Pore-scale interfacial dynamics during gas-supersaturated water injection in porous media - on nucleation, growth and advection of disconnected fluid phases (Invited)

NASA Astrophysics Data System (ADS)

Or, D.; Ioannidis, M.

2010-12-01

Degassing and in situ development of a mobile gas bubbles occur when injecting supersaturated aqueous phase into water-saturated porous media. Supersaturated water injection (SWI) has potentially significant applications in remediation of soils contaminated by non-aqueous phase liquids and in enhanced oil recovery. Pore network simulations indicate the formation of a region near the injection boundary where gas phase nuclei are activated and grow by mass transfer from the flowing supersaturated aqueous phase. Ramified clusters of gas-filled pores develop which, owing to the low prevailing Bond number, grow laterally to a significant extent prior to the onset of mobilization, and are thus likely to coalesce. Gas cluster mobilization invariably results in fragmentation and stranding, such that a macroscopic region containing few tenuously connected large gas clusters is established. Beyond this region, gas phase nucleation and mass transfer from the aqueous phase are limited by diminishing supply of dissolved gas. New insights into SWI dynamics are obtained using rapid micro-visualization in transparent glass micromodels. Using high-speed imaging, we observe the nucleation, initial growth and subsequent fate (mobilization, fragmentation, collision, coalescence and stranding) of CO2 bubbles and clusters of gas-filled pores and analyze cluster population statistics. We find significant support for the development of invasion-percolation-like patterns, but also report on hitherto unaccounted for gas bubble behavior. Additionally, we report for the first time on the acoustic emission signature of SWI in porous media and relate it to the dynamics of bubble nucleation and growth. Finally, we identify the pore-scale mechanisms associated with the mobilization and subsequent recovery of a residual non-aqueous phase liquid due to gas bubble dynamics during SWI.

Downstream processing of antibodies: single-stage versus multi-stage aqueous two-phase extraction.

PubMed

Rosa, P A J; Azevedo, A M; Ferreira, I F; Sommerfeld, S; Bäcker, W; Aires-Barros, M R

2009-12-11

Single-stage and multi-stage strategies have been evaluated and compared for the purification of human antibodies using liquid-liquid extraction in aqueous two-phase systems (ATPSs) composed of polyethylene glycol 3350 (PEG 3350), dextran, and triethylene glycol diglutaric acid (TEG-COOH). The performance of single-stage extraction systems was firstly investigated by studying the effect of pH, TEG-COOH concentration and volume ratio on the partitioning of the different components of a Chinese hamster ovary (CHO) cells supernatant. It was observed that lower pH values and high TEG-COOH concentrations favoured the selective extraction of human immunoglobulin G (IgG) to the PEG-rich phase. Higher recovery yields, purities and percentage of contaminants removal were always achieved in the presence of the ligand, TEG-COOH. The extraction of IgG could be enhanced using higher volume ratios, however with a significant decrease in both purity and percentage of contaminants removal. The best single-stage extraction conditions were achieved for an ATPS containing 1.3% (w/w) TEG-COOH with a volume ratio of 2.2, which allowed the recovery of 96% of IgG in the PEG-rich phase with a final IgG concentration of 0.21mg/mL, a protein purity of 87% and a total purity of 43%. In order to enhance simultaneously both recovery yield and purity, a four stage cross-current operation was simulated and the corresponding liquid-liquid equilibrium (LLE) data determined. A predicted optimised scheme of a counter-current multi-stage aqueous two-phase extraction was hence described. IgG can be purified in the PEG-rich top phase with a final recovery yield of 95%, a final concentration of 1.04mg/mL and a protein purity of 93%, if a PEG/dextran ATPS containing 1.3% (w/w) TEG-COOH, 5 stages and volume ratio of 0.4 are used. Moreover, according to the LLE data of all CHO cells supernatant components, it was possible to observe that most of the cells supernatant contaminants can be removed during this extraction step leading to a final total purity of about 85%.

An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry

PubMed Central

Hoffmann, Erik Hans; Tilgner, Andreas; Schrödner, Roland; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

2016-01-01

Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42−) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42− aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions. PMID:27688763

Control and measurement of the phase behavior of aqueous solutions using microfluidics

PubMed Central

Shim, Jung-uk; Cristobal, Galder; Link, Darren R.; Thorsen, Todd; Jia, Yanwei; Piattelli, Katie; Fraden, Seth

2008-01-01

A microfluidic device denoted the Phase Chip has been designed to measure and manipulate the phase diagram of multi-component fluid mixtures. The Phase Chip exploits the permeation of water through poly(dimethylsiloxane) (PDMS) in order to controllably vary the concentration of solutes in aqueous nanoliter volume microdrops stored in wells. The permeation of water in the Phase Chip is modeled using the diffusion equation and good agreement between experiment and theory is obtained. The Phase Chip operates by first creating drops of the water/solute mixture whose composition varies sequentially. Next, drops are transported down channels and guided into storage wells using surface tension forces. Finally, the solute concentration of each stored drop is simultaneously varied and measured. Two applications of the Phase Chip are presented. First, the phase diagram of a polymer/salt mixture is measured on-chip and validated off-chip and second, protein crystallization rates are enhanced through the manipulation of the kinetics of nucleation and growth. PMID:17580868

In situ observation of sol-gel transition of agarose aqueous solution by fluorescence measurement.

PubMed

Wang, Zheng; Yang, Kun; Li, Haining; Yuan, Chaosheng; Zhu, Xiang; Huang, Haijun; Wang, Yongqiang; Su, Lei; Fang, Yapeng

2018-06-01

Sol-gel transition behavior of agarose aqueous solution was investigated by using rheology and fluorescence measurement. On heating, the storage modulus G' decreased gradually, then deviated abruptly at the temperature of about 65°C, and finally decreased slowly again. For fluorescence measurement, the phase transition point kept almost at the temperature of 65°C, which was consistent with that in rheology measurement. Upon compression, it was indicated that the fluorescence lifetime for the probe in the agarose aqueous solution showed a dramatic change in the vicinity of the phase transition point. T vs. P phase diagram of agarose aqueous solution was constructed, which showed that the melting point was an increasing function of pressure. Based on the phase diagram, the agarose gels were prepared by cooling under atmospheric pressure and the pressure of 300MPa, respectively. From the result of the recovered samples studied by optical rheometry, it was found that agarose gel prepared under high pressure had a higher elasticity and lower viscosity index, compared with that under atmospheric pressure. It could be speculated that such kinds of properties might be attributed to the smaller pore size during gelation under high pressure. Copyright © 2018. Published by Elsevier B.V.

Radical-driven carbonyl-to-acid conversion and acid degradation in tropospheric aqueous systems studied by CAPRAM

NASA Astrophysics Data System (ADS)

Tilgner, A.; Herrmann, H.

2010-12-01

Model studies on the aqueous phase radical-driven processing of carbonyl compounds and acids in clouds and deliquescent particles were performed. The model exposed that aqueous radical conversions of carbonyl compounds and its oxidation products can contribute potentially to the formation of functionalised organic acids. The main identified C 2-C 4 organic gas phase precursors are ethylene glycol, glycolaldehyde, glyoxal, methylglyoxal and 1,4-butenedial. The aqueous phase is shown to contribute significantly with about 93%/63%, 47%/8%, 31%/4%, 7%/4%, 36%/8% to the multiphase oxidative fate of these compounds under remote/urban conditions. Interestingly, the studies revealed that aqueous chemical processing is not only limited to in-cloud conditions but also proceeds in deliquescent particle phase with significant fluxes. Oxalic acid is shown to be formed preferably in deliquescent particles subsequent to the in-cloud oxidations. Mean aqueous phase oxalate formation fluxes of about 12, 42 and 0.4 ng m -3 h -1 in the remote, urban and maritime scenario, respectively. Additionally, the turnovers of the oxidation of organics such as methylglyoxal by NO 3 radical reactions are identified to be competitive to their OH pendants. At the current state of CAPRAM, mean C 2-C 4 in-cloud oxidation fluxes of about 0.12 and 0.5 μg m -3 h -1 are modelled under the idealised remote and urban cloud conditions. Finally, turnovers from radical oxidations were compared with those of thermal reactions. It is demonstrated that, based on the sparse kinetic data available organic accretion reaction might be of interest in just a few cases for cloud droplets and aqueous particles but generally do not reach the oxidative conversion rates of the main radical oxidants OH and NO 3. Interestingly, oxidation reactions of H 2O 2 are shown to be competitive to the OH radical conversions in cases when H 2O 2 is not readily used up by the S(IV) oxidation.

Preparative separation of six rhynchophylla alkaloids from Uncaria macrophylla wall by pH-zone refining counter-current chromatography.

PubMed

Zhang, Qinghai; Lin, Changhu; Duan, Wenjuan; Wang, Xiao; Luo, Aiqin

2013-12-12

pH-Zone refining counter-current chromatography was successfully applied to the preparative isolation and purification of six alkaloids from the ethanol extracts of Uncaria macrophylla Wall. Because of the low content of alkaloids (about 0.2%, w/w) in U. macrophylla Wall, the target compounds were enriched by pH-zone refining counter-current chromatography using a two-phase solvent system composed of petroleum ether-ethyl acetate-isopropanol-water (2:6:3:9, v/v), adding 10 mM triethylamine in organic stationary phase and 5 mM hydrochloric acid in aqueous mobile phase. Then pH-zone refining counter-current chromatography using the other two-phase solvent system was used for final purification. Six target compounds were finally isolated and purified by following two-phase solvent system composed of methyl tert-butyl ether (MTBE)-acetonitrile-water (4:0.5:5, v/v), adding triethylamine (TEA) (10 mM) to the organic phase and HCl (5 mM) to aqueous mobile phase. The separation of 2.8 g enriched total alkaloids yielded 36 mg hirsutine, 48 mg hirsuteine, 82 mg uncarine C, 73 mg uncarine E, 163 mg rhynchophylline, and 149 mg corynoxeine, all with purities above 96% as verified by HPLC Their structures were identified by electrospray ionization-mass spectrometry (ESI-MS) and 1H-NMR spectroscopy.

Bioreactor droplets from liposome-stabilized all-aqueous emulsions

NASA Astrophysics Data System (ADS)

Dewey, Daniel C.; Strulson, Christopher A.; Cacace, David N.; Bevilacqua, Philip C.; Keating, Christine D.

2014-08-01

Artificial bioreactors are desirable for in vitro biochemical studies and as protocells. A key challenge is maintaining a favourable internal environment while allowing substrate entry and product departure. We show that semipermeable, size-controlled bioreactors with aqueous, macromolecularly crowded interiors can be assembled by liposome stabilization of an all-aqueous emulsion. Dextran-rich aqueous droplets are dispersed in a continuous polyethylene glycol (PEG)-rich aqueous phase, with coalescence inhibited by adsorbed ~130-nm diameter liposomes. Fluorescence recovery after photobleaching and dynamic light scattering data indicate that the liposomes, which are PEGylated and negatively charged, remain intact at the interface for extended time. Inter-droplet repulsion provides electrostatic stabilization of the emulsion, with droplet coalescence prevented even for submonolayer interfacial coatings. RNA and DNA can enter and exit aqueous droplets by diffusion, with final concentrations dictated by partitioning. The capacity to serve as microscale bioreactors is established by demonstrating a ribozyme cleavage reaction within the liposome-coated droplets.

Bioreactor droplets from liposome-stabilized all-aqueous emulsions.

PubMed

Dewey, Daniel C; Strulson, Christopher A; Cacace, David N; Bevilacqua, Philip C; Keating, Christine D

2014-08-20

Artificial bioreactors are desirable for in vitro biochemical studies and as protocells. A key challenge is maintaining a favourable internal environment while allowing substrate entry and product departure. We show that semipermeable, size-controlled bioreactors with aqueous, macromolecularly crowded interiors can be assembled by liposome stabilization of an all-aqueous emulsion. Dextran-rich aqueous droplets are dispersed in a continuous polyethylene glycol (PEG)-rich aqueous phase, with coalescence inhibited by adsorbed ~130-nm diameter liposomes. Fluorescence recovery after photobleaching and dynamic light scattering data indicate that the liposomes, which are PEGylated and negatively charged, remain intact at the interface for extended time. Inter-droplet repulsion provides electrostatic stabilization of the emulsion, with droplet coalescence prevented even for submonolayer interfacial coatings. RNA and DNA can enter and exit aqueous droplets by diffusion, with final concentrations dictated by partitioning. The capacity to serve as microscale bioreactors is established by demonstrating a ribozyme cleavage reaction within the liposome-coated droplets.

Mercury removal from aqueous streams utilizing microemulsion liquid membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larson, K.A.; Wiencek, J.M.

