometry. Hydroquinone was rapidly absorbed from the gastrointestinal tract and subsequently distributed throughout the body. Nearly all hydroquinone was excreted in the urine as either a glucuronide or a sulfate (78-82%) within 24 hours. All rats administered 6% hydroquinone in non-alkaline vehicle died, but the mortality rate of rats administered 6% hydroquinone in lithographic developer solution was 60%. Tissue hydroquinone was lower at one hour and 24 hours after administration in lithographic developer solution than in equal dose of hydroquinone in non-alkaline vehicle suggesting decreased absorption in an alkaline pH. Hydroquinone was not associated with gross pathologic changes of the intestine but all animals treated with lithographic developer solution or alkaline solution had congestion, hemorrhagic petechiae and purple-brown discoloration throughout the small intestine. The combination of alkaline/formaldehyde diluent with hydroquinone may delay hydroquinone absorption but increase the risk of intestinal necrosis.

  17. Effects of pH, dissolved oxygen, and ionic strength on the survival of Escherichia coli O157:H7 in organic acid solutions.

    PubMed

    Kreske, Audrey C; Bjornsdottir, Kristin; Breidt, Fred; Hassan, Hosni

    2008-12-01

    The ability of Escherichia coli O157:H7 to survive in acidified vegetable products is of concern because of previously documented outbreaks associated with fruit juices. A study was conducted to determine the survival of E. coli O157:H7 in organic acids at pH values typical of acidified vegetable products (pH 3.2 and 3.7) under different dissolved oxygen conditions (< or = 0.05 and 5 mg/liter) and a range of ionic strengths (0.086 to 1.14). All solutions contained 20 mM gluconic acid, which was used as a noninhibitory low pH buffer to compare the individual acid effect to that of pH alone on the survival of E. coli O157:H7. E. coli O157:H7 cells challenged in buffered solution with ca. 5-mg/liter dissolved oxygen (present in tap water) over a range of ionic strengths at pH 3.2 exhibited a decrease in survival over 6 h at 30 degrees C as the ionic strength was increased. Cells challenged in 40 mM protonated L-lactic and acetic acid solutions with ionic strength of 0.684 achieved a > 4.7-log CFU/ml reduction at pH 3.2. However, under oxygen-limiting conditions in an anaerobic chamber, with < or = 0.05-mg/ liter oxygen, E. coli O157:H7 cells showed < or = 1.55-log CFU/ml reduction regardless of pH, acid type, concentration, or ionic strength. Many acid and acidified foods are sold in hermetically sealed containers with oxygen-limiting conditions. Our results demonstrate that E. coli O157:H7 may survive better than previously expected from studies with acid solutions containing dissolved oxygen.

  18. Autonomous in situ measurements of seawater alkalinity.

    PubMed

    Spaulding, Reggie S; DeGrandpre, Michael D; Beck, James C; Hart, Robert D; Peterson, Brittany; De Carlo, Eric H; Drupp, Patrick S; Hammar, Terry R

    2014-08-19

    Total alkalinity (AT) is an important parameter for describing the marine inorganic carbon system and understanding the effects of atmospheric CO2 on the oceans. Measurements of AT are limited, however, because of the laborious process of collecting and analyzing samples. In this work we evaluate the performance of an autonomous instrument for high temporal resolution measurements of seawater AT. The Submersible Autonomous Moored Instrument for alkalinity (SAMI-alk) uses a novel tracer monitored titration method where a colorimetric pH indicator quantifies both pH and relative volumes of sample and titrant, circumventing the need for gravimetric or volumetric measurements. The SAMI-alk performance was validated in the laboratory and in situ during two field studies. Overall in situ accuracy was -2.2 ± 13.1 μmol kg(-1) (n = 86), on the basis of comparison to discrete samples. Precision on duplicate analyses of a carbonate standard was ±4.7 μmol kg(-1) (n = 22). This prototype instrument can measure in situ AT hourly for one month, limited by consumption of reagent and standard solutions.

  19. Three stage multilayer formation kinetics during adsorption of an anionic fluorinated surfactant onto germanium: solution pH and salt effects.

    PubMed

    Xing, Rong; Rankin, Stephen E

    2013-07-01

    The effects of solution pH, salt type and its concentration on the adsorption kinetics and the structural evolution of an anionic fluorinated surfactant, tetraethylammonium perfluorooctylsulfonate (TEA-FOS), at the hydroxylated Ge/aqueous solution interface are investigated by using Fourier transform infrared spectroscopy in attenuated total reflection mode (ATR-FTIR). The surface excess, the adsorption rate, the durations of three-stage adsorption and the molecular orientation of adsorbed TEA-FOS are all dependent on the pH of the solution. Consistent with the expected effects of solution pH on surface charge of the germanium oxide crystal surface, the most surfactant adsorbs at acidic pH 3.4 although a considerable amount still adsorbs at pH 10.0. Linear dichroism measurements suggest that the adsorbed surfactants prefer to form less-curved (flattened) multilayer admicelles, which pack more closely on the solid surface as the solution pH decreases. Under both acidic (pH 3.4) and basic (pH 10.0) conditions, the equilibrium surface excess first passes through a maximum as NaCl concentration increases, followed by a decrease. This suggests that excessive NaCl concentration is not favorable for multilayer formation due to increased electrostatic shielding which reduces the ion-pairing ability between TEA(+) and FOS(-). In addition, infrared dichroism measurements of CF2 stretching show that salt type and its concentration influence the structural evolution of adsorbed surfactants. A moderate amount of NaCl favors the assembly of adsorbed micelles into ordered flattened aggregates, but an excess of NaCl makes adsorbed surfactants assemble randomly like spherical aggregates. Compared to Na(+) and K(+) ions, Ca(2+) ions cause the adsorbed surfactants to pack more closely on the solid surface into flattened micellar aggregates. All of the effects of solution pH and salt can be rationalized based on Coulombic interactions between the substrate surface, surfactants and

  20. Contribution of solution pH and buffer capacity to suppress intergranular stress corrosion cracking of sensitized type 304 stainless steel at 95 C

    SciTech Connect

    Zhang, S.; Shibata, T.; Haruna, T. . Dept. of Materials Science and Processing)

    1999-05-01

    Controlling pH of high-temperature water to [approximately]pH 7 at 300 C by adding lithium hydroxide (LiOH) into the coolant system of a pressurized water reactor (PWR) successfully has been mitigating the corrosion of PWR component materials. The effects of solution pH and buffer capacity on intergranular stress corrosion cracking (IGSCC) of sensitized type 304 stainless steel ([SS] UNS S30400) was examined at 95 C by slow strain rate technique (SSRT) with an in-situ cracking observation system. It was found that an increase in solution pH or buffer capacity increased crack initiation time and decreased mean crack initiation frequency, but exerted almost no effect on crack propagation. This inhibition effect on IGSCC initiation was explained as resulting from a retarding effect of solution pH and buffer capacity on the decrease in pH at crack nuclei caused by the hydrolysis of metal ions dissolved when the passive film was ruptured by strain in SSRT.

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

    SciTech Connect

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

    1997-09-01

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

  2. Effects of organic ligands and pH on the leaching of copper from brake wear debris in model environmental solutions.

    PubMed

    Hur, Jin; Schlautman, Mark A; Yim, Soobin

    2004-01-01

    Copper leaching from a disc brake wear debris sample was examined in a variety of aqueous solutions to simulate potential leaching processes during rain events and in surface waters. Synthetic rainwater leached 40% of the total copper present in the brake wear debris into solution after 18 h in batch reactors, which was approximately three times more copper than that extracted by the US Environmental Protection Agency's Synthetic Precipitation Leaching Procedure. Formate and acetate were responsible for the enhanced copper leaching, as demonstrated by higher average amounts of leached copper in synthetic rainwater with- versus without the organic acids (40 versus 31% recovery). This observation suggests leaching tests that do not incorporate the appropriate types and concentrations of organic ligands present in rainwater will likely underestimate copper mobilization from brake wear debris during rain events. Leaching of copper from the brake wear debris ranged from 23 to 40% in solutions containing 3 to 15 mg C L(-1) dissolved humic substances, and was higher still in solutions containing relatively high concentrations of the synthetic metal chelating agent ethylenediaminetetraacetic acid. Static pH tests demonstrated that copper leaching from brake wear debris is highly pH dependent, with more leaching occurring at lower solution pH values. Leaching rate studies revealed that equilibrium generally was not attained within 48 h in the model solutions, indicating that additional copper can be expected to be released in environments where brake wear debris is exposed to long-term leaching processes.

  3. Relation of pH to toxicity of lampricide TFM in the laboratory

    USGS Publications Warehouse

    Bills, T.D.; Marking, L.L.; Howe, G.E.; Rach, J.J.

    1988-01-01

    In the control of larval sea lamprey (Petromyzon marinus ) with 3-trifluoromethyl-4-nitrophenol (TFM) in tributaries of the Great Lakes, occasional kills of other fishes have caused concern about the effects of the chemical on non-target organisms. Stream treatment rates have been based on previous application rates, alkalinity measurements, results of on-site toxicity tests, or combinations of these. Laboratory studies in 1987 showed that pH is the primary factor that affects the toxicity of TFM (the lower the pH, the greater the toxicity): even small changes in pH alter the toxicity, whereas substantial changes in alkalinity have little effect. In 12-h exposures, the 96-h LC50 for TFM to rainbow trout (Salmo gairdneri ) ranged from about 0.9 mg/L at pH 6.5 to > 100 mg/L at pH 9.5, but (at pH 7.5) the LC50's differed little at total alkalinities of about 18 mg/L and 207 mg/L. Decreases in pH as small as 0.5 pH unit caused nontoxic solutions to become toxic to rainbow trout. Some kills of non-target fish during stream treatments were reportedly caused by decreases in pH, and (conversely) that some stream treatments for sea lampreys were ineffective because pH increased.

  4. The iron catalyzed oxidation of sulfur(IV) in aqueous solution: Differing effects of organics at high and low pH

    NASA Astrophysics Data System (ADS)

    Martin, L. R.; Hill, M. W.; Tai, A. F.; Good, T. W.

    1991-02-01

    We have studied the oxidation of sulfur dioxide by dissolved oxygen in highly dilute solutions with a new differential optical absorption technique. We measured the rate of oxidation catalyzed by iron(III) over a wide range of pH, ionic strength, and in the presence of various organic materials. The studies indicate that noncomplexing organic molecules are highly inhibiting at "high" pH values of 5 and above and are not inhibiting at "low" pH values of 3 and below. Furthermore, the order of the reaction with respect to iron is different in the two pH regimes. This suggests that the mechanism of this reaction differs in the two pH regimes and is probably a free radical chain at high pH and a nonradical mechanism at low pH. Some of the mechanisms proposed in the literature are discussed in the light of these new data. None of the proposed mechanisms give completely satisfactory agreement with the data. We propose a modified free radical chain mechanism for the high pH regime, which correctly predicts the organic inhibitions. For the low pH regime, mechanisms proposed by Conklin and Hoffmann (1988) and by Hoffmann and Jacob (1984) give fair agreement with the pH data and correctly predict the self-inhibition, the sulfate inhibition, and the ionic strength inhibition. In view of the new data we believe that the iron(III) catalyzed reaction in tropospheric clouds can be a major contributor to the rate of sulfate formation, but there will be significant inhibition of this process by formic acid in some situations.

  5. Investigation of the solution initial pH effects on the performance of UV/Fe-ZSM5/H(2)O(2) process.

    PubMed

    Kasiri, M B; Aleboyeh, A; Aleboyeh, H

    2010-01-01

    Effect of the solution initial pH was investigated on the performance of photo-Fenton process using Fe-ZSM5 zeolite as a heterogeneous catalyst for degradation of azo dye Acid Red 14. All experiments were performed in a 1.0 L tubular closed circulation batch photo-reactor. The dye degradation quantum yield was maximal when the solution initial pH was about 5. An amount of about 0.3 mg L(-1) of Fe ions leached out of the zeolite. However, monitoring Fe ion concentration during the experiments showed that the efficiency of the process is not due to the leached Fe ions. The effect of pH on decomposition rate of hydrogen peroxide in different systems such as H(2)O(2) alone, UV/H(2)O(2), UV/Zeolite and UV/Zeolite/H(2)O(2) was explored in detail to explain the results obtained.

  6. Dolomite Dissolution in Alkaline Cementious Media

    NASA Astrophysics Data System (ADS)

    Mittermayr, Florian; Klammer, Dietmar; Köhler, Stephan; Dietzel, Martin

    2010-05-01

    Chemical alteration of concrete has gained much attention over the past years as many cases of deterioration due to sulphate attack, thaumasite formation (TSA) or alkali silica reactions (ASR) have been reported in various constructions (Schmidt et al, 2009). Much less is known about the so called alkali carbonate reaction (ACR). It is believed that dolomite aggregates can react with the alkalis from the cement, dissolve and form calcite and brucite (Katayama, 2004). Due to very low solubility of dolomite in alkaline solutions this reaction seems doubtful. In this study we are trying to gain new insides about the conditions that can lead to the dissolution of dolomite in concrete. Therefore we investigated concrete samples from Austrian tunnels that show partially dissolved dolomite aggregates. Petrological analysis such as microprobe, SEM and Raman spectroscopy as well as a hydrochemical analysis of interstitial solutions and ground water and modelling with PhreeqC (Parkhurst and Appelo, 1999) are carried out. In addition a series of batch experiments is set up. Modelling approaches by PhreeqC show a thermodynamically possibility in the alkaline range when additional Ca2+ in solution causes dolomite to become more and more undersaturated as calcite gets supersaturated. Interacting ground water is enriched in Ca2+and saturated with respect to gypsum as marine evaporites are found in situ rocks. Furthermore it is more likely that Portlandite (Ca(OH)2) plays a more important role than Na and K in the cement. Portlandite acts as an additional Ca2+ source and is much more abundant than the alkalies. Some interstitial solutions are dominated mainly by Na+ and SO42- and reach concentrations up to 30 g/l TDS. It is believed that solutions can even reach thenardite saturation as efflorescences are found on the tunnel walls. In consequence dolomite solubility increases with increasing ionic strength. pH > 11 further accelerate the process of dedolomitization by the removal

  7. Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Porous Media: Influence of Solution pH, Ionic Strength, and the Presence of Humic Acid

    EPA Science Inventory

    The influence of solution pH, ionic strength, and varying concentrations of the Suwannee River Humic Acid (SRHA) on the transport of titanium dioxide (TiO2, rutile) nanoparticle aggregates (nTiO2) in saturated porous media was investigated through systematically examining the tra...