1994-11-01

The goal of this work is the removal of mercury ion from wastewater using thermodynamically stable microemulsions as liquid membranes. The research focuses on identification and modeling of the appropriate aqueous and organic phase equilibrium reactions for mercury extraction and stripping, comparison of extraction kinetics between coarse emulsions and microemulsions, and demulsification and recovery of the emulsion components. An oleic acid microemulsion liquid membrane (water-in-oil) containing sulfuric acid as the internal phase reduces the feed phase mercury concentration from 460 mg/l to 0.84 mg/l in a single contacting. This compares favorably with a control extraction (oleic acid/no internal phase) whichmore » results in a final concentration of 20 mg/l Hg{sup +2}. Microemulsions can be demulsified using butanol as an additive. The demulsification kinetics are proportional to butanol concentration and temperature and inversely proportional to surfactant concentration. The demulsification rate is second order with respect to water concentration which implies that the rate-limiting step in the process is the rate of internal phase droplet encounters. Proof-of-principle experiments demonstrate the ability to extract mercury ion using microemulsions formulated with recycled organic phase, albeit at a somewhat reduced efficiency. The reduced efficiency is attributed to increased internal phase leakage due to residual butanol in the oil phase. Finally, the cycle is brought around full circle by recovering metallic mercury from the internal phase by electroplating. 27 refs., 11 figs., 1 tab.« less

Extraction equilibrium of indium(III) from nitric acid solutions by di(2-ethylhexyl)phosphoric acid dissolved in kerosene.

PubMed

Tsai, Hung-Sheng; Tsai, Teh-Hua

2012-01-04

The extraction equilibrium of indium(III) from a nitric acid solution using di(2-ethylhexyl) phosphoric acid (D2EHPA) as an acidic extractant of organophosphorus compounds dissolved in kerosene was studied. By graphical and numerical analysis, the compositions of indium-D2EHPA complexes in organic phase and stoichiometry of the extraction reaction were examined. Nitric acid solutions with various indium concentrations at 25 °C were used to obtain the equilibrium constant of InR₃ in the organic phase. The experimental results showed that the extraction distribution ratios of indium(III) between the organic phase and the aqueous solution increased when either the pH value of the aqueous solution and/or the concentration of the organic phase extractant increased. Finally, the recovery efficiency of indium(III) in nitric acid was measured.

Physical and chemical interactions at the interface between atmospheric pressure plasmas and aqueous solutions

NASA Astrophysics Data System (ADS)

Lindsay, Alexander; Byrns, Brandon; Knappe, Detlef; Graves, David; Shannon, Steven

2014-10-01

Transport and reactions of charged species, neutrals, and photons at the interface between plasmas and liquids must be better quantified. The work presented here combines theoretical and experimental investigations of conditions in the gas and liquid phases in proximity to the interface for various discharges. OES is used to determine rotational and vibrational temperatures of OH, NO, and N2+; the relationship between these temperatures that characterize the distribution of internal energy states and gas and electron kinetic temperatures is considered. The deviation of OH rotational states from equilibrium under high humidity conditions is also presented. In contradiction with findings of other groups, high energy rotational states appear to become underpopulated with increasing humidity. In the aqueous phase, concentrations of longer-lived species such as nitrate, nitrite, hydrogen peroxide, and ozone are determined using ion chromatography and colorimetric methods. Spin-traps and electron paramagnetic resonance (EPR) are investigated for characterization of short-lived aqueous radicals like OH, O2-, NO, and ONOO-. Finally, experimental results are compared to a numerical model which couples transport and reactions within and between the bulk gas and liquid phases.

Hydrogen evolution from aqueous-phase photocatalytic reforming of ethylene glycol over Pt/TiO2 catalysts: Role of Pt and product distribution

NASA Astrophysics Data System (ADS)

Li, Fuying; Gu, Quan; Niu, Yu; Wang, Renzhang; Tong, Yuecong; Zhu, Shuying; Zhang, Hualei; Zhang, Zizhong; Wang, Xuxu

2017-01-01

Pt nanoparticles were loaded on anatase TiO2 by the photodeposition method to investigate their photocatalytic activity for H2 evolution in an aqueous solution containing a certain amount of ethylene glycol (EG) as the sacrificial agent. The surface properties and chemical states of the Pt/TiO2 sample were characterized by X-ray powder diffraction analysis, Brunauer-Emmett-Teller surface area analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and electrochemical resistance. The aqueous-phase photocatalytic EG reforming using Pt/TiO2 and anatase TiO2 generated not only H2 and CO2, but also CO, CH4, C2H6, and C2H4. Moreover, the amount of formate and acetate complexes in the solution increased gradually. The EG adsorption and gas-phase intermediates during photocatalytic reaction processes were investigated by the in situ FTIR spectrum. Finally, the photocatalytic EG reforming reaction mechanism was elucidated. This helped to better understand the role of a sacrificial agent in a photocatalytic hydrogen production.

User`s guide for UTCHEM implicit (1.0) a three dimensional chemical flood simulator. Final report, September 30, 1992--December 31, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1996-07-01

UTCHEM IMPLICIT is a three-dimensional chemical flooding simulator. The solution scheme is fully implicit. The pressure equation and the mass conservation equations are solved simultaneously for the aqueous phase pressure and the total concentrations of each component. A third-order-in-space, second-order-in-time finite-difference method and a new total-variation-diminishing (TVD) third-order flux limiter are used to reduce numerical dispersion effects. Saturations and phase concentrations are solved in a flash routine. The major physical phenomena modeled in the simulator are: dispersion, adsorption, aqueous-oleic-microemulsion phase behavior, interfacial tension, relative permeability, capillary trapping, compositional phase viscosity, capillary pressure, phase density, polymer properties: shear thinning viscosity, inaccessiblemore » pore volume, permeability reduction, and adsorption. The following options are available in the simulator: constant or variable time-step sizes, uniform or nonuniform grid, pressure or rate constrained wells, horizontal and vertical wells.« less

AQUEOUS AND SLURRY PHASE BIOTRANSFORMATION OF AROCLOR 1242 USING TERPENES AS COSUBSTRATES. (R825540C004)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roscioli-Johnson, Kristyn M.; Zarzana, Christopher A.; Groenewold, Gary S.

In this paper, solutions of N,N-didodecyl-N',N'-dioctyldiglycolamide in n-dodecane were subjected to γ-irradiation in the presence and absence of both an aqueous nitric acid phase and air sparging. The solutions were analyzed using ultra-high-performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) to determine the rates of radiolytic decay of the extractant as well as to identify radiolysis products. The DGA concentration decreased exponentially with increasing dose, and the measured degradation rate constants were uninfluenced by the presence or absence of acidic aqueous phase, or by air sparging. Finally, the identified radiolysis products suggest that the bonds most vulnerable to radiolytic attack are thosemore » in the diglycolamide center of these molecules and not in the side chains.« less

In-cloud multiphase behaviour of acetone in the troposphere: gas uptake, Henry's law equilibrium and aqueous phase photooxidation.

PubMed

Poulain, Laurent; Katrib, Yasmine; Isikli, Estelle; Liu, Yao; Wortham, Henri; Mirabel, Philippe; Le Calvé, Stéphane; Monod, Anne

2010-09-01

Acetone is ubiquitous in the troposphere. Several papers have focused in the past on its gas phase reactivity and its impact on tropospheric chemistry. However, acetone is also present in atmospheric water droplets where its behaviour is still relatively unknown. In this work, we present its gas/aqueous phase transfer and its aqueous phase photooxidation. The uptake coefficient of acetone on water droplets was measured between 268 and 281K (γ=0.7 x 10(-2)-1.4 x 10(-2)), using the droplet train technique coupled to a mass spectrometer. The mass accommodation coefficient α (derived from γ) was found in the range (1.0-3.0±0.25) x 10(-2). Henry's law constant of acetone was directly measured between 283 and 298K using a dynamic equilibrium system (H((298K))=(29±5)Matm(-1)), with the Van't Hoff expression lnH(T)=(5100±1100)/T-(13.4±3.9). A recommended value of H was suggested according to comparison with literature. The OH-oxidation of acetone in the aqueous phase was carried out at 298K, under two different pH conditions: at pH=2, and under unbuffered conditions. In both cases, the formation of methylglyoxal, formaldehyde, hydroxyacetone, acetic acid/acetate and formic acid/formate was observed. The formation of small amounts of four hydroperoxides was also detected, and one of them was identified as peroxyacetic acid. A drastic effect of pH was observed on the yields of formaldehyde, one hydroperoxide, and, (to a lesser extent) acetic acid/acetate. Based on the experimental observations, a chemical mechanism of OH-oxidation of acetone in the aqueous phase was proposed and discussed. Atmospheric implications of these findings were finally discussed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Plasmid DNA partitioning and separation using poly(ethylene glycol)/poly(acrylate)/salt aqueous two-phase systems.

PubMed

Johansson, Hans-Olof; Matos, Tiago; Luz, Juliana S; Feitosa, Eloi; Oliveira, Carla C; Pessoa, Adalberto; Bülow, Leif; Tjerneld, Folke

2012-04-13

Phase diagrams of poly(ethylene glycol)/polyacrylate/Na(2)SO(4) systems have been investigated with respect to polymer size and pH. Plasmid DNA from Escherichia coli can depending on pH and polymer molecular weight be directed to a poly(ethylene glycol) or to a polyacrylate-rich phase in an aqueous two-phase system formed by these polymers. Bovine serum albumin (BSA) and E. coli homogenate proteins can be directed opposite to the plasmid partitioning in these systems. Two bioseparation processes have been developed where in the final step the pDNA is partitioned to a salt-rich phase giving a total process yield of 60-70%. In one of them the pDNA is partitioned between the polyacrylate and PEG-phases in order to remove proteins. In a more simplified process the plasmid is partitioned to a PEG-phase and back-extracted into a Na(2)SO(4)-rich phase. The novel polyacrylate/PEG system allows a strong change of the partitioning between the phases with relatively small changes in composition or pH. Copyright © 2012 Elsevier B.V. All rights reserved.

Methyl Chloroform Elimination from the Production of Space Shuttle Sold Rocket Motors

NASA Technical Reports Server (NTRS)

Golde, Rick P.; Burt, Rick; Key, Leigh

1997-01-01

Thiokol Space Operations manufactures the Reusable Solid Rocket Motors used to launch America's fleet of Space Shuttles. In 1989, Thiokol used more than 1.4 Mlb of methyl chloroform to produce rocket motors. The ban placed by the Environmental Protection Agency on the sale of methyl chloroform had a significant effect on future Reusable Solid Rocket Motor production. As a result, changes in the materials and processes became necessary. A multiphased plan was established by Thiokol in partnership with NASA's Marshall Space Flight Center to eliminate the use of methyl chloroform in the Reusable Solid Rocket Motor production process. Because of the extensive scope of this effort, the plan was phased to target the elimination of the majority of methyl chloroform use (90 percent) by January 1, 1996, the 3 Environmental Protection Agency deadline. Referred to as Phase I, this effort includes the elimination of two large vapor degreasers, grease diluent processes, and propellant tooling handcleaning using methyl chloroform. Meanwhile, a request was made for an essential use exemption to allow the continued use of the remaining 10 percent of methyl chloroform after the 1996 deadline, while total elimination was pursued for this final, critical phase (Phase II). This paper provides an update to three previous presentations prepared for the 1993, 1994, and 1995 CFC/Halon Alternative Conferences, and will outline the overall Ozone Depleting Compounds Elimination Program from the initial phases through the final testing and implementation phases, including facility and equipment development. Processes and materials to be discussed include low-pressure aqueous wash systems, high-pressure water blast systems- environmental shipping containers, aqueous and semi-aqueous cleaning solutions, and bond integrity and inspection criteria. Progress toward completion of facility implementation and lessons learned during the scope of the program, as well as the current development efforts and basic requirements of future methyl chloroform handcleaning elimination, will also be outlined.

The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

NASA Astrophysics Data System (ADS)

Couvidat, F.; Sartelet, K.

2014-01-01

The Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model is designed to be modular with different user options depending on the computing time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption on the aqueous phase of particles, activity coefficients, phase separation). Each surrogate can be hydrophilic (condenses only on the aqueous phase of particles), hydrophobic (condenses only on the organic phase of particles) or both (condenses on both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC thermodynamic model for short-range interactions and with the AIOMFAC parameterization for medium and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium and a dynamic representation of the organic aerosol. In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol (OA) is not at equilibrium with the gas phase because the organic phase could be semi-solid (very viscous liquid phase). The condensation or evaporation of organic compounds could then be limited by the diffusion in the organic phase due to the high viscosity. A dynamic representation of secondary organic aerosols (SOA) is used with OA divided into layers, the first layer at the center of the particle (slowly reaches equilibrium) and the final layer near the interface with the gas phase (quickly reaches equilibrium).

AQUEOUS AND SLURRY PHASE COMETABOLIC BIODEGRADATION OF AROCLOR 1242 USING TERPENES AS COSUBSTRATES. (R825540C004)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Fibrous scaffolds fabricated by emulsion electrospinning: from hosting capacity to in vivo biocompatibility

NASA Astrophysics Data System (ADS)

Spano, F.; Quarta, A.; Martelli, C.; Ottobrini, L.; Rossi, R. M.; Gigli, G.; Blasi, L.

2016-04-01

Electrospinning is a versatile method for preparing functional three-dimensional scaffolds. Synthetic and natural polymers have been used to produce micro- and nanofibers that mimic extracellular matrices. Here, we describe the use of emulsion electrospinning to prepare blended fibers capable of hosting aqueous species and releasing them in solution. The existence of an aqueous and a non-aqueous phase allows water-soluble molecules to be introduced without altering the structure and the degradation of the fibers, and means that their release properties under physiological conditions can be controlled. To demonstrate the loading capability and flexibility of the blend, various species were introduced, from magnetic nanoparticles and quantum rods to biological molecules. Cellular studies showed the spontaneous adhesion and alignment of cells along the fibers. Finally, in vivo experiments demonstrated the high biocompatibility and safety of the scaffolds up to 21 days post-implantation.Electrospinning is a versatile method for preparing functional three-dimensional scaffolds. Synthetic and natural polymers have been used to produce micro- and nanofibers that mimic extracellular matrices. Here, we describe the use of emulsion electrospinning to prepare blended fibers capable of hosting aqueous species and releasing them in solution. The existence of an aqueous and a non-aqueous phase allows water-soluble molecules to be introduced without altering the structure and the degradation of the fibers, and means that their release properties under physiological conditions can be controlled. To demonstrate the loading capability and flexibility of the blend, various species were introduced, from magnetic nanoparticles and quantum rods to biological molecules. Cellular studies showed the spontaneous adhesion and alignment of cells along the fibers. Finally, in vivo experiments demonstrated the high biocompatibility and safety of the scaffolds up to 21 days post-implantation. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00782a

Design of aqueous two-phase systems for purification of hyaluronic acid produced by metabolically engineered Lactococcus lactis.

PubMed

Rajendran, Vivek; Puvendran, Kirubhakaran; Guru, Bharath Raja; Jayaraman, Guhan

2016-02-01

Hyaluronic acid has a wide range of biomedical applications and its commercial value is highly dependent on its purity and molecular weight. This study highlights the utility of aqueous two-phase separation as a primary recovery step for hyaluronic acid and for removal of major protein impurities from fermentation broths. Metabolically engineered cultures of a lactate dehydrogenase mutant strain of Lactococcus lactis (L. lactis NZ9020) were used to produce high-molecular-weight hyaluronic acid. The cell-free fermentation broth was partially purified using a polyethylene glycol/potassium phosphate system, resulting in nearly 100% recovery of hyaluronic acid in the salt-rich bottom phase in all the aqueous two-phase separation experiments. These experiments were optimized for maximum removal of protein impurities in the polyethylene glycol rich top phase. The removal of protein impurities resulted in substantial reduction of membrane fouling in the subsequent diafiltration process, carried out with a 300 kDa polyether sulfone membrane. This step resulted in considerable purification of hyaluronic acid, without any loss in recovery and molecular weight. Diafiltration was followed by an adsorption step to remove minor impurities and achieve nearly 100% purity. The final hyaluronic acid product was characterized by Fourier-transform IR and NMR spectroscopy, confirming its purity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of solid-phase microextraction coupled with liquid chromatography for analysis of tramadol in brain tissue using its molecularly imprinted polymer.

PubMed

Habibi-Khorasani, Monireh; Mohammadpour, Amir Hooshang; Mohajeri, Seyed Ahmad

2017-02-01

In this work, performance of a molecularly imprinted polymer (MIP) as a selective solid-phase microextraction sorbent for the extraction and enrichment of tramadol in aqueous solution and rabbit brain tissue, is described. Binding properties of MIPs were studied in comparison with their nonimprinted polymer (NIP). Ten milligrams of the optimized MIP was then evaluated as a sorbent, for preconcentration, in molecularly imprinted solid-phase microextraction (MISPME) of tramadol from aqueous solution and rabbit brain tissue. The analytical method was calibrated in the range of 0.004 ppm (4 ng mL -1 ) and 10 ppm (10 μg mL -1 ) in aqueous media and in the ranges of 0.01 and 10 ppm in rabbit brain tissue, respectively. The results indicated significantly higher binding affinity of MIPs to tramadol, in comparison with NIP. The MISPME procedure was developed and optimized with a recovery of 81.12-107.54% in aqueous solution and 76.16-91.20% in rabbit brain tissue. The inter- and intra-day variation values were <8.24 and 5.06%, respectively. Finally the calibrated method was applied for determination of tramadol in real rabbit brain tissue samples after administration of a lethal dose. Our data demonstrated the potential of MISPME for rapid, sensitive and cost-effective sample analysis. Copyright © 2016 John Wiley & Sons, Ltd.

Analysis of n-alkanes at sub microgram per liter level after direct solid phase microextraction from aqueous samples.

PubMed

Farajzadeh, Mirali; Hatami, Mehdi

2002-11-01

This work describes the application of the previously presented solid phase microextraction (SPME) fiber in direct mode for sampling of C10-C20 n-alkanes from aqueous solution. The fiber has simple composition and is constructed from activated charcoal:PVC suspension in tetrahydrofuran. When the composition of the fiber was optimized that the optimum composition was 90:10 (activated charcoal:PVC) for direct mode, whereas it was 75:25 for sampling from the headspace of aqueous samples. This fiber is completely stable in contact with water. The extraction efficiency is improved in the presence of 0.1 M NaCl. The value is between 17.8-38.5% for the first extraction, which better than the efficiency of similar commercial fibers. After seven extractions, all analytes are removed from the aqueous samples nearly 100%. Single fiber repeatability and fiber-to-fiber reproducibility are good and both are less than 13% for all studied alkanes. Finally, direct mode SPME was used in the determination of n-alkanes in the range of sub microg L(-1) without any additional preconcentration procedure. Gas chromatography along with flame ionization detection were used for separation and detection of the studied analytes.

Synthetic Biology in Aqueous Compartments at the Micro- and Nanoscale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boreyko, Jonathan; Caveney, Patrick M.; Norred, Sarah L.

ABSTRACT Aqueous two-phase systems and related emulsion-based structures defined within micro- and nanoscale environments enable a bottom-up synthetic biological approach to mimicking the dynamic compartmentation of biomaterial that naturally occurs within cells. Model systems we have developed to aid in understanding these phenomena include on-demand generation and triggering of reversible phase transitions in ATPS confined in microscale droplets, morpho-logical changes in networks of femtoliter-volume aqueous droplet interface bilayers (DIBs) formulated in microfluidic channels, and temperature-driven phase transitions in interfacial lipid bilayer systems supported on micro and nanostructured substrates. For each of these cases, the dynamics were intimately linked to changesmore » in the chemical potential of water, which becomes increasingly susceptible to confinement and crowding. At these length scales, where interfacial and surface areas predominate over compartment volumes, both evaporation and osmotic forces become enhanced relative to ideal dilute solutions. Finally, consequences of confinement and crowding in cell-sized microcompartments for increasingly complex scenarios will be discussed, from single-molecule mobility measurements with fluorescence correlation spectroscopy to spatio-temporal modulation of resource sharing in cell-free gene expression bursting.« less

Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U 24

DOE PAGES

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer; ...

2018-04-18

Here, we obtained a kerosene-soluble form of the lithium salt [UO 2(O 2)(OH) 2] 24 phase (Li-U 24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U 24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U 24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U 24 inmore » both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U 24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U 24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.« less

Synthetic Biology in Aqueous Compartments at the Micro- and Nanoscale

DOE PAGES

Boreyko, Jonathan; Caveney, Patrick M.; Norred, Sarah L.; ...

2017-07-10

ABSTRACT Aqueous two-phase systems and related emulsion-based structures defined within micro- and nanoscale environments enable a bottom-up synthetic biological approach to mimicking the dynamic compartmentation of biomaterial that naturally occurs within cells. Model systems we have developed to aid in understanding these phenomena include on-demand generation and triggering of reversible phase transitions in ATPS confined in microscale droplets, morpho-logical changes in networks of femtoliter-volume aqueous droplet interface bilayers (DIBs) formulated in microfluidic channels, and temperature-driven phase transitions in interfacial lipid bilayer systems supported on micro and nanostructured substrates. For each of these cases, the dynamics were intimately linked to changesmore » in the chemical potential of water, which becomes increasingly susceptible to confinement and crowding. At these length scales, where interfacial and surface areas predominate over compartment volumes, both evaporation and osmotic forces become enhanced relative to ideal dilute solutions. Finally, consequences of confinement and crowding in cell-sized microcompartments for increasingly complex scenarios will be discussed, from single-molecule mobility measurements with fluorescence correlation spectroscopy to spatio-temporal modulation of resource sharing in cell-free gene expression bursting.« less

Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U 24

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer

Here, we obtained a kerosene-soluble form of the lithium salt [UO 2(O 2)(OH) 2] 24 phase (Li-U 24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U 24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U 24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U 24 inmore » both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U 24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U 24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.« less

MODIFICATION OF AEROSOL MASS AND SIZE DISTRIBUTION DUE TO AQUEOUS-PHASE SO2 OXIDATION IN CLOUDS: COMPARISONS OF SEVERAL MODELS. (R827929)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Dynamics of rigid microparticles at the interface of co-flowing immiscible liquids in a microchannel.

PubMed

Jayaprakash, K S; Banerjee, U; Sen, A K

2017-05-01

We report the dynamical migration behavior of rigid polystyrene microparticles at an interface of co-flowing streams of primary CP 1 (aqueous) and secondary CP 2 (oils) immiscible phases at low Reynolds numbers (Re) in a microchannel. The microparticles initially suspended in the CP 1 either continue to flow in the bulk CP 1 or migrate across the interface into CP 2 , when the stream width of the CP 1 approaches the diameter of the microparticles. Experiments were performed with different secondary phases and it is found that the migration criterion depends on the sign of the spreading parameter S and the presence of surfactant at the interface. To substantiate the migration criterion, experiments were also carried out by suspending the microparticles in CP 2 (oil phase). Our study reveals that in case of aqueous-silicone oil combination, the microparticles get attached to the interface since S<0 and the three phase contact angle, θ>90°. For complete detachment of microparticles from the interface into the secondary phase, additional energy ΔG is needed. We discuss the role of interfacial perturbation, which causes detachment of microparticles from the interface. In case of mineral and olive oils, the surfactants present at the interface prevents attachment of the microparticles to the interface due to the repulsive disjoining pressure. Finally, using a aqueous-silicone oil system, we demonstrate size based sorting of microparticles of size 25μm and 15μm respectively from that of 15μm and 10μm and study the variation of separation efficiency η with the ratio of the width of the aqueous stream to the diameter of the microparticles ρ. Copyright © 2017 Elsevier Inc. All rights reserved.

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

A Study of the γ-Radiolysis of N,N-Didodecyl-N',N'-Dioctyldiglycolamide Using UHPLC-ESI-MS Analysis

DOE PAGES

Roscioli-Johnson, Kristyn M.; Zarzana, Christopher A.; Groenewold, Gary S.; ...

2016-07-12

In this paper, solutions of N,N-didodecyl-N',N'-dioctyldiglycolamide in n-dodecane were subjected to γ-irradiation in the presence and absence of both an aqueous nitric acid phase and air sparging. The solutions were analyzed using ultra-high-performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) to determine the rates of radiolytic decay of the extractant as well as to identify radiolysis products. The DGA concentration decreased exponentially with increasing dose, and the measured degradation rate constants were uninfluenced by the presence or absence of acidic aqueous phase, or by air sparging. Finally, the identified radiolysis products suggest that the bonds most vulnerable to radiolytic attack are thosemore » in the diglycolamide center of these molecules and not in the side chains.« less

DISTRIBUTION OF URANIUM, ZIRCONIUM, NIOBIUM, RUTHENIUM AND CERIUM BETWEEN NITRIC ACID SOLUTIONS AND 10% TLA-5% OCTYL ALCOHOL/SHELL SOL-T

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez-Menchero, E.; Centeno, J.; Magni, G.

1962-03-01

The extraction of traces of Ru, Zr, Nb, Ce, and U at low concentrations (5 mg/l in aqueous solution) from nitric acid solutions using trilauryl amine (TLA) has been experimentally studied. TLA will eventually be used for final purification of plutonium. Room-temperature data on plutonium contaminant distribution between aqueous solutions of varying nitric acid concentrations and a Shellsol-T solution containing l0% TlA and 5% octyl alcohol are presented. Within the temperature and nitric acid concentration ranges tested, the extractability of uranium increased with increased acid concentrations, although acid concentration in the aqueous phase had no effect on the decontamination factorsmore » for the main fission products. (H.G.G.)« less

Aqueous dispersion polymerization: a new paradigm for in situ block copolymer self-assembly in concentrated solution.

PubMed

Sugihara, Shinji; Blanazs, Adam; Armes, Steven P; Ryan, Anthony J; Lewis, Andrew L

2011-10-05

Reversible addition-fragmentation chain transfer polymerization has been utilized to polymerize 2-hydroxypropyl methacrylate (HPMA) using a water-soluble macromolecular chain transfer agent based on poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC). A detailed phase diagram has been elucidated for this aqueous dispersion polymerization formulation that reliably predicts the precise block compositions associated with well-defined particle morphologies (i.e., pure phases). Unlike the ad hoc approaches described in the literature, this strategy enables the facile, efficient, and reproducible preparation of diblock copolymer spheres, worms, or vesicles directly in concentrated aqueous solution. Chain extension of the highly hydrated zwitterionic PMPC block with HPMA in water at 70 °C produces a hydrophobic poly(2-hydroxypropyl methacrylate) (PHPMA) block, which drives in situ self-assembly to form well-defined diblock copolymer spheres, worms, or vesicles. The final particle morphology obtained at full monomer conversion is dictated by (i) the target degree of polymerization of the PHPMA block and (ii) the total solids concentration at which the HPMA polymerization is conducted. Moreover, if the targeted diblock copolymer composition corresponds to vesicle phase space at full monomer conversion, the in situ particle morphology evolves from spheres to worms to vesicles during the in situ polymerization of HPMA. In the case of PMPC(25)-PHPMA(400) particles, this systematic approach allows the direct, reproducible, and highly efficient preparation of either block copolymer vesicles at up to 25% solids or well-defined worms at 16-25% solids in aqueous solution.