  8. Transport, retention, and long-term release behavior of ZnO nanoparticle aggregates in saturated quartz sand: Role of solution pH and biofilm coating

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The transport, retention, and long-term fate of zinc oxide nanoparticles (ZnO-NPs) were investigated in saturated, bare and biofilm (Pseudomonas putida) coated sand packed columns. Almost complete retention of ZnO-NPs occurred in bare and biofilm coated sand when the influent solution pH was 9 and t...

  9. Molecular mechanism of plasma sterilization in solution with the reduced pH method: importance of permeation of HOO radicals into the cell membrane

    NASA Astrophysics Data System (ADS)

    Takai, Eisuke; Ikawa, Satoshi; Kitano, Katsuhisa; Kuwabara, Junpei; Shiraki, Kentaro

    2013-07-01

    Sterilization of certain infected areas of the human body surface is necessary for dental and surgical therapies. Because the blood is filled with body fluid, sterilization in solution is essential. In vitro solution sterilization has been successively carried out using a combination of low-temperature atmospheric-pressure plasma and the reduced pH method, where the solution is sufficiently acidic. Here, we show the molecular mechanism of such plasma sterilization in solution based on microbiology. Three kinds of bacteria were inactivated by plasma treatment under various pH conditions. The theoretical and experimental models revealed that the sterilization was characterized by the concentration of hydroperoxy radicals (HOO·), which were dependent on the pH value. Bacterial inactivation rates were proportional to the HOO· concentrations calculated by the theoretical model. To evaluate the penetration of radicals into the cell membrane, a bacterial model using dye-included micelles was used. Decolouration rates of the model were also in proportion with the calculated HOO· concentrations. These results indicate that the key species for plasma sterilization were hydroperoxy radicals. More importantly, the high permeation of hydroperoxy radicals into the cell membrane plays a key role for efficient bactericidal inactivation using the reduced pH method.

  10. Influence of precipitant solution pH on the structural, morphological and upconversion luminescent properties of Lu 2O 3:2%Yb, 0.2%Tm nanopowders

    NASA Astrophysics Data System (ADS)

    Li, Li; Xiaochun, Wang; xiantao, Wei; Yonghu, Chen; Changxin, Guo; Min, Yin

    2011-02-01

    Lutetium oxide nanopowders codoped with Tm 3+ and Yb 3+ were synthesized by the reverse-strike co-precipitation method. Effects of precipitant solution pH on the structural, morphological and upconversion luminescent properties of Lu 2O 3:2%Yb, 0.2%Tm nanopowders had been investigated. The results show that pH value of the precipitant (NH 4HCO 3) solution has a significant effect on the particle size, morphology and upconversion emission intensity of the Lu 2O 3:2%Yb, 0.2%Tm nanopowders. All the samples obtained from different pH value of precipitant solution can be readily indexed to pure cubic phase of Lu 2O 3, indicating good crystallinity. The upconversion emission intensity of Lu 2O 3:2%Yb, 0.2%Tm nanopowders obtained from the precipitant solution with pH=11 is the strongest. The enhancement of the upconversion luminescence is suggested to be the consequence of reducing the number of OH - groups and the enlarged nanopowder size. The strong blue, weak red and near infrared emissions from the prepared nanopowders were observed under 980 nm laser excitation, and attributed to the 1G 4→ 3H 6, 1G 4→ 3F 4 and 3H 4→ 3H 6 transitions of Tm 3+ ion, respectively.

  11. Activated carbon enhanced ozonation of oxalate attributed to HO oxidation in bulk solution and surface oxidation: effect of activated carbon dosage and pH.

    PubMed

    Xing, Linlin; Xie, Yongbing; Minakata, Daisuke; Cao, Hongbin; Xiao, Jiadong; Zhang, Yi; Crittenden, John C

    2014-10-01

    Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon (AC) in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals (HO) in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol (tBA) with low dosages of AC, while it was hardly affected by tBA when the AC dosage was greater than 0.3g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05g/L, but it did not work when the AC dosage was no less than 0.1g/L. These observations indicate that HO in bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HO oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HO oxidation in basic bulk solution. A mechanism involving both HO oxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate.

  12. PhD Crisis Discourse: A Critical Approach to the Framing of the Problem and Some Australian "Solutions"

    ERIC Educational Resources Information Center

    Cuthbert, Denise; Molla, Tebeje

    2015-01-01

    A feature of HE reform discourse is the tendency to construct the rationale for reform in terms of averting calamity and risk. We refer to this risk talk as "crisis discourse." This study examines the formulation of PhD crisis discourse internationally and in Australia. We find that a key feature of PhD crisis discourse is that…

  13. Transport, retention, and long-term release behavior of ZnO nanoparticle aggregates in saturated quartz sand: Role of solution pH and biofilm coating.

    PubMed

    Han, Yosep; Hwang, Gukhwa; Kim, Donghyun; Bradford, Scott A; Lee, Byoungcheun; Eom, Igchun; Kim, Pil Je; Choi, Siyoung Q; Kim, Hyunjung

    2016-03-01

    The transport, retention, and long-term release of zinc oxide nanoparticle aggregates (denoted below as ZnO-NPs) were investigated in saturated, bare and biofilm (Pseudomonas putida) coated sand packed columns. Almost complete retention of ZnO-NPs occurred in bare and biofilm coated sand when the influent solution pH was 9 and the ionic strength (IS) was 0.1 or 10 mM NaCl, and the retention profiles were always hyper-exponential. Increasing the solution IS and biofilm coating produced enhanced retention of ZnO-NPs near the column inlet. The enhanced NPs retention at high IS was attributed to more favorable NP-silica and NP-NP interactions; this was consistent with the interaction energy calculations. Meanwhile, the greater NPs retention in the presence of biofilm was attributed to larger roughness heights which alter the mass transfer rate, the interaction energy profile, and lever arms associated with the torque balance; e.g., scanning electron and atomic force microscopy was used to determine roughness heights of 33.4 nm and 97.8 nm for bare sand and biofilm-coated sand, respectively. Interactions between NPs and extracellular polymeric substances may have also contributed to enhanced NP retention in biofilm-coated sand at low IS. The long-term release of retained ZnO-NPs was subsequently investigated by continuously injecting NP-free solution at pH 6, 9, or 10 and keeping the IS constant at 10 mM. The amount and rate of retained ZnO-NP removal was strongly dependent on the solution pH. Specifically, almost complete removal of retained ZnO-NPs was observed after 627 pore volumes when the solution pH was 6, whereas much less Zn was recovered when the eluting solution pH was buffered to pH = 9 and especially 10. This long-term removal was attributed to pH-dependent dissolution of retained ZnO-NPs because: (i) the solubility of ZnO-NPs increases with decreasing pH; and (ii) ZnO-NPs were not detected in the effluent. The presence of biofilm also decreased the

  14. Influence of the solution pH in the 6-mercaptopurine self-assembled monolayer (6MP-SAM) on a Au(111) single-crystal electrode.

    PubMed

    Madueño, Rafael; García-Raya, Daniel; Viudez, Alfonso J; Sevilla, José M; Pineda, Teresa; Blázquez, Manuel

    2007-10-23

    Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) have been prepared on a Au(111) single-crystal electrode by immersion of the metal surface in a 100 microM 6MP and 0.01 M HClO4 solution. The 6MP-SAM Au(111) single-crystal electrodes were transferred to the cell and allowed to equilibrate with the different aqueous working solutions before the electrochemical experiments. The influence of the solution pH was studied by cyclic voltammetry, double layer capacitance curves, and electrochemical impedance spectroscopy. The electrochemical behavior of the 6MP-SAM in acetic acid at pH 4 presents important differences in comparison to that obtained in 0.1 M KOH solutions. Cyclic voltammograms for the reductive desorption process in acid medium are broad and show some features that can be explained by a phase transition between a chemisorbed and a physisorbed state of the 6MP molecules. The low solubility of these molecules in acid medium could explain this phenomenon and the readsorption of the complete monolayer when the potential is scanned in the positive direction. The variation of the double-layer capacitance values in the potential range of monolayer stability with the pH suggests that the acid-base chemistry of the 6MP molecules is playing a role. This fact has been studied by following the variations of the electron-transfer rate constant of the highly charged redox probes as are Fe(CN)(6)-3/-4 and Ru(NH3)(6)+3/+2 as a function of solution pH. The apparent surface pKa value for the 6MP-SAM (pKa approximately 8) is explained by the total conversion of the different 6MP tautomers that exist in solution to the thiol species in the adsorbed state.

  15. Changes in medullary extracellular pH, sympathetic and phrenic nerve activity during brainstem perfusion with CO2 enriched solutions.

    PubMed

    König, S A; Offner, B; Czachurski, J; Seller, H

    1995-01-20

    Measurements are presented of sympathetic nerve activity (SNA), phrenic nerve activity (PNA), and local extracellular pH (ECF pH) within the rostral ventrolateral medulla (RVLM) in response to perfusions of the RVLM with CO2-enriched saline. Experiments were performed on cats anaesthetized with chloralose. The ventrolateral medullary surface was exposed, and a catheter was placed in the left vertebral artery from the axilla to allow perfusion of the RVLM. Baroreceptor and peripheral chemoreceptor denervations were performed by cutting the vagal, aortic and carotid sinus nerves. The activities of the renal and the phrenic nerve were recorded, in some experiments in parallel with the cardiac nerve. Recordings of the pH were done with ion-sensitive theta-microelectrodes. A linear relationship between the CO2 concentration of the perfusate and the evoked changes in ECF pH was found. The ECF pH did not change systematically in one or the other direction within depths between 1 and 3 mm below the surface of the medulla. The various patterns of interaction of ECF pH, SNA, and PNA are described in detail. Phrenic nerve response to perfusions was very variable; a more prolonged increase in amplitude of phasic discharges compared to the duration of changes in SNA and ECF pH was the most frequent finding, but non-phasic tonic activation and complete silence were also seen during perfusions. SNA could also deviate from ECF pH both with regard to its latency and to its time course in response to perfusions. Therefore, this study provides further evidence for deviations of cardiorespiratory adaptation from ECF pH, corroborating the notion that this parameter is not the decisive one for central chemoreception.

  16. Constituents and pH changes in protein rich hyaluronan solution affect the biotribological properties of artificial articular joints.

    PubMed

    Kitano, T; Ateshian, G A; Mow, V C; Kadoya, Y; Yamano, Y

    2001-08-01

    The relationship between the coefficient of friction and pH value or protein constituents of lubricating fluid, together with viscosity, were studied within a bearing surface model for artificial joint, ultra-high molecular weight polyethylene (UHMWPE) against stainless steel (SUS), using a mechanical spectrometer. Four lubricants were tested in this study: sodium hyaluronate (HA), HA with albumin, HA with gamma-globulin, and HA with (L)alpha-dipalmitoyl phosphatidylcholine ((L)alpha-DPPC). The coefficient of friction between UHMWPE and SUS in HA with albumin or HA with gamma-globulin varied from 0.035 to 0.070 depending on angular velocity and pH. The coefficient of friction in HA or HA with (L)alpha-DPPC varied from 0.023 to 0.045 depending on angular velocity and pH. The variation in pH for HA with albumin had a large effect on the coefficient of friction at low range of angular velocity with viscosity independence. The variation in pH for HA with gamma-globulin had a large effect on the coefficient of friction with viscosity dependence at high angular velocity. The addition of (L)alpha-DPPC showed a small effect on the coefficient of friction at low angular velocity. This study confirms that the presence of albumin in the lubricant promotes pH dependence and viscosity independence of the tribological properties at low speed while the presence of globulin promotes pH and viscosity independence at low speed and promotes pH and viscosity dependence at high speed in the lubrication of UHMWPE against SUS. This study supports the clinical hypothesis that the effect of constituents and pH changes in periprosthetic fluid for the lubrication is a clue toward resolving many complications after total joint replacement.

  17. Influence of Ca and pH on the uptake and effects of Cd in Folsomia candida exposed to simplified soil solutions.

    PubMed

    Ardestani, Masoud M; Ortiz, Maria Diez; van Gestel, Cornelis A M

    2013-08-01

    The present study sought to quantify the components of a biotic ligand model (BLM) for the effects of Cd on Folsomia candida (Collembola). Assuming that soil porewater is the main route of exposure and to exclude the effects of soil particles on metal availability, animals were exposed for 7 d to different Cd concentrations between 0.1 mM and 100 mM in simplified soil solutions at different Ca concentrations (0.2 mM, 0.8 mM, 3.2 mM, and 12.8 mM) or at different pH (5.0, 6.0, and 7.0). Higher Ca concentrations decreased the toxicity of Cd (adult survival) in test solutions, whereas toxicity was slightly lower at pH 7 and 6 than at pH 5, suggesting a mitigating effect of Ca and to a lesser extent pH on Cd toxicity to F. candida. Internal Cd concentrations in the animals increased with increasing exposure level but were significantly reduced by increasing Ca concentrations and were not significantly affected by pH. By using Langmuir isotherms, binding constants for Cd, Ca, and protons and the fraction of binding sites occupied by Cd were calculated and used to predict effects of Cd on survival. Predicted toxicity showed a good agreement with measured responses when Ca and pH were used as separate factors or combined together. The present study shows indications of protective effects of Ca but less of protons on the toxicity and uptake of Cd in F. candida on exposure to simplified soil solutions, which can be described using the principles of a biotic ligand model.

  18. Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid

    SciTech Connect

    Stevens, Joanna S.; Gainar, Adrian; Suljoti, Edlira; Xiao, Jie; Golnak, Ronny; Aziz, Emad F.; Schroeder, Sven L. M.

    2015-03-18

    Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO–LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs and σ* shape resonances in the NEXAFS spectra. Finally, this provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute–solvent interactions.

  19. Effect of shear force, solution pH and breakage period on characteristics of flocs formed by Titanium tetrachloride (TiCl4) and Polyaluminum chloride (PACl) with surface water treatment.

    PubMed

    Zhao, Y X; Gao, B Y; Shon, H K; Kim, J-H; Yue, Q Y

    2011-03-15

    The growth, breakage and regrowth nature of flocs formed by Titanium tetrachloride (TiCl(4)) and polyaluminum chloride (PACl) was comparatively evaluated with surface water treatment. A series of jar experiments were conducted to investigate the impacts of different operating parameters such as shear force, solution pH and a breakage period on floc strength and re-aggregation potential. Results indicated that the responses of flocs to different operating parameters depend on the coagulant used. The ability of floc to resist breakage decreased with the increase of shear force and breakage period. Floc strength properties were also measured in response to increasing shear force, with the results suggesting that the order of floc strength was TiCl(4)>PACl. Floc regrowth of the two coagulants after exposure to high shear was limited, and flocs formed by TiCl(4) displayed weaker recoverability. The flocs generated in acid conditions were more recoverable than those generated in alkaline conditions no matter which coagulant was used.