Morphological Differentiation of Colon Carcinoma Cell Lines in Rotating Wall Vessels

NASA Technical Reports Server (NTRS)

Jessup, J. M.

1994-01-01

The objectives of this project were to determine whether (1) microgravity permits unique, three-dimensional cultures of neoplastic human colon tissues and (2) this culture interaction produces novel intestinal growth and differentiation factors. The initial phase of this project tested the efficacy of simulated microgravity for the cultivation and differentiation of human colon carcinoma in rotating wall vessels (RWV's) on microcarrier beads. The RWV's simulate microgravity by randomizing the gravity vector in an aqueous medium under a low shear stress environment in unit gravity. This simulation achieves approximately a one-fifth g environment that allows cells to 'float' and form three-dimensional relationships with less shear stress than in other stirred aqueous medium bioreactors. In the second phase of this project we assessed the ability of human colon carcinoma lines to adhere to various substrates because adhesion is the first event that must occur to create three-dimensional masses. Finally, we tested growth factor production in the last phase of this project.

Extraction studies. Final report, May 6, 1996--September 30, 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

During the first week of this effort, an Alpkem RFA-300 4-channel automated chemical analyzer was transferred to the basement of building 42 at TA-46 for the purpose of performing extraction studies. Initially, this instrumentation was applied to soil samples known to contain DNA. Using the SFA (Segmented Flow Analysis) technique, several fluidic systems were evaluated to perform on-line filtration of several varieties of soil obtained from Cheryl Kuske and Kaysie Banton (TA-43, Bldg. 1). Progress reports were issued monthly beginning May 15, 1996. Early in 1997 there was a shift from the conventional 2-phase system (aqueous + air) to amore » 3-phase system (oil + aqueous + air) to drastically reduce sample size and reagent consumption. Computer animation was recorded on videotape for presentations. The time remaining on the subcontract was devoted to setting up existing equipment to incorporate the 3rd phase (a special fluorocarbon oil obtained from DuPont).« less

Corrosion behavior of a superduplex stainless steel in chloride aqueous solution

NASA Astrophysics Data System (ADS)

Dabalà, Manuele; Calliari, Irene; Variola, Alessandra

2004-04-01

Super duplex stainless steels (SDSS) have been widely used as structural materials for chemical plants (especially in those engaged in phosphoric acid production), in the hydrometallurgy industries, and as materials for offshore applications due to their excellent corrosion resistance in chloride environments, compared with other commercial types of ferritic stainless steels. These alloys also possess superior weldability and better mechanical properties than austenitic stainless steels. However, due to their two-phase structure, the nature of which is very dependent on their composition and thermal history, the behavior of SDSS regarding localized corrosion appears difficult to predict, especially in chloride environments. To improve their final properties, the effect of the partition of the alloying elements between the two phases, and the composition and microstructure of each phase are the key to understanding the localized corrosion phenomena of SDSS. This paper concerns the effects of the SDSS microstructure and heat treatment on the SDSS corrosion resistance in aqueous solutions, containing different amounts of NaCl at room temperature.

Simultaneous Separation of Manganese, Cobalt, and Nickel by the Organic-Aqueous-Aqueous Three-Phase Solvent Extraction

NASA Astrophysics Data System (ADS)

Shirayama, Sakae; Uda, Tetsuya

2016-04-01

This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.

Fluid Inclusion Study of Quartz Xenocrysts in Mafic Dykes from Kawant Area, Chhota Udaipur District, Gujarat, India

NASA Astrophysics Data System (ADS)

Randive, Kirtikumar; Hurai, Vratislav

2015-09-01

Unusual mafic dykes occur in the proximity of the Ambadongar Carbonatite Complex, Lower Narmada Valley, Gujarat, India. The dykes contain dense population of quartz xenocrysts within the basaltic matrix metasomatised by carbonate-rich fluids. Plagioclase feldspars, relict pyroxenes, chlorite, barite, rutile, magnetite, Fe-Ti oxides and glass were identified in the basaltic matrix. Quartz xenocrysts occur in various shapes and sizes and form an intricate growth pattern with carbonates. The xenocrysts are fractured and contain several types of primary and secondary, single phase and two-phase fluid inclusions. The two-phase inclusions are dominated by aqueous liquid, whereas the monophase inclusions are composed of carbonic gas and the aqueous inclusions homogenize to liquid between 226°C and 361°C. Majority of the inclusions are secondary in origin and are therefore unrelated to the crystallization of quartz. Moreover, the inclusions have mixed carbonic-aqueous compositions that inhibit their direct correlation with the crustal or mantle fluids. The composition of dilute CO2-rich fluids observed in the quartz xenocrysts appear similar to those exsolved during the final stages of evolution of the Amba Dongar carbonatites. However, the carbonates are devoid of fluid inclusions and therefore their genetic relation with the quartz xenocrysts cannot be established.

Effect of polyethylene glycol on the liquid–liquid phase transition in aqueous protein solutions

PubMed Central

Annunziata, Onofrio; Asherie, Neer; Lomakin, Aleksey; Pande, Jayanti; Ogun, Olutayo; Benedek, George B.

2002-01-01

We have studied the effect of polyethylene glycol (PEG) on the liquid–liquid phase separation (LLPS) of aqueous solutions of bovine γD-crystallin (γD), a protein in the eye lens. We observe that the phase separation temperature increases with both PEG concentration and PEG molecular weight. PEG partitioning, which is the difference between the PEG concentration in the two coexisting phases, has been measured experimentally and observed to increase with PEG molecular weight. The measurements of both LLPS temperature and PEG partitioning in the ternary γD-PEG-water systems are used to successfully predict the location of the liquid–liquid phase boundary of the binary γD-water system. We show that our LLPS measurements can be also used to estimate the protein solubility as a function of the concentration of crystallizing agents. Moreover, the slope of the tie-lines and the dependence of LLPS temperature on polymer concentration provide a powerful and sensitive check of the validity of excluded volume models. Finally, we show that the increase of the LLPS temperature with PEG concentration is due to attractive protein–protein interactions. PMID:12391331

Solvent extraction system for plutonium colloids and other oxide nano-particles

DOEpatents

Soderholm, Lynda; Wilson, Richard E; Chiarizia, Renato; Skanthakumar, Suntharalingam

2014-06-03

The invention provides a method for extracting plutonium from spent nuclear fuel, the method comprising supplying plutonium in a first aqueous phase; contacting the plutonium aqueous phase with a mixture of a dielectric and a moiety having a first acidity so as to allow the plutonium to substantially extract into the mixture; and contacting the extracted plutonium with second a aqueous phase, wherein the second aqueous phase has a second acidity higher than the first acidity, so as to allow the extracted plutonium to extract into the second aqueous phase. The invented method facilitates isolation of plutonium polymer without the formation of crud or unwanted emulsions.

Final report for demonstration of in situ oxidation of DNAPL using the Geo-Cleanse technology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jerome, K.M.; Riha, B.; Looney, B.B.

1997-09-23

At large industrial sites like the A/M Area of the Savannah River Site (SRS), undissolved dense non-aqueous phase liquid (DNAPL) in soil and groundwater is the most significant barrier to successful clean up. DNAPL acts as a reservoir that will continue to generate contaminant levels far above remediation concentration goals well into the future.

Different Diversity and Distribution of Archaeal Community in the Aqueous and Oil Phases of Production Fluid From High-Temperature Petroleum Reservoirs.

PubMed

Liang, Bo; Zhang, Kai; Wang, Li-Ying; Liu, Jin-Feng; Yang, Shi-Zhong; Gu, Ji-Dong; Mu, Bo-Zhong

2018-01-01

To get a better knowledge on how archaeal communities differ between the oil and aqueous phases and whether environmental factors promote substantial differences on microbial distributions among production wells, we analyzed archaeal communities in oil and aqueous phases from four high-temperature petroleum reservoirs (55-65°C) by using 16S rRNA gene based 454 pyrosequencing. Obvious dissimilarity of the archaeal composition between aqueous and oil phases in each independent production wells was observed, especially in production wells with higher water cut, and diversity in the oil phase was much higher than that in the corresponding aqueous phase. Statistical analysis further showed that archaeal communities in oil phases from different petroleum reservoirs tended to be more similar, but those in aqueous phases were the opposite. In the high-temperature ecosystems, temperature as an environmental factor could have significantly affected archaeal distribution, and archaeal diversity raised with the increase of temperature ( p < 0.05). Our results suggest that to get a comprehensive understanding of petroleum reservoirs microbial information both in aqueous and oil phases should be taken into consideration. The microscopic habitats of oil phase, technically the dispersed minuscule water droplets in the oil could be a better habitat that containing the indigenous microorganisms.

Titania-catalyzed radiofluorination of tosylated precursors in highly aqueous medium

DOE PAGES

Sergeev, Maxim E.; Morgia, Federica; Lazari, Mark; ...

2015-04-10

Nucleophilic radiofluorination is an efficient synthetic route to many positron-emission tomography (PET) probes, but removal of water to activate the cyclotron-produced [ 18F]fluoride has to be performed prior to reaction, which significantly increases overall radiolabeling time and causes radioactivity loss. In this paper, we demonstrate the possibility of 18F-radiofluorination in highly aqueous medium. The method utilizes titania nanoparticles, 1:1 (v/v) acetonitrile–thexyl alcohol solvent mixture, and tetra-n-butylammonium bicarbonate as a phase-transfer agent. Efficient radiolabeling is directly performed with aqueous [ 18F]fluoride without the need for a drying/azeotroping step to significantly reduce radiosynthesis time. High radiochemical purity of the target compound ismore » also achieved. Finally, the substrate scope of the synthetic strategy is demonstrated with a range of aromatic, aliphatic, and cycloaliphatic tosylated precursors.« less

METHOD FOR SEPARATION OF PLUTONIUM FROM URANIUM AND FISSION PRODUCTS BY SOLVENT EXTRACTION

DOEpatents

Seaborg, G.T.; Blaedel, W.J.; Walling, M.T. Jr.

1960-08-23

A process is given for separating from each other uranium, plutonium, and fission products in an aqueous nitric acid solution by the so-called Redox process. The plutonium is first oxidized to the hexavalent state, e.g., with a water-soluble dichromate or sodium bismuthate, preferably together with a holding oxidant such as potassium bromate. potassium permanganate, or an excess of the oxidizing agent. The solution is then contacted with a water-immiscible organic solvent, preferably hexone. whereby uranium and plutonium are extracted while the fission products remain in the aqueous solution. The separated organic phase is then contacted with an aqueous solution of a reducing agent, with or without a holding reductant (e.g., with a ferrous salt plus hydrazine or with ferrous sulfamate), whereby plutonium is reduced to the trivalent state and back- extracted into the aqueous solution. The uranium may finally be back-extracted from the organic solvent (e.g., with a 0.1 N nitric acid).

Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiayue; Lu, Lu; Zhao, Chen

2014-03-01

Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO 2, the selective hydrogenolysis dominates for cleaving the C aliphatic-O bond. Catalyzed by themore » dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO 2 or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.« less

Determination of sex hormones and nonylphenol ethoxylates in the aqueous matrixes of two pilot-scale municipal wastewater treatment plants.

PubMed

Esperanza, Mar; Suidan, Makram T; Nishimura, Fumitake; Wang, Zhong-Min; Sorial, George A; Zaffiro, Alan; McCauley, Paul; Brenner, Richard; Sayles, Gregory

2004-06-01

Two analytical methods were developed and refined for the detection and quantitation of two groups of endocrine-disrupting chemicals (EDCs) in the liquid matrixes of two pilot-scale municipal wastewater treatment plants. The targeted compounds are seven sex hormones (estradiol, ethinylestradiol, estrone, estriol, testosterone, progesterone, and androstenedione), a group of nonionic surfactants (nonylphenol polyethoxylates), and their biodegradation byproducts nonylphenol and nonylphenol ethoxylates with one, two, and three ethoxylates. Solid phase extraction using C-18 for steroids and graphitized carbon black for the surfactants were used for extraction. HPLC-DAD and GC/MS were used for quantification. Each of the two 20 L/h pilot-scale plants consists of a primary settling tank followed by a three-stage aeration tank and final clarification. The primary and the waste-activated sludge are digested anaerobically in one plant and aerobically in the other. The pilot plants are fed with a complex synthetic wastewater spiked with the EDCs. Once steady state was reached, liquid samples were collected from four sampling points to obtain the profile for all EDCs along the treatment system. Complete removal from the aqueous phase was obtained for testosterone, androstenedione, and progesterone. Removals for nonylphenol polyethoxylates, estradiol, estrone, and ethinylestradiol from the aqueous phase exceeded 96%, 94%, 52%, and 50%, respectively. Levels of E3 in the liquid phase were low, and no clear conclusions could be drawn concerning its removal.

Quantitative analysis of aqueous phase composition of model dentin adhesives experiencing phase separation

PubMed Central

Ye, Qiang; Park, Jonggu; Parthasarathy, Ranganathan; Pamatmat, Francis; Misra, Anil; Laurence, Jennifer S.; Marangos, Orestes; Spencer, Paulette

2013-01-01

There have been reports of the sensitivity of our current dentin adhesives to excess moisture, for example, water-blisters in adhesives placed on over-wet surfaces, and phase separation with concomitant limited infiltration of the critical dimethacrylate component into the demineralized dentin matrix. To determine quantitatively the hydrophobic/hydrophilic components in the aqueous phase when exposed to over-wet environments, model adhesives were mixed with 16, 33, and 50 wt % water to yield well-separated phases. Based upon high-performance liquid chromatography coupled with photodiode array detection, it was found that the amounts of hydrophobic BisGMA and hydrophobic initiators are less than 0.1 wt % in the aqueous phase. The amount of these compounds decreased with an increase in the initial water content. The major components of the aqueous phase were hydroxyethyl methacrylate (HEMA) and water, and the HEMA content ranged from 18.3 to 14.7 wt %. Different BisGMA homologues and the relative content of these homologues in the aqueous phase have been identified; however, the amount of crosslinkable BisGMA was minimal and, thus, could not help in the formation of a crosslinked polymer network in the aqueous phase. Without the protection afforded by a strong crosslinked network, the poorly photoreactive compounds of this aqueous phase could be leached easily. These results suggest that adhesive formulations should be designed to include hydrophilic multimethacrylate monomers and water compatible initiators. PMID:22331596

POLONIUM SEPARATION PROCESS

DOEpatents

Karraker, D.G.

1959-07-14

A liquid-liquid extraction process is presented for the recovery of polonium from lead and bismuth. According to the invention an acidic aqueous chloride phase containing the polonium, lead, and bismuth values is contacted with a tributyl phosphate ether phase. The polonium preferentially enters the organic phase which is then separated and washed with an aqueous hydrochloric solution to remove any lead or bismuth which may also have been extracted. The now highly purified polonium in the organic phase may be transferred to an aqueous solution by extraction with aqueous nitric acid.

Solar Powered Remediation and pH Control

DTIC Science & Technology

2017-04-13

Kitanidis, and P.L. McCarty. 2004. Possible factors controlling the effectiveness of bioenhanced dissolution of non -aqueous phase tetrachloroethene...FINAL REPORT Solar Powered Remediation and pH Control ESTCP Project ER-201033 APRIL 2017 David Lippincott, PG CB&I Federal... control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ORGANIZATION. 1. REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 3. DATES COVERED (From - To

Mechanism of Hg(II) Immobilization in Sediments by Sulfate-Cement Amendment.

PubMed

Serrano, Susana; Vlassopoulos, Dimitri; O'Day, Peggy A

2016-04-01

Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO 4 amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg L III - and S K-edge. In amended sediments, XRD, SEM and sulfur K-edge XANES indicated formation of gypsum in seawater experiments or ettringite-type (Ca 6 Al 2 (SO 4 ) 3 (OH) 12 . 26H 2 O) phases in fresh water experiments, depending on the final solution pH (seawater ∼8.5; freshwater ∼10.5). Analysis of Hg EXAFS spectra showed Cl and Hg ligands in the first- and second-coordination shells at distances characteristic of a polynuclear chloromercury(II) salt, perhaps as a nanoparticulate phase, in both seawater and fresh water experiments. In addition to the chloromercury species, a smaller fraction (∼20-25%) of Hg was bonded to O atoms in fresh water sample spectra, suggesting the presence of a minor sorbed Hg fraction. In the absence of amendment treatment, Hg sorption and resistance to extraction can be accounted for by relatively strong binding by reduced S species present in the marsh sediment detected by S XANES. Thermodynamic calculations predict stable aqueous Hg-Cl species at seawater final pH, but higher final pH in fresh water favors aqueous Hg-hydroxide species. The difference in Hg coordination between aqueous and solid phases suggests that the initial Hg-Cl coordination was stabilized in the cement hydration products and did not re-equilibrate with the bulk solution with aging. Collectively, results suggest physical encapsulation of Hg as a polynuclear chloromercury(II) salt as the primary immobilization mechanism.

CLEPS 1.0: A new protocol for cloud aqueous phase oxidation of VOC mechanisms

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, Camille; Deguillaume, Laurent; Monod, Anne; Perroux, Hélène; Rose, Clémence; Ghigo, Giovanni; Long, Yoann; Leriche, Maud; Aumont, Bernard; Patryl, Luc; Armand, Patrick; Chaumerliac, Nadine

2017-03-01

A new detailed aqueous phase mechanism named the Cloud Explicit Physico-chemical Scheme (CLEPS 1.0) is proposed to describe the oxidation of water soluble organic compounds resulting from isoprene oxidation. It is based on structure activity relationships (SARs) which provide global rate constants together with branching ratios for HOṡ abstraction and addition on atmospheric organic compounds. The GROMHE SAR allows the evaluation of Henry's law constants for undocumented organic compounds. This new aqueous phase mechanism is coupled with the MCM v3.3.1 gas phase mechanism through a mass transfer scheme between gas phase and aqueous phase. The resulting multiphase mechanism has then been implemented in a model based on the Dynamically Simple Model for Atmospheric Chemical Complexity (DSMACC) using the Kinetic PreProcessor (KPP) that can serve to analyze data from cloud chamber experiments and field campaigns. The simulation of permanent cloud under low-NOx conditions describes the formation of oxidized monoacids and diacids in the aqueous phase as well as a significant influence on the gas phase chemistry and composition and shows that the aqueous phase reactivity leads to an efficient fragmentation and functionalization of organic compounds.

Experiment and Optimization for Simultaneous Carbonation of Ca2+ and Mg2+ in A Two-phase System of Insoluble Diisobutylamine and Aqueous Solution

NASA Astrophysics Data System (ADS)

Wang, Wenlong; Wang, Man; Liu, Xin; Wang, Peng; Xi, Zhenqian

2015-06-01

An optimized approach of CO2 fixation in Ca2+/Mg2+-rich aqueous solutions using insoluble amine as an enhancing medium was reported. Apparent basicity was verified to be an effective indicator for the selection and optimization of organic amine systems and finally the diisobutylamine + n-octanol system was selected to enhance the carbonation reactions of CO2 in an artificial Ca2+/Mg2+-rich solution. In our experiments, when the volume ratio of insoluble organic phase to aqueous one was 2:1 and the reaction temperature was 28 °C, 92% of Ca2+ and 80% of Mg2+ could be converted to calcium and magnesium carbonate precipitates within 5 min of reaction with the bubbling-in of CO2. The organic amine system could be regenerated by using carbide slag as the regeneration agent and could still show attractive enhancement performances after 7 rounds of carbonation-regeneration experiments. In this way, the CO2 capture and sequestration was realized within one single process, with value-added Ca/Mg carbonates being the byproducts. In view of the vast availability of Ca2+/Mg2+-rich aqueous solutions and the feasible technical coordination with desalination industry, this novel process may have a good application potential in the future.

Development of cost-effective surfactant flooding technology. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pope, G.A.; Sepehrnoori, K.

1996-11-01

Task 1 of this research was the development of a high-resolution, fully implicit, finite-difference, multiphase, multicomponent, compositional simulator for chemical flooding. The major physical phenomena modeled in this simulator are dispersion, heterogeneous permeability and porosity, adsorption, interfacial tension, relative permeability and capillary desaturation, compositional phase viscosity, compositional phase density and gravity effects, capillary pressure, and aqueous-oleic-microemulsion phase behavior. Polymer and its non-Newtonian rheology properties include shear-thinning viscosity, permeability reduction, inaccessible pore volume, and adsorption. Options of constant or variable space grids and time steps, constant-pressure or constant-rate well conditions, horizontal and vertical wells, and multiple slug injections are also availablemore » in the simulator. The solution scheme used in this simulator is fully implicit. The pressure equation and the mass-conservation equations are solved simultaneously for the aqueous-phase pressure and the total concentrations of each component. A third-order-in-space, second-order-in-time finite-difference method and a new total-variation-diminishing (TVD) third-order flux limiter are used that greatly reduce numerical dispersion effects. Task 2 was the optimization of surfactant flooding. The code UTCHEM was used to simulate surfactant polymer flooding.« less

Simultaneous enantioselective determination of six pesticides in aqueous environmental samples by chiral liquid chromatography with tandem mass spectrometry.

PubMed

Zhao, Pengfei; Lei, Shuo; Xing, Mingming; Xiong, Shihang; Guo, Xingjie

2018-03-01

A robust and sensitive method was developed for the enantiomeric analysis of six chiral pesticides (including metalaxyl, epoxiconazole, myclobutanil, hexaconazole, napropamide, and isocarbophos) in aquatic environmental samples. The optimized chromatographic conditions for the quantification of all the 12 enantiomers were performed with Chiralcel OD-RH column using mobile phase consisting of 0.1% aqueous formic acid and acetonitrile operated under reversed-phase conditions and then analyzed using liquid chromatography with tandem mass spectrometry. Twelve enantiomers were detected in multiple reaction monitoring mode. Solid-phase extraction and dispersive liquid-liquid microextraction were employed in this study. Response surface methodology was applied to assist in the dispersive liquid-liquid microextraction optimization. Under the optimum conditions, recoveries of pesticides enantiomers varied from 83.0 to 103.2% at two spiked levels with relative standard deviation less than 11.5%. The concentration factors were up to 1000 times. Method detection and quantification limits varied from 0.11 to 0.48 ng/L and from 0.46 to 1.49 ng/L, respectively. Finally, this method was used to determination of the enantiomers composition of the six pesticides in environmental aqueous matrices, which will help better understand the behavior of individual enantiomer and make accurate risk assessment to ecosystems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Treatment of aqueous phase of bio-oil by granular activated carbon and evaluation of biogas production.

PubMed

Shanmugam, Saravanan R; Adhikari, Sushil; Wang, Zhouhang; Shakya, Rajdeep

2017-01-01

Hydrothermal liquefaction of wet biomass such as algae is a promising thermochemical process for the production of bio-oil. Bio-oil aqueous phase generated during liquefaction process is rich in complex organics and can be utilized for biogas production following its pre-treatment with granular activated carbon. In our study, use of 30% activated carbon resulted in higher chemical oxygen demand (COD) reduction (53±0.3%) from aqueous phase. Higher CH 4 production (84±12mL/gCOD) was also observed in 30% carbon-treated aqueous phase fed cultures, whereas only 32±6mLCH 4 /gCOD was observed in control (non-carbon treated) cultures. The results from this study indicate that almost 67±0.3% initial COD of aqueous phase can be reduced using a combination of both carbon treatment and biogas production. This study shows that aqueous phase can be utilized for CH 4 production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling Degradation Product Partitioning in Chlorinated-DNAPL Source Zones

NASA Astrophysics Data System (ADS)

Boroumand, A.; Ramsburg, A.; Christ, J.; Abriola, L.

2009-12-01

Metabolic reductive dechlorination degrades aqueous phase contaminant concentrations, increasing the driving force for DNAPL dissolution. Results from laboratory and field investigations suggest that accumulation of cis-dichloroethene (cis-DCE) and vinyl chloride (VC) may occur within DNAPL source zones. The lack of (or slow) degradation of cis-DCE and VC within bioactive DNAPL source zones may result in these dechlorination products becoming distributed among the solid, aqueous, and organic phases. Partitioning of cis-DCE and VC into the organic phase may reduce aqueous phase concentrations of these contaminants and result in the enrichment of these dechlorination products within the non-aqueous phase. Enrichment of degradation products within DNAPL may reduce some of the advantages associated with the application of bioremediation in DNAPL source zones. Thus, it is important to quantify how partitioning (between the aqueous and organic phases) influences the transport of cis-DCE and VC within bioactive DNAPL source zones. In this work, abiotic two-phase (PCE-water) one-dimensional column experiments are modeled using analytical and numerical methods to examine the rate of partitioning and the capacity of PCE-DNAPL to reversibly sequester cis-DCE. These models consider aqueous-phase, nonaqueous phase, and aqueous plus nonaqueous phase mass transfer resistance using linear driving force and spherical diffusion expressions. Model parameters are examined and compared for different experimental conditions to evaluate the mechanisms controlling partitioning. Biot number, a dimensionless number which is an index of the ratio of the aqueous phase mass transfer rate in boundary layer to the mass transfer rate within the NAPL, is used to characterize conditions in which either or both processes are controlling. Results show that application of a single aqueous resistance is capable to capture breakthrough curves when DNAPL is distributed in porous media as low-saturation ganglia, while diffusion within the DNAPL should be considered for larger NAPL pools. These results offer important insights to the monitoring and interpretation of bioremediation strategies employed within DNAPL source zones.

Cloud Chemistry in the United States: Problems and Prospects

NASA Astrophysics Data System (ADS)

Carlton, A. G.; Barth, M. C.; Lance, S.; Fahey, K.; McNeill, V. F.; Weber, R. J.

2017-12-01

Clouds cover 60% of the Earth's surface at a given time and are the primary means by which atmospheric trace species are lofted from the polluted boundary layer to the free troposphere. Clouds also play an important role as atmospheric aqueous phase reactors, scavenging soluble gas phase precursors and providing a medium for oxidation reactions that yield lower volatility products that contribute to increased aerosol mass when cloud drops evaporate. On a global average, most sulfate particles are formed during cloud processing, and organic particles known to form through aqueous phase pathways are found above clouds. However, atmospheric chemistry observations are generally biased for clear sky conditions. For example, aircraft field deployments typically avoid clouds. Satellite retrievals impacted by clouds are often screened from the final data products. This hinders knowledge of cloud chemistry and the impacts on tropospheric composition. In this work, we explore temporal and geospatial trends in trace species related to cloud processing in the U.S. with a focus on organic chemistry. We apply 3-dimensional and 0-dimensional models to recent campaigns and mountaintop cloud sampling sites, and compare to measurements.