  20. Single and multi-component adsorptive removal of bisphenol A and 2,4-dichlorophenol from aqueous solutions with transition metal modified inorganic-organic pillared clay composites: Effect of pH and presence of humic acid.

    PubMed

    Ortiz-Martínez, Krisiam; Reddy, Pratap; Cabrera-Lafaurie, Wilman A; Román, Félix R; Hernández-Maldonado, Arturo J

    2016-07-15

    Pillared clay based composites containing transition metals and a surfactant, namely MAlOr-NaBt (Bt=bentonite; Or=surfactant; M=Ni(2+), Cu(2+)or Co(2+)), were prepared to study selectivity and capacity toward single and multiple-component adsorption of bisphenol A (BPA) and 2,4-diclorophenol (DCP) from water. Tests were also performed to account for the presence of natural organic matter in the form of humic acid (HA). Equilibrium adsorption capacities for single components increased as follows: NaBtpH conditions and ambient temperature, representing an ordered of magnitude increase over the unmodified pillared clay capacities. Inclusion of the transition metal brought an increase of nearly two-fold in adsorption capacity over the materials modified only with surfactant. The MAlOr-NaBt adsorbents displayed remarkable selectivity for BPA. Multi-component fixed-bed tests, however, revealed competition between the adsorbates, with the exception of the CuAlOr-NaBt beds. Inclusion of HA, surprisingly, enhanced the phenols adsorption capacity. Preliminary regeneration tests suggested that the adsorbent capacity can be recovered via thermal treatment or by washing with alkaline solutions. The former strategy, however, requires surfactant replenishment. More complex schemes would be needed to deal with absorbed HA.

  1. Coupling the Alkaline-Surfactant-Polymer Technology and The Gelation Technology to Maximize Oil Production

    SciTech Connect

    Malcolm Pitts; Jie Qi; Dan Wilson; David Stewart; Bill Jones

    2005-10-01

    Gelation technologies have been developed to provide more efficient vertical sweep efficiencies for flooding naturally fractured oil reservoirs or more efficient areal sweep efficiency for those with high permeability contrast ''thief zones''. The field proven alkaline-surfactant-polymer technology economically recovers 15% to 25% OOIP more oil than waterflooding from swept pore space of an oil reservoir. However, alkaline-surfactant-polymer technology is not amenable to naturally fractured reservoirs or those with thief zones because much of injected solution bypasses target pore space containing oil. This work investigates whether combining these two technologies could broaden applicability of alkaline-surfactant-polymer flooding into these reservoirs. A prior fluid-fluid report discussed interaction of different gel chemical compositions and alkaline-surfactant-polymer solutions. Gel solutions under dynamic conditions of linear corefloods showed similar stability to alkaline-surfactant-polymer solutions as in the fluid-fluid analyses. Aluminum-polyacrylamide, flowing gels are not stable to alkaline-surfactant-polymer solutions of either pH 10.5 or 12.9. Chromium acetate-polyacrylamide flowing and rigid flowing gels are stable to subsequent alkaline-surfactant-polymer solution injection. Rigid flowing chromium acetate-polyacrylamide gels maintained permeability reduction better than flowing chromium acetate-polyacrylamide gels. Silicate-polyacrylamide gels are not stable with subsequent injection of either a pH 10.5 or a 12.9 alkaline-surfactant-polymer solution. Chromium acetate-xanthan gum rigid gels are not stable to subsequent alkaline-surfactant-polymer solution injection. Resorcinol-formaldehyde gels were stable to subsequent alkaline-surfactant-polymer solution injection. When evaluated in a dual core configuration, injected fluid flows into the core with the greatest effective permeability to the injected fluid. The same gel stability trends to subsequent

  2. A study of the molecular sources of nonideal osmotic pressure of bovine serum albumin solutions as a function of pH.

    PubMed

    Kanal, K M; Fullerton, G D; Cameron, I L

    1994-01-01

    The nonideal osmotic pressure of bovine serum albumin (BSA) solutions was studied extensively by Scatchard and colleagues. The extent of pH- and salt-dependent nonideality changes are large and unexplained. In 1992, Fullerton et al. derived new empirical expressions to describe solution nonideal colligative properties including osmotic pressure (Fullerton et al. 1992. Biochem. Cell Biol. 70:1325-1331). These expressions are based on the concepts of volume occupancy and hydration force. Nonideality is accurately described by a solute/solvent interaction parameter I and an "effective" osmotic molecular weight Ae. This paper uses the interaction-corrected nonideal expressions for osmotic pressure to calculate the hydration I values and "effective" osmotic molecular weight of BSA, Ae, as a function of pH. Both factors vary in a predictable manner due to denaturing of the BSA molecule. Both contribute to an increase in osmotic pressure for the same protein concentration as the solution pH moves away from the isoelectric point. Increased nonideality is caused by larger hydration resulting from larger solvent-accessible surface areas and by the decrease in "effective" osmotic molecular weight, Ae, due to segmental motion of denatured (filamentous) molecules.

  3. A study of the molecular sources of nonideal osmotic pressure of bovine serum albumin solutions as a function of pH.

    PubMed Central

    Kanal, K M; Fullerton, G D; Cameron, I L

    1994-01-01

    The nonideal osmotic pressure of bovine serum albumin (BSA) solutions was studied extensively by Scatchard and colleagues. The extent of pH- and salt-dependent nonideality changes are large and unexplained. In 1992, Fullerton et al. derived new empirical expressions to describe solution nonideal colligative properties including osmotic pressure (Fullerton et al. 1992. Biochem. Cell Biol. 70:1325-1331). These expressions are based on the concepts of volume occupancy and hydration force. Nonideality is accurately described by a solute/solvent interaction parameter I and an "effective" osmotic molecular weight Ae. This paper uses the interaction-corrected nonideal expressions for osmotic pressure to calculate the hydration I values and "effective" osmotic molecular weight of BSA, Ae, as a function of pH. Both factors vary in a predictable manner due to denaturing of the BSA molecule. Both contribute to an increase in osmotic pressure for the same protein concentration as the solution pH moves away from the isoelectric point. Increased nonideality is caused by larger hydration resulting from larger solvent-accessible surface areas and by the decrease in "effective" osmotic molecular weight, Ae, due to segmental motion of denatured (filamentous) molecules. PMID:8130335

  4. Anditalea andensis ANESC-ST--An Alkaliphilic Halotolerant Bacterium Capable of Electricity Generation under Alkaline-Saline Conditions.

    PubMed

    Shi, Wei; Wang, Victor Bochuan; Zhao, Cui-E; Zhang, Qichun; Loo, Say Chye Joachim; Yang, Liang; Xu, Chenjie

    2015-01-01

    A great challenge in wastewater bioremediation is the sustained activity of viable microorganisms, which can contribute to the breakdown of waste contaminants, especially in alkaline pH conditions. Identification of extremophiles with bioremediation capability can improve the efficiency of wastewater treatment. Here, we report the discovery of an electrochemically active alkaliphilic halotolerant bacterium, Anditalea andensis ANESC-ST (=CICC10485T=NCCB 100412T), which is capable of generating bioelectricity in alkaline-saline conditions. A. andensis ANESC-ST was shown to grow in alkaline conditions between pH 7.0-11.0 and also under high salt condition (up to 4 wt% NaCl). Electrical output was further demonstrated in microbial fuel cells (MFCs) with an average current density of ~0.5 µA/cm2, even under the harsh condition of 4 wt% NaCl and pH 9.0. Subsequent introduction of secreted extracellular metabolites into MFCs inoculated with Escherichia coli or Pseudomonas aeruginosa yielded enhanced electrical output. The ability of A. andensis ANESC-ST to generate energy under alkaline-saline conditions points towards a solution for bioelectricity recovery from alkaline-saline wastewater. This is the first report of A.andensis ANESC-ST producing bioelectricity at high salt concentration and pH.

  5. Alkalinity production in intertidal sands intensified by lugworm bioirrigation

    PubMed Central

    Rao, Alexandra M.F.; Malkin, Sairah Y.; Montserrat, Francesc; Meysman, Filip J.R.

    2014-01-01

    Porewater profiles and sediment-water fluxes of oxygen, nutrients, pH, calcium, alkalinity, and sulfide were measured in intertidal sandflat sediments from the Oosterschelde mesotidal lagoon (The Netherlands). The influence of bioturbation and bioirrigation by the deep-burrowing polychaete Arenicola marina on the rates and sources of benthic alkalinity generation was examined by comparing measurements in intact and defaunated sediment cores before and after the addition of A. marina in summer and fall 2011. Higher organic matter remineralization rates, shallower O2 penetration, and greater sediment-water solute fluxes were observed in summer, consistent with higher sediment community metabolic rates at a higher temperature. Lugworm activity stimulated porewater exchange (5.1 × in summer, 1.9 × in fall), organic matter remineralization (6.2 × in summer, 1.9 × in fall), aerobic respiration (2.4 × in summer, 2.1 × in fall), alkalinity release (4.7 × in summer, 4.0 × in fall), nutrient regeneration, and iron cycling. The effects of lugworm activity on net sediment-water fluxes were similar but more pronounced in summer than in fall. Alkalinity release in fall was entirely driven by metabolic carbonate dissolution, while this process explained between 22 and 69% of total alkalinity production in summer, indicating the importance of other processes in this season. By enhancing organic matter remineralization and the reoxidation of reduced metabolites by the sediment microbial community, lugworm activity stimulated the production of dissolved inorganic carbon and metabolic acidity, which in turn enhanced metabolic CaCO3 dissolution efficiency. In summer, evidence of microbial long distance electron transport (LDET) was observed in defaunated sediment. Thus, alkalinity production by net carbonate dissolution was likely supplemented by anaerobic respiration and LDET in summer. PMID:25431515

  6. Effects of pH and dissolved oxygen on the photodegradation of 17α-ethynylestradiol in dissolved humic acid solution.

    PubMed

    Ren, Dong; Huang, Bin; Bi, Tingting; Xiong, Dan; Pan, Xuejun

    2016-01-01

    To probe the mechanisms responsible for pH and dissolved oxygen (DO) affecting the photodegradation of 17α-ethynylestradiol (EE2) in dissolved humic acid (HA) solution, EE2 aqueous solutions with pH values ranging from 3.0 to 11.0 and different DO conditions were irradiated by using a 300 W mercury lamp equipped with 290 nm light cutoff filters. In 5.0 mg L(-1) HA solutions (pH 8.0), EE2 was degraded at a rate of 0.0739 h(-1) which was about 4-fold faster than that in Milli-Q water. The degradation of EE2 was mainly caused by the oxidation of photogenerated reactive species (RS), and the contribution of direct photodegradation to EE2 degradation was always lower than 27%. Both the direct and indirect photodegradation of EE2 were closely dependent on the EE2 initial concentration, pH value and DO concentration. The photodegradation rate of EE2 decreased with increased initial concentration of EE2 due to the limitation of photon flux. With pH and DO increasing, the degradation rate of EE2 increased significantly due to the increase in the yields of excited EE2 and RS. Among the photogenerated RS, HO˙ and (3)HA* were determined to be the key contributors, and their global contribution to EE2 photodegradation was about 50%. Although HA could generate more (1)O2 than HO˙, the contribution of (1)O2 to EE2 degradation was lower than 13% due to its low reactivity towards EE2. This study could enlarge our knowledge on the photochemical behaviors of steroid estrogens in natural sunlit waters.

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

    PubMed

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

    2013-04-01

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

  8. Linking the solution viscosity of an IgG2 monoclonal antibody to its structure as a function of pH and temperature.

    PubMed

    Cheng, Weiqiang; Joshi, Sangeeta B; Jain, Nishant Kumar; He, Feng; Kerwin, Bruce A; Volkin, David B; Middaugh, C Russell

    2013-12-01

    Although the viscosity of concentrated antibody solutions has been the focus of many recent studies, less attention has been concentrated on how changes in protein structure impact viscosity. This study examines viscosity profiles of an immunoglobulin G (IgG) 2 monoclonal antibody at 150 mg/mL as a function of temperature and pH. Although the structure of the antibody at pH 4.0-7.0 was comparable at lower temperatures as measured by second derivative UV absorbance and Fourier transform infrared spectroscopy, differences in 8-anilino-1-naphthalene sulfonate (ANS) fluorescence intensity indicated small structural alterations as a function of pH. Below the structural transition onset temperature, the viscosity profiles were pH dependent and linearly correlated with fluorescence intensity, and followed semilogarithmic behavior as a function of temperature. The transitions of the viscosity profiles correlated well with the major structure transitions at a protein concentration of 150 mg/mL. The viscosity correlated particularly well with ANS fluorescence intensity at 0.2 mg/mL below and above the structural transition temperatures. These results suggest: (1) ANS can be an important measure of the overall structure and (2) hydrophobic interactions and charge-charge interactions are the two major physical factors that contribute collectively to the high viscosity of concentrated IgG solutions.

  9. pH dependence of melanoma cell migration: protons extruded by NHE1 dominate protons of the bulk solution.

    PubMed

    Stüwe, Laura; Müller, Markus; Fabian, Anke; Waning, Judith; Mally, Sabine; Noël, Josette; Schwab, Albrecht; Stock, Christian

    2007-12-01

    Migration and morphology of human melanoma cells (MV3) depend on extracellular pH (pHe) and the activity of the Na+/H+ exchanger NHE1. To distinguish effects of NHE1 activity per se from effects of pHe we compared an NHE1-deficient mutant with rescued and wild-type cells. Time lapse video microscopy was used to investigate migratory and morphological effects caused by pHe and NHE1 activity, and a membrane-bound fluorescein conjugate was employed for ratiometric pH measurements at the outer leaflet of the cell membrane. As long as NHE1 remained inactive due to deficiency or inhibition by cariporide (HOE642) neither migration nor morphology was affected by changes in pHe. Under these conditions pH at the outer leaflet of the plasma membrane was uniform all over the cell surface. The typical pH dependence of MV3 cell migration and morphology could be reconstituted by restoring NHE1 activity. At the same time the proton gradient at the outer leaflet of the plasma membrane with the higher proton concentration at the leading edge and the lower one at the cell rear was re-established as well. Hence, NHE1 activity generates a proton gradient at the cell surface accompanied by the cells' ability to respond to changes in pHe (bulk pH). We conclude that NHE1 activity contributes to the generation of a well-defined cell surface pH by creating a proton gradient at the outer leaflet of the plasma membrane that is needed for (i) the development of a variety of morphologies including a distinct polarity and (ii) migration. A missing proton gradient at the cell surface cannot be compensated for by varying pHe.

  10. Cadmium and zinc removal from aqueous solutions by Bacillus jeotgali: pH, salinity and temperature effects.

    PubMed

    Green-Ruiz, Carlos; Rodriguez-Tirado, Victor; Gomez-Gil, Bruno

    2008-06-01

    Effects of pH, salinity and temperature on biosorption of Cd and Zn by bacteria Bacillus jeotgali strain U3 were evaluated in batch experiments. Traditional and Subsequent Addition Methods (SAM) were used to carry out the bioassays. Sorption of metals was higher when pH or temperature was increased, or when salinity was reduced. The Langmuir isotherm better fit the biosorption data for Cd, while the Freundlich model fitted better for Zn biosorption. A comparison with similar biosorbents suggested that Bacillus jeotgali strain U3 could be considered a good biosorbent for Cd and Zn recovery.

  11. Influence of the pH value of a colloidal gold solution on the absorption spectra of an LSPR-assisted sensor

    SciTech Connect

    Zhu, Jin; Li, Wenbin; Zhu, Mao; Zhang, Wei; Niu, Wencheng; Liu, Guohua

    2014-03-15

    The localized surface plasmon resonances (LSPRs) of gold particles assembled on a crystal plate are a powerful tool for biological sensors. Here, we prepare gold colloids in different pH solutions. We monitor the effects of the particle radius and particle coverage on the absorption spectra of AT-cut (r-face dihedral angle of about 3°) crystal plates supporting gold nanoparticles. The surface morphologies were monitored on silicon dioxide substrates using ultraviolet and visible (UV-vis) spectroscopy, and atomic force microscopy (AFM). The results showed that the gold particle coverage decreases with increasing pH value of the gold colloid solution. This phenomenon demonstrates that self-assembled gold surfaces were formed via the electrostatic adsorption of gold particles on the positively charged, ionized amino groups on the crystal plates in the acidic solution. The spectrum of gold nanoparticles with different coverage degree on the crystal plates showed that the LSPR properties are highly dependent on pH.

  12. The influence of pH on the degradation kinetics of some organophosphorous pesticides in aqueous solutions.

    PubMed

    Garcia-Repetto, R; Martinez, D; Repetto, M

    1994-06-01

    This paper reports on the stability of 6 organophosphorous insecticides in ethanol-water at pH 2.0, 7.5 and 8.5. The kinetics of insecticide degradation and the corresponding parameters were calculated from the data obtained by analyses of the residual parental compounds. Pesticide degradation was found to proceed by 2 distinct mechanisms.

  13. EFFECTS OF PH, SOLID/SOLUTION RATIO, IONIC STRENGTH, AND ORGANIC ACIDS ON PB AND CD SOPRTION ON KAOLINITE

    EPA Science Inventory

    Potentiometric and ion-selective electrode titrations together with batch sorption/desorption experiments, were performed to explain the aqueous and surface complexation reactions between kaolinite, Pb, Cd and three organic acids. Variables included pH, ionic strength, metal conc...

  14. Permeability Modification Using a Reactive Alkaline-Soluble Biopolymer

    SciTech Connect

    Snadra L. Fox; X. Xie; K. D. Schaller; E. P. Robertson; G. A. Bala

    2003-10-01

    Polymer injection has been used in reservoirs to alleviate contrasting permeability zones. Current technology relies on the use of cross-linking agents to initiate gelation. The use of biological polymers are advantageous in that they can block high permeability areas, are environmentally friendly, and have potential to form reversible gels without the use of hazardous cross-linkers. Recent efforts at the Idaho National Engineering and Environmental Laboratory (INEEL) have produced a reactive alkaline-soluble biopolymer from Agrobacterium sp. ATCC no. 31749 that gels upon decreasing the pH of the polymeric solution. The focus of this study was to determine the impact an alkaline-soluble biopolymer can have on sandstone permeability. Permeability modification was investigated by injecting solubilized biopolymer into Berea sandstone cores and defining the contribution of pH, salt, temperature, and Schuricht crude oil on biopolymer gelation. The biopolymer was soluble in KOH at a pH greater than 11.4 and gelled when the pH dropped below 10.8. The Berea sandstone core buffered the biopolymer solution, decreasing the pH sufficiently to form a gel, which subsequently decreased the permeability. The effluent pH of the control cores injected with 0.01 {und M} KOH (pH 12.0) and 0.10{und M} KOH (pH 13.0) decreased to 10.6 and 12.7, respectively. The permeability of the sandstone core injected with biopolymer was decreased to greater than 95% of the original permeability at 25 C in the presence of 2% NaCl, and Schuricht crude oil; however, the permeability increased when the temperature of the core was increased to 60 C. Residual resistance factors as high as 792 were seen in Berea cores treated with biopolymer. The buffering capacity of sandstone has been demonstrated to reduce the pH of a biopolymer solution sufficiently to cause the polymer to form a stable in-situ gel. This finding could potentially lead to alternate technology for permeability modification, thus

  15. Zinc electrode in alkaline electrolyte

    SciTech Connect

    McBreen, J.

    1995-12-31

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

  16. On the Solution of the Three-Dimensional Flowfield About a Flow-Through Nacelle. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Compton, William Bernard

    1985-01-01

    The solution of the three dimensional flow field for a flow through nacelle was studied. Both inviscid and viscous inviscid interacting solutions were examined. Inviscid solutions were obtained with two different computational procedures for solving the three dimensional Euler equations. The first procedure employs an alternating direction implicit numerical algorithm, and required the development of a complete computational model for the nacelle problem. The second computational technique employs a fourth order Runge-Kutta numerical algorithm which was modified to fit the nacelle problem. Viscous effects on the flow field were evaluated with a viscous inviscid interacting computational model. This model was constructed by coupling the explicit Euler solution procedure with a flag entrainment boundary layer solution procedure in a global iteration scheme. The computational techniques were used to compute the flow field for a long duct turbofan engine nacelle at free stream Mach numbers of 0.80 and 0.94 and angles of attack of 0 and 4 deg.

  17. Electrophoretic separation of alkaline and acid phosphatase isoenzymes from the pulp of monkey teeth.

    PubMed

    Franzén, A; Hasselgren, G

    1978-01-01

    Monkey pulps were homogenized in a Triton tris solution. After three centrifugation steps (800, 20000, and 105000 g) the supernatant was applied on acryl amide columns at pH 7.5 in a tris-diethyl barbituric acid buffer. Electrophoresis was performed at a constant current of 2.5 mA per gel column at 18--20 degrees C. Incubations for alkaline phosphatase (E.C. 3.1.3.1) were carried out at pH 8.3 using naphthol-AS-MX-phosphate as substrate and Fast Red Violet LB salt as coupler. Incubations for acid phosphatase (E.C. 3.1.3.2) were undertaken at pH 5.0 using alpha-naphtyl phosphate as substrate and hexazotized pararosanilin as coupling agent. After the incubations for alkaline phosphatase as well as acid phosphatase two bands showing enzyme activity were demonstrated. By means of treatment with heat (56 degrees C) prior to incubation or addition of vanadate or pyrophosphate to the incubation medium it was shown that the main part of the fast moving alkaline phosphatase band was sensitive to these procedures. The alkaline phosphatase of the slow moving band appeared to be resistant to heat or the addition of inhibitors.

  18. The Effect of Micro/Nano-metrics Size on the Interaction of Jordanian Aluminosilicate Raw Materials with High pH Solution

    NASA Astrophysics Data System (ADS)

    Aldabsheh, Islam; Garcia-Valles, Maite; Martinez, Salvador

    2014-05-01

    Environmental preservation has become a driving force behind the search for new sustainable and environmentally friendly composites to replace conventional concrete produced from ordinary Portland cement (OPC). Current researches concentrate on developing building products (geopolymers) through geopolymerization. The goal is to produce low cost construction materials for green housing. Geopolymerization is the process of polymerizing minerals with high silica and alumina at low temperature by the use of alkali solutions. Dissolution is the most important process for supplying the high initial Al and Si concentrations to produce the gel phase that is responsible for geopolymerization. This study has been focused on the influence of different micrometric particle sizes of three Jordanian raw materials on their dissolution behavior in sodium hydroxide solution. The samples are kaolinite, volcanic tuff and silica sand. The dissolution properties of each material, alone and mixed with the other two materials were studied in different concentrations (5 and 10 M) using (NaOH) at 25ºC, and shaking time for 24 and 168 h. To better understand the dissolution process, the alkaline solution was renewed after the desired time in order to know if the Al-Si raw material is completely dissolved or not. Different analytical techniques were used to characterize raw materials physically, mineralogically, chemically and thermally. All processed samples either centrifuged solutions or solid residues were fully characterized. The leached concentrations of Al and Si were determined by inductively coupled plasma (ICP). X-ray Diffraction Technique (XRD), Scanning Electron Microscopy (SEM), and Thermo Gravimetric Analysis (TGA) were used to evaluate the solid residue characterization compared with the original ones. The three aluminosilicate raw materials have indicated variable degrees of solubility under highly alkaline conditions. The method for the size reduction of the used raw

  19. Peribulbar anesthesia for cataract surgery: Effect of lidocaine warming and alkalinization on injection pain, motor and sensory nerve blockade

    PubMed Central

    Jaichandran, Venkatakrishnan; Vijaya, Lingam; George, Ronnie Jacob; InderMohan, Bhanulakshmi

    2010-01-01

    Aim: To compare self-reported pain and efficacy of warmed, alkalinized, and warmed alkalinized lidocaine with plain 2% lidocaine at room temperature for peribulbar anesthesia in cataract surgery. Materials and Methods: Through a prospective, single-blinded, randomized, controlled clinical trial 200 patients were divided into four groups. They received either lidocaine at operating room temperature 18°C, control group (Group C), lidocaine warmed to 37°C (Group W), lidocaine alkalinized to a pH of 7.09 ± 0.10 (Group B) or lidocaine at 37°C alkalinized to a pH of 6.94 ± 0.05 (Group WB). All solutions contained Inj. Hyaluronidase 50 IU/ml. Pain was assessed using a 10-cm visual analog score scale. Time of onset of sensory and motor blockade and time to onset of postoperative pain were recorded by a blinded observer. Results: Mean pain score was significantly lower in Group B and WB compared with Group C (P < 0.001). Onset of analgesia was delayed in Group C compared with Group B (P = 0.021) and WB (P < 0.001). Mean time taken for the onset of complete akinesia and supplementation required for the block was significantly lower in Group B. Time of onset of pain after operation was significantly earlier in Group W compared with Group C (P = 0.036). Conclusion: Alkalinized lidocaine with or without warming produced less pain than lidocaine injected at room temperature. Alkalinization enhances the effect of warming for sensory nerve blockade, but warming does not enhance alkalinization, in fact it reduces the efficacy of alkalinized solution for blocking the motor nerves in the eye. PMID:20195031

  20. Dry matter and nitrogen accumulation are not affected by superoptimal concentration of ammonium in flowing solution culture with pH control

    NASA Technical Reports Server (NTRS)

    Rideout, J. W.; Raper, C. D. Jr; Raper CD, J. r. (Principal Investigator)

    1994-01-01

    While it is known that superoptimal concentrations of the nitrate (NO3-) ion in solution culture do not increase NO3- uptake or dry matter accumulation, the same is not known for the ammonium (NH4+) ion. An experiment was conducted utilizing flowing solution culture with pH control to investigate the influence of superoptimal NH4+ concentrations on dry matter, nitrogen (N), potassium (K), calcium (Ca), and magnesium (Mg) accumulation by nonnodulated soybean plants. Increasing the NH4+ concentration in solution from 1 to 10 mM did not affect dry matter or N accumulation. Accumulations of K, Ca, and Mg were slightly decreased with increased NH4+ concentration. The NH4+ uptake system, which is saturated at less than 1mM NH4+, is able to regulate uptake of NH4+ at concentrations as high as 10 mM.

  1. The use of alkaline hydrolysis as a novel strategy for chloroform remediation: the feasibility of using construction wastes and evaluation of carbon isotopic fractionation.

    PubMed

    Torrentó, Clara; Audí-Miró, Carme; Bordeleau, Geneviève; Marchesi, Massimo; Rosell, Mònica; Otero, Neus; Soler, Albert

    2014-01-01

    Laboratory and field-scale pilot experiments were performed to evaluate the feasibility of chloroform degradation by alkaline hydrolysis and the potential of δ(13)C values to assess this induced reaction process at contaminated sites. In batch experiments, alkaline conditions were induced by adding crushed concrete (pH 12.33 ± 0.07), a filtered concrete solution (pH 12.27 ± 0.04), a filtered cement solution (pH 12.66 ± 0.02) and a pH 12 buffer solution (pH 11.92 ± 0.11). The resulting chloroform degradation after 28 days was 94, 96, 99, and 72%, respectively. The experimental data were described using a pseudo-first-order kinetic model, resulting in pseudo-first-order rate constant values of 0.10, 0.12, 0.20, and 0.05 d(-1), respectively. Furthermore, the significant chloroform carbon isotopic fractionation associated with alkaline hydrolysis of chloroform (-53 ± 3‰) and its independence from pH in the admittedly limited tested pH range imply a great potential for the use of δ(13)C values for in situ monitoring of the efficacy of remediation approaches based on alkaline hydrolysis. The carbon isotopic fractionation obtained at the lab scale allowed the calculation of the percentage of chloroform degradation in field-scale pilot experiments where alkaline conditions were induced in two recharge water interception trenches filled with concrete-based construction wastes. A maximum of approximately 30-40% of chloroform degradation was achieved during the two studied recharge periods. Although further research is required, the treatment of chloroform in groundwater through the use of concrete-based construction wastes is proposed. This strategy would also imply the recycling of construction and demolition wastes for use in value-added applications to increase economic and environmental benefits.