CHARMM Drude Polarizable Force Field for Aldopentofuranoses and Methyl-aldopentofuranosides

PubMed Central

Jana, Madhurima; MacKerell, Alexander D.

2015-01-01

An empirical all-atom CHARMM polarizable force filed for aldopentofuranoses and methyl-aldopentofuranosides based on the classical Drude oscillator is presented. A single electrostatic model is developed for eight different diastereoisomers of aldopentofuranoses by optimizing the existing electrostatic and bonded parameters as transferred from ethers, alcohols and hexopyranoses to reproduce quantum mechanical (QM) dipole moments, furanose-water interaction energies and conformational energies. Optimization of selected electrostatic and dihedral parameters was performed to generate a model for methyl-aldopentofuranosides. Accuracy of the model was tested by reproducing experimental data for crystal intramolecular geometries and lattice unit cell parameters, aqueous phase densities, and ring pucker and exocyclic rotamer populations as obtained from NMR experiments. In most cases the model is found to reproduce both QM data and experimental observables in an excellent manner, while for the remainder the level of agreement is in the satisfactory regimen. In aqueous phase simulations the monosaccharides have significantly enhanced dipoles as compared to the gas phase. The final model from this study is transferrable for future studies on carbohydrates and can be used with the existing CHARMM Drude polarizable force field for biomolecules. PMID:26018564

Continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process: An efficient diesel treatment by injection of the aqueous phase.

PubMed

Rahimi, Masoud; Shahhosseini, Shahrokh; Movahedirad, Salman

2017-11-01

A new continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process was developed in order to decrease energy and aqueous phase consumption. In this process the aqueous phase is injected below the horn tip leading to enhanced mixing of the phases. Diesel fuel as the oil phase with sulfur content of 1550ppmw and an appropriate mixture of hydrogen peroxide and formic acid as the aqueous phase were used. At the first step, the optimized condition for the sulfur removal has been obtained in the batch mode operation. Hence, the effect of more important oxidation parameters; oxidant-to-sulfur molar ratio, acid-to-sulfur molar ratio and sonication time were investigated. Then the optimized conditions were obtained using Response Surface Methodology (RSM) technique. Afterwards, some experiments corresponding to the best batch condition and also with objective of minimizing the residence time and aqueous phase to fuel volume ratio have been conducted in a newly designed double-compartment reactor with injection of the aqueous phase to evaluate the process in a continuous flow operation. In addition, the effect of nozzle diameter has been examined. Significant improvement on the sulfur removal was observed specially in lower sonication time in the case of dispersion method in comparison with the conventional contact between two phases. Ultimately, the flow pattern induced by ultrasonic device, and also injection of the aqueous phase were analyzed quantitatively and qualitatively by capturing the sequential images. Copyright © 2017 Elsevier B.V. All rights reserved.

Conversion of raw lignocellulosic biomass into branched long-chain alkanes through three tandem steps.

PubMed

Li, Chunrui; Ding, Daqian; Xia, Qineng; Liu, Xiaohui; Wang, Yanqin

2016-07-07

Synthesis of branched long-chain alkanes from renewable biomass has attracted intensive interest in recent years, but the feedstock for this synthesis is restricted to platform chemicals. Here, we develop an effective and energy-efficient process to convert raw lignocellulosic biomass (e.g., corncob) into branched diesel-range alkanes through three tandem steps for the first time. Furfural and isopropyl levulinate (LA ester) were prepared from hemicellulose and cellulose fractions of corncob in toluene/water biphasic system with added isopropanol, which was followed by double aldol condensation of furfural with LA ester into C15 oxygenates and the final hydrodeoxygenation of C15 oxygenates into branched long-chain alkanes. The core point of this tandem process is the addition of isopropanol in the first step, which enables the spontaneous transfer of levulinic acid (LA) into the toluene phase in the form of LA ester through esterification, resulting in LA ester co-existing with furfural in the same phase, which is the basis for double aldol condensation in the toluene phase. Moreover, the acidic aqueous phase and toluene can be reused and the residues, including lignin and humins in aqueous phase, can be separated and carbonized to porous carbon materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel three-stage kinetic model for aqueous benzene adsorption on activated carbon.

PubMed

Choi, Jae-Woo; Choi, Nag-Choul; Lee, Soon-Jae; Kim, Dong-Ju

2007-10-15

We propose a novel kinetic model for adsorption of aqueous benzene onto both granular activated carbon (GAC) and powdered activated carbon (PAC). The model is based on mass conservation of benzene coupled with three-stage adsorption: (1) the first portion for an instantaneous stage or external surface adsorption, (2) the second portion for a gradual stage with rate-limiting intraparticle diffusion, and (3) the third portion for a constant stage in which the aqueous phase no longer interacts with activated carbon. An analytical solution of the kinetic model was validated with the kinetic data obtained from aqueous benzene adsorption onto GAC and PAC in batch experiments with two different solution concentrations (C(0)=300 mg L(-1), 600 mg L(-1)). Experimental results revealed that benzene adsorption for the two concentrations followed three distinct stages for PAC but two stages for GAC. The analytical solution could successfully describe the kinetic adsorption of aqueous benzene in the batch reaction system, showing a fast instantaneous adsorption followed by a slow rate-limiting adsorption and a final long constant adsorption. Use of the two-stage model gave incorrect values of adsorption coefficients in the analytical solution due to inability to describe the third stage.

On the vibrational characteristics of single- and double-walled carbon nanotubes containing ice nanotube in aqueous environment

NASA Astrophysics Data System (ADS)

Ansari, R.; Ajori, S.; Ameri, A.

2015-10-01

The properties and behavior of carbon nanotubes (CNTs) in aqueous environment due to their considerable potential applications in nanobiotechnology and designing nanobiosensors have attracted the attention of researchers. In this study, molecular dynamics simulations are carried out to investigate the vibrational characteristics of single- and double-walled CNTs containing ice nanotubes (a new phase of ice) in vacuum and aqueous environments. The results demonstrate that formation of ice nanotubes inside the CNTs reduces the natural frequency of pure CNTs. Moreover, it is demonstrated that increasing the number of walls considerably reduces the sensitivity of frequency to the presence of ice nanotube inside CNT. Additionally, it is shown that increasing the length decreases the effect of ice nanotube on reducing the frequency. The calculation of natural frequency of CNTs in aqueous media demonstrates that the interaction of CNTs with water molecules considerably reduces the natural frequency up to 50 %. Finally, it is demonstrated that in the case of CNTs with one free end in aqueous environment, the CNT does not vibrate in its first mode, and its frequency is between the frequencies of first and second modes of vibration.

Electroactivity of Aptamer at Soft Microinterface Arrays.

PubMed

Felisilda, Bren Mark B; Arrigan, Damien W M

2018-06-26

The electrochemical behavior of a synthetic oligonucleotide, thrombin-binding aptamer (TBA, 15-mer), was explored at a liquid-organogel microinterface array. TBA did not display any response when only background electrolytes were present in both phases. On the basis of literature reports that surfactants can influence nucleic acid detection, the response in the presence of cetyltrimethylammonium (CTA + ) was examined. With both TBA and CTA + in the aqueous phase, the transfer current for CTA + was diminished, signifying the interaction of CTA + with TBA. Experiments with CTA + spiked into the organic phase revealed a sharp current peak, consistent with the interfacial formation of a CTA + -TBA complex. However, use of CTA + as the organic phase electrolyte cation, as the salt with tetrakis(4-chlorophenyl)borate, greatly improved the response to TBA. In this case, a distinctive peak response (at ca. -0.25 V) was attributed to the transfer of CTA + across the soft interface to complex with aqueous phase TBA. Employing this process as a detection step enabled a detection limit of 0.11 μM TBA (by cyclic voltammetry). Furthermore, the presence of magnesium cations at physiological concentration resulted in the disappearance of the TBA response because of Mg 2+ -induced folding of TBA. Also, the current response of TBA was decreased by the addition of thrombin, indicating TBA interacted with this binding partner. Finally, the interfacial surfactant-aptamer interaction was explored in a synthetic urine matrix that afforded a detection limit of 0.29 μM TBA. These results suggest that aptamer-binding interactions can be monitored by electrochemistry at aqueous-organic interfaces and open up a new possibility for detection in aptamer-binding assays.

Biphasic catalysis in water/carbon dioxide micellar systems

DOEpatents

Jacobson, Gunilla B.; Tumas, William; Johnston, Keith P.

2002-01-01

A process is provided for catalyzing an organic reaction to form a reaction product by placing reactants and a catalyst for the organic reaction, the catalyst of a metal complex and at least one ligand soluble within one of the phases of said aqueous biphasic system, within an aqueous biphasic system including a water phase, a dense phase fluid, and a surfactant adapted for forming an emulsion or microemulsion within the aqueous biphasic system, the reactants soluble within one of the phases of the aqueous biphasic system and convertible in the presence of the catalyst to a product having low solubility in the phase in which the catalyst is soluble; and, maintaining the aqueous biphasic system under pressures, at temperatures, and for a period of time sufficient for the organic reaction to occur and form the reaction product and to maintain sufficient density on the dense phase fluid, the reaction product characterized as having low solubility in the phase in which the catalyst is soluble.

Effect of Coriolis force on counter-current chromatographic separation by centrifugal partition chromatography.

PubMed

Ikehata, Jun-Ichi; Shinomiya, Kazufusa; Kobayashi, Koji; Ohshima, Hisashi; Kitanaka, Susumu; Ito, Yoichiro

2004-02-06

The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems.

Three phases hollow fiber LPME combined with HPLC-UV for extraction, preconcentration and determination of valerenic acid in Valeriana officinalis.

PubMed

Mirzaei, Mohamad; Dinpanah, Hossein

2011-07-01

In the present work, the applicability of hollow fiber-based liquid phase microextraction (HF-LPME) was evaluated for the extraction and preconcentration of valerenic acid prior to its determination by reversed-phase HPLC/UV. The target drug was extracted from 5.0 mL of aqueous solution with pH 3.5 into an organic extracting solvent (dihexyl ether) impregnated in the pores of a hollow fiber and finally back extracted into 10 μ L of aqueous solution with pH 9.5 located inside the lumen of the hollow fiber. In order to obtain high extraction efficiency, the parameters affecting the HF-LPME, including pH of the donor and acceptor phases, type of organic phase, ionic strength, the volume ratio of donor to acceptor phase, stirring rate and extraction time were studied and optimized. Under the optimized conditions, enrichment factor up to 446 was achieved and the relative standard deviation (RSD) of the method was 4.36% (n = 9). The linear range was 7.5-850 μg L⁻¹ with correlation coefficient (r²=0.999), detection limits was 2.5 μg L⁻¹ and the LOQ was 7.5 μg L⁻¹. The proposed method was evaluated by extraction and determination of valerenic acid in some Iranian wild species of Valerianaceae. Copyright © 2011 Elsevier B.V. All rights reserved.

Application of aqueous two-phase micellar system to improve extraction of adenoviral particles from cell lysate.

PubMed

Molino, João Vitor Dutra; Lopes, André Moreni; Viana Marques, Daniela de Araújo; Mazzola, Priscila Gava; da Silva, Joas Lucas; Hirata, Mario Hiroyuki; Hirata, Rosário Dominguez Crespo; Gatti, Maria Silvia Viccari; Pessoa, Adalberto

2017-12-04

Viral vectors are important in medical approaches, such as disease prevention and gene therapy, and their production depends on efficient prepurification steps. In the present study, an aqueous two-phase micellar system (ATPMS) was evaluated to extract human adenovirus type 5 particles from a cell lysate. Adenovirus was cultured in human embryonic kidney 293 (HEK-293) cells to a concentration of 1.4 × 10 10 particles/mL. Cells were lysed, and the system formed by direct addition of Triton X-114 in a 2 3 full factorial design with center points. The systems were formed with Triton X-114 at a final concentration of 1.0, 6.0, and 11.0% (w/w), cell lysate pH of 6.0, 6.5, and 7.0, and incubation temperatures at 33, 35, and 37 °C. Adenovirus particles recovered from partition phases were measured by qPCR. The best system condition was with 11.0% (w/w) of Triton X-114, a cell lysate pH of 7.0, and an incubation temperature at 33 °C, yielding 3.51 × 10 10 adenovirus particles/mL, which increased the initial adenovirus particles concentration by 2.3-fold, purifying it by 2.2-fold from the cell lysate, and removing cell debris. In conclusion, these results demonstrated that the use of an aqueous two-phase micellar system in the early steps of downstream processing could improve viral particle extraction from cultured cells while integrating clarification, concentration, and prepurification steps. © 2017 International Union of Biochemistry and Molecular Biology, Inc.