  2. A newly high alkaline lipase: an ideal choice for application in detergent formulations

    PubMed Central

    2011-01-01

    Background Bacterial lipases received much attention for their substrate specificity and their ability to function in extreme environments (pH, temperature...). Many staphylococci produced lipases which were released into the culture medium. Reports of thermostable lipases from Staphylococcus sp. and active in alkaline conditions are not previously described. Results A newly soil-isolated Staphylococcus sp. strain ESW secretes an induced lipase in the culture medium. The effects of temperature, pH and various components in a detergent on the activity and stability of Staphylococcus sp. lipase (SL1) were studied in a preliminary evaluation for use in detergent formulation solutions. The enzyme was highly active over a wide range of pH from 9.0 to 13.0, with an optimum at pH 12.0. The relative activity at pH 13.0 was about 60% of that obtained at pH 12.0. It exhibited maximal activity at 60°C. This novel lipase, showed extreme stability towards non-ionic and anionic surfactants after pre-incubation for 1 h at 40°C, and relative stability towards oxidizing agents. Additionally, the crude enzyme showed excellent stability and compatibility with various commercial solid and liquid detergents. Conclusions These properties added to the high activity in high alkaline pH make this novel lipase an ideal choice for application in detergent formulations. PMID:22123072

  3. An Implicit Finite Difference Solution to the Viscous Radiating Shock Layer with Strong Blowing. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Garrett, L. B.

    1971-01-01

    An implicit finite difference scheme is developed for the fully coupled solution of the viscous radiating stagnation line equations, including strong blowing. Solutions are presented for both air injection and carbon phenolic ablation products injection into air at conditions near the peak radiative heating point in an earth entry trajectory from interplanetary return missions. A detailed radiative transport code that accounts for the important radiative exchange processes for gaseous mixtures in local thermodynamic and chemical equilibrium is utilized.

  4. Passive behaviour of alloy corrosion-resistant steel Cr10Mo1 in simulating concrete pore solutions with different pH

    NASA Astrophysics Data System (ADS)

    Ai, Zhiyong; Jiang, Jinyang; Sun, Wei; Song, Dan; Ma, Han; Zhang, Jianchun; Wang, Danqian

    2016-12-01

    The passive behaviour of new alloy corrosion-resistant steel Cr10Mo1 and plain carbon steel (as a comparison) in simulating concrete pore solutions of different pH (ranging from 13.5 to 9.0) under open circuit potential conditions, was evaluated by various electrochemical techniques: potentiodynamic polarization, capacitance measurements and electrochemical impedance spectroscopy. The chemical composition and structure of passive films were investigated by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). The electrochemical responses of passive films show that Cr10Mo1 steel has an increasing passivity with pH decreasing while carbon steel dose conversely, revealing carbonation does no negative effect on passivation of the corrosion-resistant steel. SIMS reveals that the passive film on the corrosion-resistant steel presents a bilayer structure: an outer layer mainly consisting of Fe oxides and hydroxides, and an inner layer enriched in Cr species, while only a Fe-concentrated layer for carbon steel. According to the XPS analysis results, as the pH decreases, more stable and protective Cr oxides are enriched in the film on Cr10Mo1 steel while Fe oxides gradually decompose. Higher content of Cr oxides in the film layer provides Cr10Mo1 corrosion-resistant steel more excellent passivity at lower pH.

  5. Basalt as a solid source of calcium and alkalinity for the sequestration of carbon dioxide in building materials

    NASA Astrophysics Data System (ADS)

    Johnson, N. C.; Westfield, I.; Lu, P.; Bourcier, W. L.; Kendall, T.; Constantz, B. R.

    2010-12-01

    Motivated by the idea of converting waste carbon dioxide into usable building products, Calera Corporation has developed a multi-step process that sequesters CO2 as carbonate minerals in cementitious materials. Process inputs include dissolved divalent cations and alkalinity, both of which can be extracted from basalt. In one mode of the Calera process, the electrochemical production of alkalinity generates large volumes of hydrochloric acid as a by-product, which has been shown to effectively leach divalent cations from basalt while being neutralized by the basalt dissolution reaction. Using a 10:1 1M HCl solution to rock ratio, 3500 ppm Ca was extracted while the initial solution was neutralized to a pH of 2.60 in two weeks at a temperature of 80oC in an anoxic batch reactor. In this scenario, mineral carbonation occurs via three steps: electrochemical production of alkalinity, CO2 absorption by the alkaline stream, then precipitation by mixing the basalt-derived divalent cation stream and the CO2-containing alkaline stream. In a second scenario, alkalinity is extracted from basalt using an alkalinity capacitor, a weak acid. This solution may contain a proton source, such as ammonium chloride, or a hydroxyl acceptor, such as boric acid, but the main design constraint is that the pKa of the capacitor be high enough to deprontonate carbonic acid. The weak acid solution is mixed with basalt in an anoxic batch reactor and the dissolving rock consumes protons from the weak acid, generating the conjugate base. The solution rich in conjugate base then absorbs CO2 and the carbonate-rich solution is mixed with a calcium-rich stream to precipitate carbonate minerals. We have extracted up to 1100 mmol alkalinity per kg rock using an alkalinity capacitor, versus no more than 50 mmol alkalinity per kg rock using DI water as a solvent. Again, carbon sequestration occurs via three steps: alkalinity extraction from basalt, CO2 absorption, and finally carbonate precipitation

  6. A theoretical kinetic model of the temperature and pH dependent dimerization of orthosilicic acid in aqueous solution.

    PubMed

    McIntosh, Grant J

    2012-01-14

    The first steps in a pH- and temperature-dependent theoretical kinetic model of silicate polymerization and dissolution are examined in this work with a combined ab initio and transition state theory based study of the dimerization of H(4)SiO(4). The role of solvation has been of primary concern in this work, and its influence on theoretical activation energies and pre-exponential factors has been thoroughly benchmarked. Relatively inexpensive MP2/6-31+G(d)//HF/6-31+G(d) calculations of octahydrate clusters, with conductor-like polarizable continuum model corrections obtained in the MP2-level single-point calculations, have been shown to lead to a good description of the limited experimentally determined energetics of dimerization for most elementary reactions. Pre-exponential factors computed from this level of theory are found to be relatively insensitive to the level of theory utilized for geometry optimizations, the number of explicit waters, hindered rotor corrections, and variational effects arising from the minimization of rate constants. Within this framework, a kinetic model of the chemistry of H(4)SiO(4) and H(3)SiO(4)(-), forming H(6)Si(2)O(7) and H(5)Si(2)O(7)(-), has been compiled. Numerical simulations over pH = 3-12 show that a number of pH- and temperature dependent trends in reaction rates and positions of equilibrium are well described with this simple dimerization model. More specifically to the dimerization process, we obtain dimerization constants, log K(dim), of 1.85 and -7.15 for the formation of H(6)Si(2)O(7) and H(5)Si(2)O(7)(-) respectively, which compare well with experimentally determined values of 1.2 and -8.5, respectively.

  7. Numerical simulation study of silica and calcite dissolution around a geothermal well by injecting high pH solutions with chelating agent.

    SciTech Connect

    Xu, Tianfu; Rose, Peter; Fayer, Scott; Pruess, Karsten

    2009-02-01

    Dissolution of silica, silicate, and calcite minerals in the presence of a chelating agent (NTA) at a high pH has been successfully performed in the laboratory using a high-temperature flow reactor. The mineral dissolution and porosity enhancement in the laboratory experiment has been reproduced by reactive transport simulation using TOUGHREACT. The chemical stimulation method has been applied by numerical modeling to a field geothermal injection well system, to investigate its effectiveness. Parameters from the quartz monzodiorite unit at the Enhanced Geothermal System (EGS) site at Desert Peak (Nevada) were used. Results indicate that the injection of a high pH chelating solution results in dissolution of both calcite and plagioclase minerals, and avoids precipitation of calcite at high temperature conditions. Consequently reservoir porosity and permeability can be enhanced especially near the injection well.

  8. An improved method for analysis of hydroxide and carbonate in alkaline electrolytes containing zinc

    NASA Technical Reports Server (NTRS)

    Reid, M. A.

    1978-01-01

    A simplified method for titration of carbonate and hydroxide in alkaline battery electrolyte is presented involving a saturated KSCN solution as a complexing agent for zinc. Both hydroxide and carbonate can be determined in one titration, and the complexing reagent is readily prepared. Since the pH at the end point is shifted from 8.3 to 7.9 - 8.0, m-cresol purple or phenol red are used as indicators rather than phenolphthalein. Bromcresol green is recommended for determination of the second end point of a pH of 4.3 to 4.4.

  9. An improved method for analysis of hydroxide and carbonate in alkaline electrolytes containing zinc

    NASA Technical Reports Server (NTRS)

    Reid, M. A.

    1978-01-01

    A simplified method for titration of carbonate and hydroxide in alkaline battery electrolyte is presented involving a saturated KSCN solution as a complexing agent for zinc. Both hydroxide and carbonate can be determined in one titration, and the complexing reagent is readily prepared. Since the pH at the end point is shifted from 8.3 to 7.9-8.0, m-cresol purple or phenol red are used as indicators rather than phenolphthalein. Bromcresol green is recommended for determination of the second end point of a pH of 4.3 to 4.4.

  10. Effect of dosing sequence and solution pH on floc properties of the compound bioflocculant-aluminum sulfate dual-coagulant in kaolin-humic acid solution treatment.

    PubMed

    Bo, Xiaowen; Gao, Baoyu; Peng, Nana; Wang, Yan; Yue, Qinyan; Zhao, Yingcan

    2012-06-01

    The compound bioflocculant (CBF)-aluminum sulfate (AS) dual-coagulant and AS were comparatively studied for the coagulation of kaolin-humic acid solution. Floc properties including floc growth rate, size, strength, recoverability and fractal dimension under different pH conditions were investigated by Mastersizer 2000. Results indicated that, the flocs formed by AS-CBF (AS dosed first) showed the largest size and the best recoverability across the pH range investigated. While flocs formed by CBF-AS gave the most compact structure. The three coagulants exhibited similar floc growth rate and strength. Moreover, flocs formed in acidic conditions were stronger and more recoverable but showed lower growth rate, smaller size and looser structure compared to those formed at pH>6 regardless of the coagulant used. Charge neutralization was the dominant mechanism for AS at low pH, while the coagulation mechanism transformed to enmeshment as the pH increased. There was an additional adsorption bridging effect for AS-CBF and CBF-AS.

  11. Effect of pH on anodic formation of nanoporous gold films in chloride solutions: optimization of anodization for ultrahigh porous structures.

    PubMed

    Kim, Minju; Kim, Jongwon

    2014-04-29

    Nanoporous gold (NPG) structures have useful applications based on their unique physical and chemical properties; therefore, the development of NPG preparation methods is the subject of extensive research. Recently, the anodization of Au surfaces was suggested as an efficient method for preparing porous Au structures. In this work, the mechanistic aspects of the anodization of Au in Cl(-)-containing solutions for the preparation of NPG layers were investigated. The effects of the experimental parameters of the anodization reaction on the porosity of the NPG layers in terms of the roughness factor (Rf) were examined. The anodic formation of NPG was more effective in buffered solutions than in unbuffered electrolytes. The Rf of the NPG layer was sensitive to the electrolyte pH; this was ascribed to the efficient formation of protecting layers of gold oxide on the newly formed NPG structures. In buffer solutions at pH 8, ultrahigh porous NPG layers with Rf values of 1300 were obtained within 15 min. The ultrahigh porous NPG layers were used for the electrochemical detection of glucose; a high sensitivity of 135 μA mM(-1) cm(-2) was achieved in the presence of 0.1 M Cl(-). This straightforward and time-saving preparation of NPG surfaces will provide new opportunities for applications of NPG structures.

  12. Interfacial activity in alkaline flooding enhanced oil recovery

    SciTech Connect

    Chan, M.K.

    1981-01-01

    The ionization of long-chained organic acids in the crude oil to form soaps was shown to be primarily responsible for the lowering of oil-water interfacial tension at alkaline pH. These active acids can be concentrated by silica gel chromatography into a minor polar fraction. An equilibrium chemical model was proposed based on 2 competing reactions: the ionization of acids to form active anions, and the formation of undissociated soap between acid anions and sodium ions. It correlates the interfacial activity with the interfacial concentration of active acid anions which is expressed in terms of the concentrations of the chemical species in the system. The model successfully predicts the observed oil-alkaline solution interfacial phenomenon, including its dependence on pH, alkali and salt concentrations, type of acid present and type of soap formed. Flooding at different alkali concentrations to activate different acid species present in the crude was shown to give better recovery than flooding at a single high alkali concentration. Treating the crude oil with a dilute solution of mineral acids liberates additional free active acids and yields better interfacial activity during subsequent alkali contact.

  13. High-Sensitivity Surface-Enhanced Raman Scattering (SERS) Substrate Based on a Gold Colloid Solution with a pH Change for Detection of Trace-Level Polycyclic Aromatic Hydrocarbons in Aqueous Solution.

    PubMed

    Shi, Xiaofeng; Liu, Shu; Han, Xiaohong; Ma, Jun; Jiang, Yongchao; Yu, Guifeng

    2015-05-01

    In this study, a gold colloid solution whose parameters were optimized, and without any surfactants, was developed as a surface-enhanced Raman scattering (SERS) substrate for the detection of trace-level polycyclic aromatic hydrocarbons (PAHs). A gold colloid solution with 57 nm gold particles and pH 13 was prepared to be the SERS substrate. It had impressive enhancement that was two orders of magnitude higher than that of a gold colloid solution with 57 nm gold particles and without pH change (pH 6). Even with a compact field-based Raman spectrometer, naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene were detected, with limits of detection at 6.8 nM, 3.4 nM, 1.8 nM, 0.68 nM (680 pM), and 0.44 nM (440 pM), respectively. The significant enhancement was ascribed to an electromagnetic mechanism and a charge-transfer mechanism. Quantitative analyses for these five PAHs in water were also performed. The SERS intensities of PAHs were found to have good linear dependence relations with the concentrations in low concentration. This high-sensitivity, easily prepared substrate offers a promising technology for the quantitative detection of trace-level PAHs.

  14. Aggregation Kinetics and Self-Assembly Mechanisms of Graphene Quantum Dots in Aqueous Solutions: Cooperative Effects of pH and Electrolytes.

    PubMed

    Li, Qingqing; Chen, Baoliang; Xing, Baoshan

    2017-02-07

    The cooperative effects of pH and electrolytes on the aggregation of GQDs and the aggregate morphologies are characterized. Because GQDs have an average size of 9 nm with abundant O-functionalized edges, their suspension was very stable even in a high electrolyte concentration and low pH solution. Divalent cations (Mg(2+) and Ca(2+)) excelled at aggregating the GQD nanoplates, while monovalent cations (Na(+) and K(+)) did not disturb the stability. For Na(+) and K(+), positive linear correlations were observed between the critical coagulation concentration (CCC) and pH levels. For Mg(2+) and Ca(2+), negative, but nonlinear, correlations between CCC and pH values could not be explained and predicted by the traditional DLVO theory. Three-step mechanisms are proposed for the first time to elucidate the complex aggregation of GQDs. The first step is the protonation/deprotonation of GQDs under different pH values and the self-assembly of GQDs into GQD-water-GQD. The second step is the self-assembly of small GQD pieces into large plates (graphene oxide-like) induced by the coexisting Ca(2+) and then conversion into 3D structures via π-π stacking. The third step is the aggregation of the 3D-assembled GQDs into precipitates via the suppression of the electric double layer. The self-assembly of GQDs prior to aggregation was supported by SEM and HRTEM imaging. Understanding of the colloidal behavior of ultrasmall nanoparticles like GQDs is significantly important for the precise prediction of their environmental fate and risk.

  15. Étude du comportement associatif du copolymère tribloc poly(1,4-phénylène)-b-polystyrène-b-poly(1,4-phénylène) en solution

    NASA Astrophysics Data System (ADS)

    Mignard, E.; Tachon, C.; François, B.

    1998-06-01

    Poly(1,4-phenylene)-b-polystyrene-b-poly(1,4-phenylene) (PPP-b- PS-b-PPP) block copolymers were synthesized by chemical modification of a precursor copolymer. After characterization by Size Exclusion Chromatography (S.E.C) and U.V. spectroscopy, PPP-b-PS-b-PPP copolymers were studied in THF solution at room temperature by viscosimetry and light-scattering analysis. We have shown the associative behavior of these triblock copolymers by their ability to form, with this molecular weight distribution, aggregates with a possible “flower-like" morphology constituted of a PPP “core" surrounded by PS “petals". Des copolymères à blocs poly(1,4-phénylène)-b-polystyrène-b-poly (1,4-phénylène) (PPP-b-PS-b-PPP) ont été synthétisés par modification chimique d'un copolymère précurseur. Après caractérisation par Chromatographie d'Exclusion Stérique (C.E.S.) et par spectroscopie U.V., les copolymères PPP-b-PS-b-PPP ont été étudiés en solution dans le THF à température ambiante par viscosimétrie et diffusion de la lumière. Nous avons observé le comportement associatif de ces copolymères triblocs par leur aptitude à former, pour la distribution de masses molaires étudiée, des agrégats ayant vraisemblablement une morphologie semblable à celle d'une “fleur" possédant un “cour" de PPP et des “pétales" de PS.

  16. Performed surfactant-optimized aqueous alkaline flood

    SciTech Connect

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

    1991-11-26

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

  17. Numerical solution of the Navier-Stokes equations for super-sonic flows with strong shocks. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Devarayalu, K.

    1978-01-01

    The numerical solution of the full Navier-Stokes Equations for viscous flows with high Mach numbers and a strong detached bow shock was obtained. Two dimensional flows around a circular cylinder, and a circular cylinder with an aft-body in the form of a fairing, were considered. The solution of the compressible N.S. equations was accomplished by the method of finite differences. An implicit scheme of solution, the S.O.R., was used with the optimum acceleration parameters determined by trial and error. The tensor notation was used in writing the N-S Equations transformed into general curvilinear coordinates. The equations for the generation of the coordinate system were solved, followed by the solution of the N.S. equations, at the end of a set of given number of time steps. "Wiggles", constituted the one major problem that needed to be overcome. These oscillations give rise to quantities such as negative temperatures, which ultimately caused the computational program to break down. Certain dissipative finite-difference schemes damped these oscillations.

  18. An inorganic CO2 diffusion and dissolution process explains negative CO2 fluxes in saline/alkaline soils.

    PubMed

    Ma, Jie; Wang, Zhong-Yuan; Stevenson, Bryan A; Zheng, Xin-Jun; Li, Yan

    2013-01-01

    An 'anomalous' negative flux, in which carbon dioxide (CO2) enters rather than is released from the ground, was studied in a saline/alkaline soil. Soil sterilization disclosed an inorganic process of CO2 dissolution into (during the night) and out of (during the day) the soil solution, driven by variation in soil temperature. Experimental and modeling analysis revealed that pH and soil moisture were the most important determinants of the magnitude of this inorganic CO2 flux. In the extreme cases of air-dried saline/alkaline soils, this inorganic process was predominant. While the diurnal flux measured was zero sum, leaching of the dissolved inorganic carbon in the soil solution could potentially effect net carbon ecosystem exchange. This finding implies that an inorganic module should be incorporated when dealing with the CO2 flux of saline/alkaline land. Neglecting this inorganic flux may induce erroneous or misleading conclusions in interpreting CO2 fluxes of these ecosystems.

  19. Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid

    DOE PAGES

    Stevens, Joanna S.; Gainar, Adrian; Suljoti, Edlira; ...

    2015-03-18

    Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO–LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs andmore » σ* shape resonances in the NEXAFS spectra. Finally, this provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute–solvent interactions.« less

  20. A fluorescent sensing of nerve agent simulant with dual emissions at wide pH range in aqueous solution.

    PubMed

    Kim, Youngsam; Jang, Yoon Jeong; Mulay, Sandip V; Nguyen, Thuy-Tien T; Churchill, David G

    2017-03-23

    A new 1,8-naphthalimide-based fluorescent probe for the detection of diethyl cyanophosphonate, a very common nerve agent simulant, was designed, synthesized and characterized fully. The probe showed around 50-fold enhancement of fluorescence intensity over other nerve agent simulants. Importantly, the probe is able to work under aqueous conditions at wide pH range. Two reactive groups, the oxime and phenol, allowed a dual emission with different kinetic reaction. The reaction of diethyl cyanophosphonate with the oxime group occurred in advance; the resulting time-response of fluorescence enhancement was observed within ~30 s. After the oxime underwent reaction, then phenol also underwent substitution reaction with diethyl cyanophosphate resulting blue emission. To show real application of this new probe, silica plate assays for the detection of diethyl cyanophosphonate in gas and liquid phase through dual emissions channel were carried out.

  1. α-Cyclodextrin/aminobenzoic acid binding in salt solutions at different pH: dependence on guest structure.

    PubMed

    Romanova, Anastasia; Chibunova, Ekaterina; Kumeev, Roman; Fedorov, Maxim; Terekhova, Irina

    2013-06-01

    Influence of Na(+) and K(+) cations on α-cyclodextrin guest-host complex formation with isomeric aminobenzoic acids was examined at different pH and temperature of 298.15 K by (1)H NMR and calorimetry methods. More pronounced influence of Na(+) on inclusion complex formation of α-CD with aminobenzoic acid anions compare to the effects of Na(+) on α-CD complex formation with zwitterionic aminobenzoic acid molecules was revealed. For the first time, the dependence of salt effects on the structure, ionization and the hydration state of the guest molecule was demonstrated and analysed on the basis of the obtained thermodynamic parameters of complex formation and calculated free energy of hydration of different ionized forms of aminobenzoic acids.

  2. Automatic online buffer capacity (alkalinity) measurement of wastewater using an electrochemical cell.

    PubMed

    Cheng, Liang; Charles, Wipa; Cord-Ruwisch, Ralf

    2016-10-01

    The use of an automatic online electrochemical cell (EC) for measuring the buffer capacity of wastewater is presented. pH titration curves of different solutions (NaHCO3, Na2HPO4, real municipal wastewater, and anaerobic digester liquid) were obtained by conventional chemical titration and compared to the online EC measurements. The results show that the pH titration curves from the EC were comparable to that of the conventional chemical titration. The results show a linear relationship between the response of the online EC detection system and the titrimetric partial alkalinity and total alkalinity of all tested samples. This suggests that an EC can be used as a simple online titration device for monitoring the buffer capacity of different industrial processes including wastewater treatment and anaerobic digestion processes.

  3. Reflecting Solutions of High Order Elliptic Differential Equations in Two Independent Variables Across Analytic Arcs. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Carleton, O.

    1972-01-01

    Consideration is given specifically to sixth order elliptic partial differential equations in two independent real variables x, y such that the coefficients of the highest order terms are real constants. It is assumed that the differential operator has distinct characteristics and that it can be factored as a product of second order operators. By analytically continuing into the complex domain and using the complex characteristic coordinates of the differential equation, it is shown that its solutions, u, may be reflected across analytic arcs on which u satisfies certain analytic boundary conditions. Moreover, a method is given whereby one can determine a region into which the solution is extensible. It is seen that this region of reflection is dependent on the original domain of difinition of the solution, the arc and the coefficients of the highest order terms of the equation and not on any sufficiently small quantities; i.e., the reflection is global in nature. The method employed may be applied to similar differential equations of order 2n.

  4. Effect of pH and uranium concentration on interaction of uranium(VI) and uranium(IV) with organic ligands in aqueous solutions

    SciTech Connect

    Li, W.C.; Victor, D.M.; Chakrabarti, C.L.

    1980-03-01

    The effect of pH and uranium concentration on the interactions of uranium(VI) and uranium(IV) with organic ligands was studied by employing dialysis and ultrafiltration techniques. The interactions of U(VI) and U(IV) with organic ligands in nitrate or chloride aqueous solution have been found to be pH-dependent. The stability constants of uranium-organic complexes decrease in the order: fulvic acid>humic acid>tannic acid for U(VI) and humic acid>tannic acid>fulvic acid for U(IV). Scatchard plots for the uranium-organic acid systems indicate two types of binding sites with a difference in stability constants of about 10/sup 2/. Ultrafiltration of uranium-humic acid complexes indicates that U(VI) and U(IV) ions are concentrated in larger molecular size fractions (>5.1 nm) at pH less than or equal to 3 and in smaller molecular size fractions (in the range 5.1 to 3.1 nm and 2.4 to 1.9 nm) at pH greater than or equal to 5. 7 figures, 4 tables.

  5. Specific detection of cysteine and homocysteine in biological fluids by tuning the pH values of fluorosurfactant-stabilized gold colloidal solution.

    PubMed

    Xiao, Qunyan; Shang, Fei; Xu, Xuechen; Li, Qianqian; Lu, Chao; Lin, Jin-Ming

    2011-12-15

    This study describes the use of 14 nm nonionic fluorosurfactant-capped gold nanoparticles (FSN-capped AuNPs) for the simultaneous detection of cysteine (Cys) and homocysteine (Hcy) using colorimetric method, requiring no use of separation techniques. It was found that the kinetics of Cys/Hcy-induced aggregation of the 14 nm FSN-capped AuNPs strongly depends on the pH value of gold colloidal solution. At a pH of 6.5, the Cys-induced aggregation kinetics of the FSN-capped AuNPs was almost identical to that induced by Hcy, facilitating simultaneous detection of total Cys and Hcy up to a concentration as low as 0.15 μM; while at pH 12.0, the kinetics of Cys-induced aggregation was much faster than that inducted by Hcy, leading to selective detection of Cys at concentration as low as 1.0 μM in the presence of Hcy. The applicability of the method was validated by spiking known amount of Cys and Hcy in human urine and plasma samples, obtaining a recovery of 95.4-105.5%. The present approach is simple, high selective and provides high reproducibility, and has a great potentiality in disease diagnosis.

  6. Cloning and Overexpression of Alkaline Phosphatase PhoK from Sphingomonas sp. Strain BSAR-1 for Bioprecipitation of Uranium from Alkaline Solutions▿

    PubMed Central

    Nilgiriwala, Kayzad S.; Alahari, Anuradha; Rao, Amara Sambasiva; Apte, Shree Kumar

    2008-01-01

    Cells of Sphingomonas sp. strain BSAR-1 constitutively expressed an alkaline phosphatase, which was also secreted in the extracellular medium. A null mutant lacking this alkaline phosphatase activity was isolated by Tn5 random mutagenesis. The corresponding gene, designated phoK, was cloned and overexpressed in Escherichia coli strain BL21(DE3). The resultant E. coli strain EK4 overexpressed cellular activity 55 times higher and secreted extracellular PhoK activity 13 times higher than did BSAR-1. The recombinant strain very rapidly precipitated >90% of input uranium in less than 2 h from alkaline solutions (pH, 9 ± 0.2) containing 0.5 to 5 mM of uranyl carbonate, compared to BSAR-1, which precipitated uranium in >7 h. In both strains BSAR-1 and EK4, precipitated uranium remained cell bound. The EK4 cells exhibited a much higher loading capacity of 3.8 g U/g dry weight in <2 h compared to only 1.5 g U/g dry weight in >7 h in BSAR-1. The data demonstrate the potential utility of genetically engineering PhoK for the bioprecipitation of uranium from alkaline solutions. PMID:18641147

  7. [In vitro effects of the alkalinization of 0.25% bupivacaine and 2% lidocaine].

    PubMed

    Berrada, R; Chassard, D; Bryssine, S; Berthier, S; Bryssine, B; Boulétreau, P

    1994-01-01

    Recent clinical studies have suggested that alkalinization of local anaesthetic agents may shorten the onset time and lengthen their duration of action. In clinical practice, sodium bicarbonate 1.4 and 4.2% are often added to local anaesthetic agents to obtain these effects. We evaluated pH changes of 4 local anaesthetic solutions commonly used for obstetrical epidural anaesthesia, in order to develop titration curves with sodium bicarbonate 1.4 and 4.2%. Local anaesthetic agents tested included lidocaine 2% and bupivacaine 0.25% with and without epinephrine. Each one was divided in 10 mL aliquots, and supplemented with 25 micrograms of sufentanil (1 mL). The pH measurement were made with a pH-meter P 500 with a combined electrode (TBC 12/HS) in the standard solution and after incremental addition of 0.5 mL of 1.4 or 4.2% sodium bicarbonate. The percentage of the free form of local anaesthetic was calculated for each step, using the Henderson-Hasselbalch equation. Results showed that alkalinization is not beneficial with epinephrine free solutions. Increasing volumes of sodium bicarbonate, buffered the acidic effect of sodium bisulfite present in solutions containing epinephrine, and increased the percentage of the free form of local anaesthetic to the level of epinephrine free solutions. From this pH point upwards, the gain is poor and precipitates are generated. This study suggests that 1 mL of 4.2% sodium bicarbonate for 10 mL of local anaesthetic solution is the best theorical choice for alkalinization of a local anaesthetic associated with epinephrine.