Reversible, on-demand generation of aqueous two-phase microdroplets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collier, Charles Patrick; Retterer, Scott Thomas; Boreyko, Jonathan Barton

The present invention provides methods of on-demand, reversible generation of aqueous two-phase microdroplets core-shell microbeads, microparticle preparations comprising the core-shell microbeads, and drug delivery formulation comprising the microparticle preparations. Because these aqueous microdroplets have volumes comparable to those of cells, they provide an approach to mimicking the dynamic microcompartmentation of biomaterial that naturally occurs within the cytoplasm of cells. Hence, the present methods generate femtoliter aqueous two-phase droplets within a microfluidic oil channel using gated pressure pulses to generate individual, stationary two-phase microdroplets with a well-defined time zero for carrying out controlled and sequential phase transformations over time. Reversible phasemore » transitions between single-phase, two-phase, and core-shell microbead states are obtained via evaporation-induced dehydration and water rehydration.« less

Polarimetric glucose sensing using Brewster reflection applying a rotating retarder analyzer

NASA Astrophysics Data System (ADS)

Boeckle, Stefan; Rovati, Luigi L.; Ansari, Rafat R.

2003-10-01

Previously, we proposed a polarimetric method, that exploits the Brewster-reflection with the final goal of application to the human eye (reflection off the eye lens) for non-invasive glucose sensing. The linearly polarized reflected light of this optical scheme is rotated by the glucose molecules present in the aqueous humor, thus carries the blood glucose concentration information. A proof-of-concept experimental bench-top setup is presented, applying a multi-wavelength true phase measurement approach and a rotating phase retarder as an analyzer to measure the very small rotation angles and the complete polarization state of the measurement light.

Characterizing Fullerene Nanoparticles in Aqueous Suspensions

EPA Science Inventory

Studies have indicated that fullerenes can form stable colloidal suspensions in water when introduced to the aqueous phase through solvent exchange, sonication, or extended mixing. The colloidal suspensions created using these techniques have effective aqueous phase concentratio...

Measurement of Biologically Available Naphthalene in Gas and Aqueous Phases by Use of a Pseudomonas putida Biosensor

PubMed Central

Werlen, Christoph; Jaspers, Marco C. M.; van der Meer, Jan Roelof

2004-01-01

Genetically constructed microbial biosensors for measuring organic pollutants are mostly applied in aqueous samples. Unfortunately, the detection limit of most biosensors is insufficient to detect pollutants at low but environmentally relevant concentrations. However, organic pollutants with low levels of water solubility often have significant gas-water partitioning coefficients, which in principle makes it possible to measure such compounds in the gas rather than the aqueous phase. Here we describe the first use of a microbial biosensor for measuring organic pollutants directly in the gas phase. For this purpose, we reconstructed a bioluminescent Pseudomonas putida naphthalene biosensor strain to carry the NAH7 plasmid and a chromosomally inserted gene fusion between the sal promoter and the luxAB genes. Specific calibration studies were performed with suspended and filter-immobilized biosensor cells, in aqueous solution and in the gas phase. Gas phase measurements with filter-immobilized biosensor cells in closed flasks, with a naphthalene-contaminated aqueous phase, showed that the biosensor cells can measure naphthalene effectively. The biosensor cells on the filter responded with increasing light output proportional to the naphthalene concentration added to the water phase, even though only a small proportion of the naphthalene was present in the gas phase. In fact, the biosensor cells could concentrate a larger proportion of naphthalene through the gas phase than in the aqueous suspension, probably due to faster transport of naphthalene to the cells in the gas phase. This led to a 10-fold lower detectable aqueous naphthalene concentration (50 nM instead of 0.5 μM). Thus, the use of bacterial biosensors for measuring organic pollutants in the gas phase is a valid method for increasing the sensitivity of these valuable biological devices. PMID:14711624

Production of a metal-binding exopolysaccharide by Paenibacillus jamilae using two-phase olive-mill waste as fermentation substrate.

PubMed

Morillo, Jose Antonio; Aguilera, Margarita; Ramos-Cormenzana, Alberto; Monteoliva-Sánchez, Mercedes

2006-09-01

The present study investigated the use of two-phase olive mill waste (TPOMW) as substrate for the production of exopolysaccharide (EPS) by the endospore-forming bacilli Paenibacillus jamilae. This microorganism was able to grow and produce EPS in aqueous extracts of TPOMW as a unique source of carbon. The effects of substrate concentration and the addition of inorganic nutrients were investigated. Maximal polymer yield in 100-ml batch-culture experiments (2 g l(-1)) was obtained in cultures prepared with an aqueous extract of 20% TPOMW (w/v). An inhibitory effect was observed on growth and EPS production when TPOMW concentration was increased. Nutrient supplementation (nitrate, phosphate, and other inorganic nutrients) did not increase yield. Finally, an adsorption experiment of Pb (II), Cd (II), Cu (II), Zn (II), Co (II), and Ni (II) by EPS is reported. Lead was preferentially complexed by the polymer, with a maximal uptake of 230 mg/g EPS.

[Isolation and purification of alpha-glycerophosphate oxidase in a polyethylene glycol/(NH4 )2SO4 aqueous two-phase system].

PubMed

Meng, Yao; Jin, Jiagui; Liu, Shuangfeng; Yang, Min; Zhang, Qinglian; Wan, Li; Tang, Kun

2014-02-01

Alpha-glycerophosphate oxidase (alpha-GPO) from Enterococcus casseli flavus was successfully isolated and purified by using polyethylene glycol (PEG)/(NH4)2SO4 aqueous two-phase system (ATPS). The results showed that the chosen PEG/(NH4)2SO4 ATPS could be affected by PEG molecular weight, pH, concentration of PEG and (NH4)2SO4, and inorganic salt as well as additional amount of crude enzyme. After evaluating these influencing factors, the final optimum purification strategy was formed by 16.5% (m/m) PEG2000, 13.2% (m/m) (NH4)2SO4, pH 7.5 and 30% (m/m) additive crude enzyme, respectively. The NaCl was a negative influencing factor which would lead to lower purification fold and activity recovery. These conditions eventually resulted in the activity recovery of 89% (m/m), distribution coefficient of 1.2 and purification fold of 7.0.

Laboratory studies of aqueous-phase oxidation of polyols in submicron particles

NASA Astrophysics Data System (ADS)

Daumit, K. E.; Carrasquillo, A. J.; Hunter, J. F.; Kroll, J. H.

2013-12-01

Aqueous-phase oxidation has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. However most aqueous oxidation studies are performed in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation is carried out within submicron particles, allowing for gas-particle partitioning of reactants, intermediates, and products. Using Fenton chemistry as a source of hydroxyl radicals, and a high-resolution aerosol mass spectrometer (AMS) for online characterization of particle composition, we find that aqueous oxidation can be quite rapid. The formation of high concentrations of oxalic acid is observed in the particle phase with some loss of carbon to the gas phase, indicating the formation of volatile products. We see a rapid degradation of condensed-phase oxidation products upon exposure to ultraviolet lights (centered at 350 nm) suggesting that these products may exist as iron(III)-oxalate complexes. Similar results are also seen when oxidation is carried out in bulk solution (with AMS analysis of the atomized solution); however in some cases the mass loss is less than is observed for submicron particles, likely due to differences in partitioning of early-generation products. Such products can partition out of the aqueous phase at the low liquid water contents in the chamber but remain in solution for further aqueous processing in bulk oxidation experiments. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different than those in bulk oxidation, pointing to the need to carry out aqueous oxidation studies under atmospherically relevant partitioning conditions (with liquid water contents mimicking those of cloud droplets or wet aerosol).

Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields

NASA Astrophysics Data System (ADS)

Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort

2014-10-01

Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) × 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 ± 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H [Idaho Falls, ID; Todd, Terry A [Aberdeen, ID; Tranter, Troy J [Idaho Falls, ID; Horwitz, E Philip [Naperville, IL

2009-10-06

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Tranter, Troy J.; Horwitz, E. Philip

2007-01-02

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Method and apparatus for the removal of bioconversion of constituents of organic liquids

DOEpatents

Scott, Timothy; Scott, Charles D.

1994-01-01

A method and apparatus for the removal or conversion of constituents from bulk organic liquids. A countercurrent biphasic bioreactor system is utilized to disperse and recoalesce a biocatalyst contained in the aqueous liquid phase into the organic liquid phase containing the constituent. Two transient, high-intensity electrical fields rupture the aqueous drops into a plurality of microdroplets and induce continuous coalescence and redispersion as the microdroplets travel through the organic phase, thus increasing surface area. As the aqueous microdroplets progress through the organic phase, the biocatalyst then reacts with the constituent to produce a product which is then removed from the bioreactor in the aqueous phase or retained in the organic phase. The organic liquid, now free of the original constituents, is ready for immediate use or further processing.

Method for separating water soluble organics from a process stream by aqueous biphasic extraction

DOEpatents

Chaiko, David J.; Mego, William A.

1999-01-01

A method for separating water-miscible organic species from a process stream by aqueous biphasic extraction is provided. An aqueous biphase system is generated by contacting a process stream comprised of water, salt, and organic species with an aqueous polymer solution. The organic species transfer from the salt-rich phase to the polymer-rich phase, and the phases are separated. Next, the polymer is recovered from the loaded polymer phase by selectively extracting the polymer into an organic phase at an elevated temperature, while the organic species remain in a substantially salt-free aqueous solution. Alternatively, the polymer is recovered from the loaded polymer by a temperature induced phase separation (cloud point extraction), whereby the polymer and the organic species separate into two distinct solutions. The method for separating water-miscible organic species is applicable to the treatment of industrial wastewater streams, including the extraction and recovery of complexed metal ions from salt solutions, organic contaminants from mineral processing streams, and colorants from spent dye baths.

Ionic liquid-salt aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of sulfonamides in water and food.

PubMed

Han, Juan; Wang, Yun; Liu, Yan; Li, Yanfang; Lu, Yang; Yan, Yongsheng; Ni, Liang

2013-02-01

Ionic liquid-salt aqueous two-phase extraction coupled with high-performance liquid chromatography with ultraviolet detection was developed for the determination of sulfonamides in water and food samples. In the procedure, the analytes were extracted from the aqueous samples into the ionic liquid top phase in one step. Three sulfonamides, sulfamerazine, sulfamethoxazole, and sulfamethizole were selected here as model compounds for developing and evaluating the method. The effects of various experimental parameters in extraction step were studied using two optimization methods, one variable at a time and Box-Behnken design. The results showed that the amount of sulfonamides did not have effect on the extraction efficiency. Therefore, a three-level Box-Behnken experimental design with three factors, which combined the response surface modeling, was used to optimize sulfonamides extraction. Under the most favorable extraction parameters, the detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target compounds were achieved within the range of 0.15-0.3 ng/mL and 0.5-1.0 ng/mL from spiked samples, respectively, which are lower than or comparable with other reported approaches applied to the determination of the same compounds. Finally, the proposed method was successfully applied to the determination of sulfonamide compounds in different water and food samples and satisfactory recoveries of spiked target compounds in real samples were obtained.

Responsive copolymers for enhanced petroleum recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCormick, Charles; Hester, Roger

The objectives of this work were to: synthesize responsive, amphiphilic systems; characterize molecular structure and solution behavior; measure rheological properties of the aqueous fluids including behavior in fixed geometry flow profiles and beds; and to tailor final polymer compositions for in situ rheology control under simulated reservoir conditions. This report focuses on the first phase of the research emphasizing synthesis and the development of photophysical techniques and rheological means of following segmental organization at the structural level.

Adsorptive separation in bioprocess engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, E.W.Y.

1987-01-01

The invention and development of an energy-efficient separation technique for recovery of desired chemicals from biomass conversion would greatly enhance the economic viability of this bioprocess. Adsorptive separation of several chemicals from aqueous solution was studied in this thesis. The desired species were recovered from the dilute aqueous solution by using crosslinked polyvinylpyridine resin to effect selective sorption. The sorbed chemicals were then removed from the resin by either thermal regeneration or elution with some appropriate desorbents. The effects of temperature, pH value, and solute concentration on resin swelling were investigated. The adsorption equilibrium isotherms, resin capacities and resin selectivitiesmore » of methanol, ethanol, 1-propanol, isopropanol, glycerol, acetone, 1-butanol, tert-butanol, and 2,3-butanediol were determined to study the homologies. Furthermore, acetic acid, butyric acid, hydrochloric acid, lactic acid, and sulfuric acid were recovered from very dilute aqueous solutions. The concentration of the sorbed chemical in the stationary phase can be many times higher than in the mobile phase for some acids. Finally, different types of equilibrium isotherms were used to fit the experimental data. A mathematical model was developed by using the theory of interference to predict the breakthrough curves and the process efficiency to provide information for large-scale process design and development.« less

Tube Radial Distribution Flow Separation in a Microchannel Using an Ionic Liquid Aqueous Two-Phase System Based on Phase Separation Multi-Phase Flow.

PubMed

Nagatani, Kosuke; Shihata, Yoshinori; Matsushita, Takahiro; Tsukagoshi, Kazuhiko

2016-01-01

Ionic liquid aqueous two-phase systems were delivered into a capillary tube to achieve tube radial distribution flow (TRDF) or annular flow in a microspace. The phase diagram, viscosity of the phases, and TRDF image of the 1-butyl-3-methylimidazolium chloride and NaOH system were examined. The TRDF was formed with inner ionic liquid-rich and outer ionic liquid-poor phases in the capillary tube. The phase configuration was explained using the viscous dissipation principle. We also examined the distribution of rhodamine B in a three-branched microchannel on a microchip with ionic liquid aqueous two-phase systems for the first time.