  8. 4-(8-Quinolyl)amino-7-nitro-2,1,3-benzoxadiazole as a new selective and sensitive fluorescent and colorimetric pH probe with dual-responsive ranges in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Li, Xutian; Zhang, Min; Liang, Haipeng; Huang, Zhaowei; Tang, Jiang; Chen, Zhi; Yang, Liting; Ma, Li-Jun; Wang, Yuhai; Xu, Baiping

    2016-01-01

    Fluorescent and colorimetric pH probe possess many advantages including rapid response time, nondestructive testing, and excellent pH sensitivity. However, they usually cannot be utilized simultaneously in both acidic and basic pH ranges. In this study, a new selective and sensitive fluorescent and colorimetric pH probe, 4-(8- quinolyl)amino-7-nitro-2,1,3-benzoxadiazole (1), was designated and synthesized. The optical probe exhibited dual-responsive pH ranges to both acidic and basic aqueous solutions. When the solution pH was gradually increased from 8.5 to 13.3, the absorption spectra of 1 showed an obvious hyperchromicity, accompanied with a red shift of the absorption band at 340 nm, a blue shift of the absorption band at 482 nm, and a distinct color change from orange to violet pink to yellow. Within the pH range from 2.2 to 0.2, the fluorescent spectra of 1 showed a "turn-on" response signal to solution pH. In order to understand the response mechanism of the probe to solution pH, the probe molecule was split into two parts, 8-aminoquinoline (2) and 4-amino-7- nitro-benzofurazan (3). UV-vis absorption and fluorescent experiments of 2 and 3 indicated that both are sensitive optical pH probes. Furthermore, the NMR experiment of 1 was explored in basic and acidic conditions. The results indicated that the colorimetric responses of 1 to pH under basic condition should be attributed to the deprotonation of the imino group on the quinolyl ring, and the fluorescent recognition of 1 to pH under acidic condition was probably due to the protonation of the nitrogen atoms from the benzofurazan and quinolyl rings.

  9. Numerical solution of the incompressible Navier-Stokes equations. Ph.D. Thesis - Stanford Univ., Mar. 1989

    NASA Technical Reports Server (NTRS)

    Rogers, Stuart E.

    1990-01-01

    The current work is initiated in an effort to obtain an efficient, accurate, and robust algorithm for the numerical solution of the incompressible Navier-Stokes equations in two- and three-dimensional generalized curvilinear coordinates for both steady-state and time-dependent flow problems. This is accomplished with the use of the method of artificial compressibility and a high-order flux-difference splitting technique for the differencing of the convective terms. Time accuracy is obtained in the numerical solutions by subiterating the equations in psuedo-time for each physical time step. The system of equations is solved with a line-relaxation scheme which allows the use of very large pseudo-time steps leading to fast convergence for steady-state problems as well as for the subiterations of time-dependent problems. Numerous laminar test flow problems are computed and presented with a comparison against analytically known solutions or experimental results. These include the flow in a driven cavity, the flow over a backward-facing step, the steady and unsteady flow over a circular cylinder, flow over an oscillating plate, flow through a one-dimensional inviscid channel with oscillating back pressure, the steady-state flow through a square duct with a 90 degree bend, and the flow through an artificial heart configuration with moving boundaries. An adequate comparison with the analytical or experimental results is obtained in all cases. Numerical comparisons of the upwind differencing with central differencing plus artificial dissipation indicates that the upwind differencing provides a much more robust algorithm, which requires significantly less computing time. The time-dependent problems require on the order of 10 to 20 subiterations, indicating that the elliptical nature of the problem does require a substantial amount of computing effort.

  10. Electrochemical characteristics of bioresorbable binary MgCa alloys in Ringer's solution: Revealing the impact of local pH distributions during in-vitro dissolution.

    PubMed

    Mareci, D; Bolat, G; Izquierdo, J; Crimu, C; Munteanu, C; Antoniac, I; Souto, R M

    2016-03-01

    Biodegradable magnesium-calcium (MgCa) alloy is a very attractive biomaterial. Two MgCa alloys below the solid solubility of Ca were considered, as to solely investigate the effect of Ca content on the behavior of magnesium and the pH changes associated to metal dissolution. X-ray diffraction analysis and optical microscopy showed that both Mg-0.63Ca and Mg-0.89Ca alloys were solely composed of α(Mg) phase. Degradation characteristics and electrochemical characterization of MgCa alloys were investigated during exposure to Ringer's solution at 37 °C by electrochemical impedance spectroscopy and scanning electrochemical microscopy. The impedance behavior showed both capacitive and inductive features that are related to the alloy charge transfer reaction and the relaxation of the absorbed corrosion compounds, and can be described in terms of an equivalent circuit. Scanning electron microscopy (SEM) was employed to view the surface morphology of the MgCa samples after 1 week immersion in Ringer's solution showing extensive precipitation of corrosion products, whereas the substrate shows evidence of a non-uniform corrosion process. Energy dispersive analysis showed that the precipitates contained oxygen, calcium, magnesium and chlorine, and the Mg:Ca ratios were smaller than in the alloys. Scanning electrochemical microscopy (SECM) was used to visualize local pH changes associated to these physicochemical processes with high spatial resolution. The occurrence of pH variations in excess of 3 units between anodic and cathodic half-cell reactions was monitored in situ.

  11. Dissolution kinetics of granular calcium carbonate in concentrated aqueous sodium dichromate solution at pH 6.0-7.0 and 110-130 degrees C.

    PubMed

    Wang, Tiangui; Li, Zuohu

    2005-01-01

    An understanding of the factors controlling calcite dissolution is important for modeling geochemical cycles and impacts of greenhouse gases on climate, diagenesis of sediments, and sedimentary rocks. It also has practical significance in the investigation of behavior of carbonates in petroleum and natural gas reservoirs and in the preservation of buildings and monuments constructed from limestone and marble. A large number of papers have been published on dissolution kinetics of calcium carbonate in aqueous solutions. But few involved the near-equilibrium region, especially at elevated temperatures and in concentrated solutions. In this paper, the dissolution kinetics of calcium carbonate in concentrated aqueous sodium dichromate solutions at pH 6.0-7.0 and 110-130 degrees C were studied in a 2-L autoclave. The results indicate that the dissolution reaction is mix-controlled, with surface reaction as the prevailing factor. The concentration of calcium ions in solution hardly affects the dissolution rate, but carbon dioxide in the vapor phase inhibits the dissolution reaction. The dissolution rate can be expressed by R = k(1)a(2)(H+) + k(2), and the apparent activation energy is 55-84 kJ mol(-1).

  12. Evaluation of the 5 and 8 pH point titration methods for monitoring anaerobic digesters treating solid waste.

    PubMed

    Vannecke, T P W; Lampens, D R A; Ekama, G A; Volcke, E I P

    2015-01-01

    Simple titration methods certainly deserve consideration for on-site routine monitoring of volatile fatty acid (VFA) concentration and alkalinity during anaerobic digestion (AD), because of their simplicity, speed and cost-effectiveness. In this study, the 5 and 8 pH point titration methods for measuring the VFA concentration and carbonate system alkalinity (H2CO3*-alkalinity) were assessed and compared. For this purpose, synthetic solutions with known H2CO3*-alkalinity and VFA concentration as well as samples from anaerobic digesters treating three different kind of solid wastes were analysed. The results of these two related titration methods were verified with photometric and high-pressure liquid chromatography measurements. It was shown that photometric measurements lead to overestimations of the VFA concentration in the case of coloured samples. In contrast, the 5 pH point titration method provides an accurate estimation of the VFA concentration, clearly corresponding with the true value. Concerning the H2CO3*-alkalinity, the most accurate and precise estimations, showing very similar results for repeated measurements, were obtained using the 8 pH point titration. Overall, it was concluded that the 5 pH point titration method is the preferred method for the practical monitoring of AD of solid wastes due to its robustness, cost efficiency and user-friendliness.

  13. Crystal structure of alkaline cellulase K: insight into the alkaline adaptation of an industrial enzyme.

    PubMed

    Shirai, T; Ishida, H; Noda, J; Yamane, T; Ozaki, K; Hakamada, Y; Ito, S

    2001-07-27

    The crystal structure of the catalytic domain of alkaline cellulase K was determined at 1.9 A resolution. Because of the most alkaliphilic nature and it's highest activity at pH 9.5, it is used commercially in laundry detergents. An analysis of the structural bases of the alkaliphilic character of the enzyme suggested a mechanism similar to that previously proposed for alkaline proteases, that is, an increase in the number of Arg, His, and Gln residues, and a decrease in Asp and Lys residues. Some ion pairs were formed by the gained Arg residues, which is similar to what has been found in the alkaline proteases. Lys-Asp ion pairs are disfavored and partly replaced with Arg-Asp ion pairs. The alkaline adaptation appeared to be a remodeling of ion pairs so that the charge balance is kept in the high pH range.

  14. Effect of electrolyte valency, alginate concentration and pH on engineered TiO₂ nanoparticle stability in aqueous solution.

    PubMed

    Loosli, Frédéric; Le Coustumer, Philippe; Stoll, Serge

    2015-12-01

    Agglomeration and disagglomeration processes are expected to play a key role on the fate of engineered nanoparticles in natural aquatic systems. These processes are investigated here in detail by studying first the stability of TiO2 nanoparticles in the presence of monovalent and divalent electrolytes at different pHs (below and above the point of zero charge of TiO2) and discussing the importance of specific divalent cation adsorption with the help of the DLVO theory as well as the importance of the nature of the counterions. Then the impact of one polysaccharide (alginate) on the stability of agglomerates formed under pH and water hardness representative of Lake Geneva environmental conditions is investigated. In these conditions the large TiO2 agglomerates (diameter>1μm) are positively charged due to Ca(2+) and Mg(2+) specific adsorption and alginate, which is negatively charged, adsorbs onto the agglomerate surface. Our results indicate that the presence of alginate at typical natural organic matter concentration (1-10 mg L(-1)) strongly modifies the TiO2 agglomerate (50 mg L(-1)) stability by inducing their partial and rapid disagglomeration. The importance of disagglomeration is found dependent on the alginate concentration with maximum of disagglomeration obtained for alginate concentration ≥8 mg L(-1) and leading to 400 nm fragments. From an environmental point of view partial restabilization of TiO2 agglomerates in the presence of alginate constitutes an important outcome. Disagglomeration will enhance their transport and residence time in aquatic systems which is an important step in the current knowledge on risk assessment associated to engineered nanoparticles.

  15. Application of saccharose as copper(II) ligand for electroless copper plating solutions.

    PubMed

    Norkus, Eugenijus; Prusinskas, Kestutis; Vaskelis, Algirdas; Jaciauskiene, Jane; Stalnioniene, Irena; Macalady, Donald L

    2007-01-15

    Saccharose, forming sufficiently stable complexes with copper(II) ions in alkaline solutions, was found to be a suitable ligand for copper(II) chelating in alkaline (pH>12) electroless copper deposition solutions. Reduction of copper(II)-saccharose complexes by hydrated formaldehyde was investigated and the copper deposits formed were characterized. The thickness of the compact copper coatings obtained under optimal operating conditions in 1h reaches ca. 2 microm at ambient temperature. The plating solutions were stable and no signs of Cu(II) reduction in the bulk solution were observed. Results were compared with those systems operating with other copper(II) ligands.

  16. Acid-base equilibria in aqueous solutions of meta-cresolsulfophthalein in the temperature range of 25 to 200°C

    NASA Astrophysics Data System (ADS)

    Stepanchikova, S. A.; Galay, G. I.

    2017-01-01

    Values of the second thermodynamic ionization constant of pH indicator m-Cresol Purple are determined spectrophotometrically in slightly alkaline aqueous solutions in the temperature range of 25 to 200°C at saturated vapor pressure. Data required for studies on acid-base equilibria in weakly alkaline aqueous solution of rare-earth elements at elevated temperatures are obtained to characterize their behavior in geochemical systems.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  18. Evolution of oxidation dynamics of histidine: non-reactivity in the gas phase, peroxides in hydrated clusters, and pH dependence in solution.

    PubMed

    Liu, Fangwei; Lu, Wenchao; Fang, Yigang; Liu, Jianbo

    2014-10-28

    Oxidation of histidine by (1)O2 is an important process associated with oxidative damage to proteins during aging, diseases and photodynamic therapy of tumors and jaundice, and photochemical transformations of biological species in the troposphere. However, the oxidation mechanisms and products of histidine differ dramatically in these related environments which range from the gas phase through aerosols to aqueous solution. Herein we report a parallel gas- and solution-phase study on the (1)O2 oxidation of histidine, aimed at evaluating the evolution of histidine oxidation pathways in different media and at different ionization states. We first investigated the oxidation of protonated and deprotonated histidine ions and the same systems hydrated with explicit water molecules in the gas phase, using guided-ion-beam-scattering mass spectrometry. Reaction coordinates and potential energy surfaces for these systems were established on the basis of density functional theory calculations, Rice-Ramsperger-Kassel-Marcus modeling and direct dynamics simulations. Subsequently we tracked the oxidation process of histidine in aqueous solution under different pH conditions, using on-line UV-Vis spectroscopy and electrospray mass spectrometry monitoring systems. The results show that two different routes contribute to the oxidation of histidine depending on its ionization states. In each mechanism hydration is essential to suppressing the otherwise predominant dissociation of reaction intermediates back to reactants. The oxidation of deprotonated histidine in the gas phase involves the formation of 2,4-endoperoxide and 2-hydroperoxide of imidazole. These intermediates evolve to hydrated imidazolone in solution, and the latter either undergoes ring-closure to 6α-hydoxy-2-oxo-octahydro-pyrrolo[2,3-d]imidazole-5-carboxylate or cross-links with another histidine to form a dimeric product. In contrast, the oxidation of protonated histidine is mediated by 2,5-endoperoxide and 5

  19. Characterization of the low pH solution structure and dynamics of the region 4 of Escherichia coli RNA polymerase sigma70 subunit.

    PubMed

    Poznański, Jarosław; Bolewska, Krystyna; Zhukov, Igor; Wierzchowski, Kazimierz L

    2003-11-25

    Solution structure of the region 4 of sigma(70) subunit of Escherichia coli RNA polymerase, whose 4.2 subregion is involved in specific recognition of the -35 element of cognate promoters, has not been yet studied. Using multinuclear NMR spectroscopy, we have assigned recently all the backbone and aliphatic side-chain (13)C resonances for a recombinant His(6)-tagged protein containing the whole region 4 and a part of region 3.2 of sigma(70) in aqueous solution at pH 2.8 (Poznański, J., Zhukov, I., Bolewska, K., and Wierzchowski, K. L. (2001) J. Biomol. NMR 20, 181-2). The protein proved to be sufficiently soluble and did not aggregate only in the protonated state. In this paper, the structure and dynamics of this state at pH 2.8 have been extensively examined using CD and NMR spectroscopy. Both analysis of CD spectra and NMR observables (secondary chemical shifts of the (13)Calpha, (13)CO, and (1)Halpha nuclei and of vicinal (3)J(HNH)(alpha) coupling constants) indicated that a significant amount of helical structure remained in the protonated protein. The amount of this structure increased upon deprotonation of carboxylic amino acids, as shown by pH titration CD experiments. 2,2,2-Trifluoroethanol induced an even more extensive build up of this structure. Distribution along the protein sequence of the secondary shifts and (3)J(HNH)(alpha) couplings demonstrated partition of the helical secondary structure into three helices located similarly as in the crystal structures of the homologous region 4 of the sigma(A) subunit of Thermus aquaticus RNA polymerase (Campbell, E. A., Muzzin, O., Chlenov, M., Sun, J. L., Olson, A., Weinman, O., Trester-Zedlitz, M. L., and Darst, S. A. (2002) Mol. Cell 9, 527-39) and sigma(70) of the Thermus thermophilus RNA polymerase (Vassylyev, D. G., Sekine, S., Laptenko, O., Lee, J., Vassylyeva, M. N., Borukhov, S., and Yokoyama, S. (2002) Nature 417, 712-9.). Spectral density analysis of NMR relaxation parameters, R(1) and R(2), and [(1

  20. Permeability Modification Using a Reactive Alkaline-Soluble Biopolymer

    SciTech Connect

    Sandra L. Fox; Xina Xie; Greg Bala

    2004-11-01

    Polymer injection has been used in reservoirs to alleviate contrasting permeability zones to enhance oil recovery (EOR). Polymer technology relies mainly on the use of polyacrylamides cross-linked by a hazardous metal or organic. Contemporary polymer plugging has investigated the stimulation of in-situ microorganisms to produce polymers (Jenneman et. al., 2000) and the use of biocatalysts to trigger gelling (Bailey et. al., 2000). The use of biological polymers are advantageous in that they can block high permeability areas, are environmentally friendly, and have potential to form reversible gels without the use of hazardous cross-linkers. Recent efforts have produced a reactive alkaline-soluble biopolymer from Agrobacterium species ATCC # 31749 that gels upon decreasing the pH of the polymeric solution. Microbial polymers are of interest due to their potential cost savings, compared to conventional use of synthetic chemical polymers. Numerous microorganisms are known to produce extracellular polysaccharides. One microbiological polymer of interest is curdlan, â - (1, 3) glucan, which has demonstrated gelling properties by a reduction in pH. The focus of this study was to determine the impact an alkaline-soluble biopolymer can have on sandstone permeability.

  1. Surfactant-enhanced alkaline flooding for light oil recovery. Quarterly report, January 1--March 31, 1994

    SciTech Connect

    Wasan, D.T.

    1994-06-01

    The overall objective of this project is to develop a very cost-effective method for formulating a successful surfactant-enhanced alkaline flood by appropriately choosing mixed alkalis which form inexpensive buffers to obtain the desired pH (between 8.5 and 12.0) for ultimate spontaneous emulsification and ultra-low tension. In addition, the novel concept of pH gradient design to optimize flood water conditions will be tested. Last quarter we investigated the phase behavior and the regions where in the middle phase occurs. The optimum phase was found to go through a maximum with pH, sodium concentration and surfactant concentration. The optimum pH is about 12.0 to 13.5, the optimum sodium concentration is about 0.513 mol/liter, and the optimum surfactant concentration is about 0.2%. The effect of surfactant type was also investigated. Petrostep B-105 was found to give the most middle phase production. This quarter, we investigated the contact angle of Long Beach oil, Adena oil, and a model oil on a solid glass surface in contact with an aqueous alkaline solution both with and without added preformed surfactant. The contact angle with Long Beach and Adena oils showed oil-wet conditions, whereas the model oil showed both oil-wet and water-wet conditions depending on the pH of the aqueous phase. The addition of surfactant to the alkaline solution resulted in making the system less oil-wet. Spreading of the oil on the glass surface was observed in all three systems investigated.

  2. Surfactant-enhanced alkaline flooding with weak alkalis

    SciTech Connect

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

    1991-02-01

    The objective of Project BE4B in FY90 was to develop cost-effective and efficient chemical flooding formulations using surfactant-enhanced, lower pH (weak) alkaline chemical systems. Chemical systems were studied that mitigate the deleterious effects of divalent ions. The experiments were conducted with carbonate mixtures and carbonate/phosphate mixtures of pH 10.5, where most of the phosphate ions exist as the monohydrogen phosphate species. Orthophosphate did not further reduce the deleterious effect of divalent ions on interfacial tension behavior in carbonate solutions, where the deleterious effect of the divalent ions is already very low. When added to a carbonate mixture, orthophosphate did substantially reduce the adsorption of an atomic surfactant, which was an expected result; however, there was no correlation between the amount of reduction and the divalent ion levels. For acidic oils, a variety of surfactants are available commercially that have potential for use between pH 8.3 and pH 9.5. Several of these surfactants were tested with oil from Wilmington (CA) field and found to be suitable for use in that field. Two low-acid crude oils, with acid numbers of 0.01 and 0.27 mg KOH/g of oil, were studied. It was shown that surfactant-enhanced alkaline flooding does have merit for use with these low-acid crude oils. However, each low-acid oil tested was found to behave differently, and it was concluded that the applicability of the method must be experimentally determined for any given low-acid crude oil. 19 refs., 10 figs. 4 tabs.

  3. The role of chemistry and pH of solid surfaces for specific adsorption of biomolecules in solution--accurate computational models and experiment.

    PubMed

    Heinz, Hendrik

    2014-06-18

    Adsorption of biomolecules and polymers to inorganic nanostructures plays a major role in the design of novel materials and therapeutics. The behavior of flexible molecules on solid surfaces at a scale of 1-1000 nm remains difficult and expensive to monitor using current laboratory techniques, while playing a critical role in energy conversion and composite materials as well as in understanding the origin of diseases. Approaches to implement key surface features and pH in molecular models of solids are explained, and distinct mechanisms of peptide recognition on metal nanostructures, silica and apatite surfaces in solution are described as illustrative examples. The influence of surface energies, specific surface features and protonation states on the structure of aqueous interfaces and selective biomolecular adsorption is found to be critical, comparable to the well-known influence of the charge state and pH of proteins and surfactants on their conformations and assembly. The representation of such details in molecular models according to experimental data and available chemical knowledge enables accurate simulations of unknown complex interfaces in atomic resolution in quantitative agreement with independent experimental measurements. In this context, the benefits of a uniform force field for all material classes and of a mineral surface structure database are discussed.

  4. The effect of pH on the corrosion behavior of intermetallic compounds Ni{sub 3}(Si,Ti) and Ni{sub 3}(Si,Ti) + 2Mo in sodium chloride solutions

    SciTech Connect

    Priyotomo, Gadang Nuraini, Lutviasari; Kaneno, Yasuyuki

    2015-12-29

    The corrosion behavior of the intermetallic compounds, Ni{sub 3}(Si,Ti) (L1{sub 2}: single phase) and Ni{sub 3}(Si,Ti) + 2Mo (L1{sub 2} and (L12 + Ni{sub ss}) mixture region), has been investigated using an immersion test, electrochemical method and surface analytical method (SEM; scanning electron microscope and EDAX: Energy Dispersive X-ray) in 0.5 kmol/m{sup 3} NaCl solutions at various pH. The corrosion behavior of nickel alloy C-276 was studied under the same experimental conditions as a reference. It was found that the uniform attack was observed on Ni{sub 3}(Si,Ti) for the immersion test at lower pH, while the pitting attack was observed on this compound for this test at neutral solution. Furthermore, Ni{sub 3}(Si,Ti)+2Mo had the preferential dissolution of L1{sub 2} compared to (L1{sub 2} + Ni{sub ss}) mixture region at lower pH, while pitting attack occurred in (L1{sub 2} + Ni{sub ss}) mixture region at neutral solution. For both intermetallic compounds, the magnitude of pitting and uniform attack decrease with increasing pH of solutions. From the immersion test and polarization curves, the corrosion resistance of Ni{sub 3}(Si,Ti)+2Mo is lower than that of Ni{sub 3}(Si,Ti), while the nickel alloy C-276 is the highest one at various pH of solutions. On the other hand, in the lower pH of solutions, the corrosion resistance of tested materials decreased significantly compared to those in neutral and higher pH of solutions.

  5. A New Mechanism in Electrochemical Process for Arsenic Oxidation: Production of H2O2 from Anodic O2 Reduction on the Cathode under Automatically Developed Alkaline Conditions.

    PubMed

    Qian, Ao; Yuan, Songhu; Zhang, Peng; Tong, Man

    2015-05-05

    Electrochemical cathodes are often used to reduce contaminants or produce oxidizing substances (i.e., H2O2). Alkaline conditions develop automatically around the cathode in electrochemical processes, and O2 diffuses onto the cathode easily. However, limited attention is paid to contaminant transformation by the reactive species produced on the cathode under oxic and alkaline conditions due to the inapplicability of pH for Fenton reaction. In this study, a new oxidation mechanism on the cathode is presented for contaminant transformation under automatically developed alkaline conditions. In an electrochemical sand column, 6.67 μM As(III) was oxidized by 36% when it passed through the cathode under the conditions of 30 mA current, an initial pH of 7.5 and a flow rate of 2 mL/min. Under the alkaline conditions (pH 10.0-11.0) that developed automatically around the cathode, the reduction potential of As(III) decreased greatly, allowing a pronounced oxidation by the small quantities of H2O2 produced from O2 reduction on the cathode. As(III) oxidation was further increased by the presence of soil pore water and groundwater solutes of HCO3-, Ca2+, Mg2+ and humic acid. The new oxidation mechanism found for the cathode under localized alkaline conditions supplements the fundamentals of contaminant transformation in electrochemical processes.

  6. Elucidating how bamboo salt interacts with supported lipid membranes: influence of alkalinity on membrane fluidity.

    PubMed

    Jeong, Jong Hee; Choi, Jae-Hyeok; Kim, Min Chul; Park, Jae Hyeon; Herrin, Jason Scott; Kim, Seung Hyun; Lee, Haiwon; Cho, Nam-Joon

    2015-07-01

    Bamboo salt is a traditional medicine produced from sea salt. It is widely used in Oriental medicine and is an alkalizing agent with reported antiinflammatory, antimicrobial and chemotherapeutic properties. Notwithstanding, linking specific molecular mechanisms with these properties has been challenging to establish in biological systems. In part, this issue may be related to bamboo salt eliciting nonspecific effects on components found within these systems. Herein, we investigated the effects of bamboo salt solution on supported lipid bilayers as a model system to characterize the interaction between lipid membranes and bamboo salt. The atomic composition of unprocessed and processed bamboo salts was first analyzed by mass spectrometry, and we identified several elements that have not been previously reported in other bamboo salt preparations. The alkalinity of hydrated samples was also measured and determined to be between pH 10 and 11 for bamboo salts. The effect of processed bamboo salt solutions on the fluidic properties of a supported lipid bilayer on glass was next investigated by fluorescence recovery after photobleaching (FRAP) analysis. It was demonstrated that, with increasing ionic strength of the bamboo salt solution, the fluidity of a lipid bilayer increased. On the contrary, increasing the ionic strength of near-neutral buffer solutions with sodium chloride salt diminished fluidity. To reconcile these two observations, we identified that solution alkalinity is critical for the effects of bamboo salt on membrane fluidity, as confirmed using three additional commercial bamboo salt preparations. Extended-DLVO model calculations support that the effects of bamboo salt on lipid membranes are due to the alkalinity imparting a stronger hydration force. Collectively, the results of this work demonstrate that processing of bamboo salt strongly affects its atomic composition and that the alkalinity of bamboo salt solutions contributes to its effect on membrane

  7. pH adjustment schedule for the amide local anesthetics.

    PubMed

    Ikuta, P T; Raza, S M; Durrani, Z; Vasireddy, A R; Winnie, A P; Masters, R W

    1989-01-01

    Several studies have indicated that the addition of sodium bicarbonate to solutions of local anesthetics to raise the pH closer to the pKa shortens the latency, increases the intensity, and prolongs the duration of the resultant neural blockade. However, the addition of too much bicarbonate will cause precipitation, and this may result in the injection of particulate free base along with the solution. The present study was carried out to determine the maximal amount of sodium bicarbonate that can be added to each of the amide local anesthetics without the formation of a precipitate, and, thus, to construct a pH adjustment schedule to simplify the alkalinization of local anesthetics in clinical practice.

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

    PubMed Central

    Hou, Guanhua

    2011-01-01

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

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

    PubMed

    Hou, Guanhua; Cui, Qiang

    2012-01-11

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

  10. De Novo Transcriptional Analysis of Alfalfa in Response to Saline-Alkaline Stress

    PubMed Central

    An, Yi-Min; Song, Li-Li; Liu, Ying-Rui; Shu, Yong-Jun; Guo, Chang-Hong

    2016-01-01

    Saline-alkaline stress, caused by high levels of harmful carbonate salts and high soil pH, is a major abiotic stress that affects crop productivity. Alfalfa is a widely cultivated perennial forage legume with some tolerance to biotic and abiotic stresses, especially to saline-alkaline stress. To elucidate the mechanism underlying plant saline-alkaline tolerance, we conducted transcriptome analysis of whole alfalfa seedlings treated with saline-alkaline solutions for 0 day (control), 1 day (short-term treatment), and 7 days (long-term treatment) using ion torrent sequencing technology. A transcriptome database dataset of 53,853 unigenes was generated, and 2,286 and 2,233 genes were differentially expressed in the short-term and long-term treatment, respectively. Gene ontology analysis revealed 14 highly enriched pathways and demonstrated the differential response of metabolic pathways between the short-term and long-term treatment. The expression levels of 109 and 96 transcription factors were significantly altered significantly after 1 day and 7 days of treatment, respectively. Specific responses of peroxidase, flavonoids, and the light pathway component indicated that the antioxidant capacity was one of the central mechanisms of saline-alkaline stress tolerance response in alfalfa. Among the 18 differentially expressed genes examined by real time PCR, the expression levels of eight genes, including inositol transporter, DNA binding protein, raffinose synthase, ferritin, aldo/keto reductase, glutathione S-transferase, xyloglucan endotrans glucosylase, and a NAC transcription factor, exhibited different patterns in response to saline and alkaline stress. The expression levels of the NAC transcription factor and glutathione S-transferase were altered significantly under saline stress and saline-alkaline stress; they were upregulated under saline-alkaline stress and downregulated under salt stress. Physiology assays showed an increased concentration of reactive oxygen

  11. Effect of environment pH on the photophysics of fisetin in solid lipid nanoparticles.

    PubMed

    Das, Shrabanti; Maity, Arnab; Purkayastha, Pradipta

    2015-12-01

    Photophysical modulation of fiseti