Final Report: Molecular Mechanisms of Interfacial Reactivity in Near Surface and Extreme Geochemical Environments (DE-SC0009362)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dixon, David A

2016-03-27

The prediction of the long-term stability and safety of geologic sequestration of greenhouse gases requires a detailed understanding of subsurface transport and chemical interactions between the disposed greenhouse gases and the geologic media. In this regard, mineral-fluid interactions are of prime importance since reactions that occur on or near the interface can assist in the long term sequestration of CO2 by trapping in mineral phases such as carbonates, as well as influencing the subsurface migration of the disposed fluids via creation or plugging of pores or fractures in the host rock strata. Previous research on mineral-fluid interaction for subsurface CO2more » storage has focused almost entirely on the aqueous phase, i.e., reactivity with aqueous solutions or brines containing dissolved CO2. However, interactions with neat to water-saturated non-aqueous fluids are of equal if not greater importance since supercritical CO2 (scCO2) is less dense than the aqueous phase or oil which will create a buoyant scCO2 plume that ultimately will dominate the pore volume within the caprock, and the injected scCO2 will contain water soon after injection and this water can be highly reactive. Collectively, therefore, mineral interactions with water-saturated scCO2-dominated fluids are pivotal and could result in the stable sequestration of CO2 by trapping in mineral phases such as metal carbonates within otherwise permeable zones in the caprock. The primary objective is to unravel the molecular mechanisms governing the reactivity of mineral phases important in the geologic sequestration of CO2 with variably wet supercritical carbon dioxide as a function of T, P, and mineral structure using computational chemistry. This work is in close collaboration with the PNNL Geosciences effort. The focus of the work at The University of Alabama is computational studies of the formation of magnesium and calcium carbonates and oxides and their reactivity and providing computational support of the experimental efforts at PNNL, especially for energetics, structural properties, and interpretation of spectra.« less

Biochemical characterization of sap (latex) of a few Indian mango varieties.

PubMed

John, K Saby; Bhat, S G; Prasada Rao, U J S

2003-01-01

Mango sap (latex) from four Indian varieties was studied for its composition. Sap was separated into non-aqueous and aqueous phases. Earlier, we reported that the non-aqueous phase contained mainly mono-terpenes having raw mango aroma (Phytochemistry 52 (1999) 891). In the present study biochemical composition of the aqueous phase was studied. Aqueous phase contained little amount of protein (2.0-3.5 mg/ml) but showed high polyphenol oxidase (147-214 U/mg protein) and peroxidase (401-561 U/mg protein) activities. It contained low amounts of polyphenols and protease activities. On native PAGE, all the major protein bands exhibited both polyphenol oxidase and peroxidase activities. Both polyphenol oxidase and peroxidase activities were found to be stable in the aqueous phase of sap at 4 degrees C. Sap contained large amount of non-dialyzable and non-starchy carbohydrate (260-343 mg/ml sap) which may be responsible for maintaining a considerable pressure of fluid in the ducts. Thus, the mango sap could be a valuable by-product in the mango industry as it contains some of the valuable enzymes and aroma components.

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

Stable Aqueous Foams from Cellulose Nanocrystals and Methyl Cellulose.

PubMed

Hu, Zhen; Xu, Richard; Cranston, Emily D; Pelton, Robert H

2016-12-12

The addition of cellulose nanocrystals (CNC) greatly enhanced the properties of methylcellulose (MC) stabilized aqueous foams. CNC addition decreased air bubble size, initial foam densities and drainage rates. Mixtures of 2 wt % CNC + 0.5 wt % MC gave the lowest density foams. This composition sits near the onset of nematic phase formation and also near the overlap concentration of methylcellulose. More than 94% of the added CNC particles remained in the foam phase, not leaving with the draining water. We propose that the nanoscale CNC particles bind to the larger MC coils both in solution and with MC at the air/water interface, forming weak gels that stabilize air bubbles. Wet CNC-MC foams were sufficiently robust to withstand high temperature (70 °C for 6 h) polymerization of water-soluble monomers giving macroporous CNC composite hydrogels based on acrylamide (AM), 2-hydroxyethyl methacrylate (HEMA), or polyethylene glycol diacrylate (PEGDA). At high temperatures, the MC was present as a fibrillar gel phase reinforced by CNC particles, explaining the very high foam stability. Finally, our CNC-MC foams are based on commercially available forms of CNC and MC, already approved for many applications. This is a "shovel-ready" technology.

In situ continuous derivatization/pre-concentration of carbonyl compounds with 2,4-dinitrophenylhydrazine in aqueous samples by solid-phase extraction Application to liquid chromatography determination of aldehydes.

PubMed

Baños, Clara-Eugenia; Silva, Manuel

2009-03-15

A rapid and straightforward continuous solid-phase extraction system has been developed for in situ derivatization and pre-concentration of carbonyl compounds in aqueous samples. Initially 2,4-dinitrophenylhydrazine, the derivatizing agent, was adsorbed on a C(18) mini-column and then 15-ml of sample were continuously aspirated into the flow system, where the derivatization and pre-concentration of the analytes (low-molecular mass aldehydes) were performed simultaneously. Following elution, 20 microl of the extract were injected into a LC-DAD system, in which hydrazones were successfully separated in 12 min on a RP-C(18) column using a linear gradient mobile phase of acetonitrile-water of 60-100% acetonitrile for 8 min, flowing at 0.5 ml/min. The whole analytical process can be accomplished within ca. 35 min. Under optimum conditions, limits of detection were obtained between 0.3 and 1.0 microg/l and RSDs (inter-day precision) from 1.2 to 4.6%. Finally, some applications on water samples are presented with recoveries ranged from 95.8 to 99.4%.

Evaluation of amorphous magnesium phosphate (AMP) based non-exothermic orthopedic cements.

PubMed

Babaie, Elham; Lin, Boren; Goel, Vijay K; Bhaduri, Sarit B

2016-10-07

This paper reports for the first time the development of a biodegradable, non-exothermic, self-setting orthopedic cement composition based on amorphous magnesium phosphate (AMP). The occurrence of undesirable exothermic reactions was avoided through using AMP as the solid precursor. The phenomenon of self-setting with optimum rheology is achieved by incorporating a water soluble biocompatible/biodegradable polymer, polyvinyl alcohol (PVA). Additionally, PVA enables a controlled growth of the final phase via a biomimetic process. The AMP powder was synthesized using a precipitation method. The powder, when in contact with the aqueous PVA solution, forms a putty resulting in a nanocrystalline magnesium phosphate phase of cattiite. The as-prepared cement compositions were evaluated for setting times, exothermicity, compressive strength, biodegradation, and microstructural features before and after soaking in SBF, and in vitro cytocompatibility. Since cattiite is relatively unexplored in the literature, a first time evaluation reveals that it is cytocompatible, just like the other phases in the MgO-P 2 O 5 (Mg-P) system. The cement composition prepared with 15% PVA in an aqueous medium achieved clinically relevant setting times, mechanical properties, and biodegradation. Simulated body fluid (SBF) soaking resulted in coating of bobierrite onto the cement particle surfaces.

The Secondary Organic Aerosol Processor (SOAP v1.0) model: a unified model with different ranges of complexity based on the molecular surrogate approach

NASA Astrophysics Data System (ADS)

Couvidat, F.; Sartelet, K.

2015-04-01

In this paper the Secondary Organic Aerosol Processor (SOAP v1.0) model is presented. This model determines the partitioning of organic compounds between the gas and particle phases. It is designed to be modular with different user options depending on the computation time and the complexity required by the user. This model is based on the molecular surrogate approach, in which each surrogate compound is associated with a molecular structure to estimate some properties and parameters (hygroscopicity, absorption into the aqueous phase of particles, activity coefficients and phase separation). Each surrogate can be hydrophilic (condenses only into the aqueous phase of particles), hydrophobic (condenses only into the organic phases of particles) or both (condenses into both the aqueous and the organic phases of particles). Activity coefficients are computed with the UNIFAC (UNIversal Functional group Activity Coefficient; Fredenslund et al., 1975) thermodynamic model for short-range interactions and with the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) parameterization for medium- and long-range interactions between electrolytes and organic compounds. Phase separation is determined by Gibbs energy minimization. The user can choose between an equilibrium representation and a dynamic representation of organic aerosols (OAs). In the equilibrium representation, compounds in the particle phase are assumed to be at equilibrium with the gas phase. However, recent studies show that the organic aerosol is not at equilibrium with the gas phase because the organic phases could be semi-solid (very viscous liquid phase). The condensation-evaporation of organic compounds could then be limited by the diffusion in the organic phases due to the high viscosity. An implicit dynamic representation of secondary organic aerosols (SOAs) is available in SOAP with OAs divided into layers, the first layer being at the center of the particle (slowly reaches equilibrium) and the final layer being near the interface with the gas phase (quickly reaches equilibrium). Although this dynamic implicit representation is a simplified approach to model condensation-evaporation with a low number of layers and short CPU (central processing unit) time, it shows good agreements with an explicit representation of condensation-evaporation (no significant differences after a few hours of condensation).

Method and apparatus for the removal or bioconversion of constituents of organic liquids

DOEpatents

Scott, T.; Scott, C.D.

1994-10-25

A method and apparatus are disclosed for the removal or conversion of constituents from bulk organic liquids. A countercurrent biphasic bioreactor system is utilized to disperse and recoalesce a biocatalyst contained in the aqueous liquid phase into the organic liquid phase containing the constituent. Two transient, high-intensity electrical fields rupture the aqueous drops into a plurality of microdroplets and induce continuous coalescence and redispersion as the microdroplets travel through the organic phase, thus increasing surface area. As the aqueous microdroplets progress through the organic phase, the biocatalyst then reacts with the constituent to produce a product which is then removed from the bioreactor in the aqueous phase or retained in the organic phase. The organic liquid, now free of the original constituents, is ready for immediate use or further processing. 1 fig.

Impact of In-Cloud Aqueous Processes on the Chemistry and Transport of Biogenic Volatile Organic Compounds

NASA Astrophysics Data System (ADS)

Li, Yang; Barth, Mary C.; Patton, Edward G.; Steiner, Allison L.

2017-10-01

We investigate the impacts of cloud aqueous processes on the chemistry and transport of biogenic volatile organic compounds (BVOC) using the National Center for Atmospheric Research's large-eddy simulation code with an updated chemical mechanism that includes both gas- and aqueous-phase reactions. We simulate transport and chemistry for a meteorological case with a diurnal pattern of nonprecipitating cumulus clouds from the Baltimore-Washington area DISCOVER-AQ campaign. We evaluate two scenarios with and without aqueous-phase chemical reactions. In the cloud layer (2-3 km), the addition of aqueous phase reactions decreases HCHO by 18% over the domain due to its solubility and the fast depletion from aqueous reactions, resulting in a corresponding decrease in radical oxidants (e.g., 18% decrease in OH). The decrease of OH increases the mixing ratios of isoprene and methacrolein (MACR) (100% and 15%, respectively) in the cloud layer because the reaction rate is lower. Aqueous-phase reactions can modify the segregation between OH and BVOC by changing the sign of the segregation intensity, causing up to 55% reduction in the isoprene-OH reaction rate and 40% reduction for the MACR-OH reaction when clouds are present. Analysis of the isoprene-OH covariance budget shows the chemistry term is the primary driver of the strong segregation in clouds, triggered by the decrease in OH. All organic acids except acetic acid are formed only through aqueous-phase reactions. For acids formed in the aqueous phase, turbulence mixes these compounds on short time scales, with the near-surface mixing ratios of these acids reaching 20% of the mixing ratios in the cloud layer within 1 h of cloud formation.

Carrier mediated hollow fiber liquid phase microextraction combined with HPLC-UV for preconcentration and determination of some tetracycline antibiotics.

PubMed

Shariati, Shahab; Yamini, Yadollah; Esrafili, Ali

2009-02-01

In the present study, a simple and efficient preconcentration method was developed using carrier mediated three phase liquid phase microextraction prior to HPLC-UV for simultaneous extraction and determination of trace amounts of highly hydrophilic tetracycline antibiotics including tetracycline (TCN), oxytetracycline (OTCN) and doxycycline (DCN) in bovine milk, human plasma and water samples. For extraction, 11.0 mL of the aqueous sample containing TCNs and 0.05 M Na(2)HPO(4) (9.10.995). Finally, applicability of the proposed method was successfully confirmed by extraction and determination of the drugs in water and plasma samples as well as in bovine milk samples with low and high fat contents. Comparing to the traditional methods, the proposed method exhibits high sensitivity and high preconcentration factors as well as good precision. The extraction setup is simple and due to active transport of analytes, high cleanup effect and good selectivity are obtained in extraction process.

Synthesis and Characterization of Functional Mesostructures Using Colloidal Crystal Templating

DTIC Science & Technology

2004-01-01

fluorescent probes in aqueous polymer solutions . Khoury and co-workers measured the diffusion coefficient of several fluorescein-labeled proteins in...diffraction naq refractive index of the aqueous solution phase xvii ni refractive index of component i ngel refractive index of the hydrogel...phase Tg glass transition temperature α angle of diffraction φaq volume fraction of the aqueous solution phase φi volume fraction of

Ca(2+) -complex stability of GAPAGPLIVPY peptide in gas and aqueous phase, investigated by affinity capillary electrophoresis and molecular dynamics simulations and compared to mass spectrometric results.

PubMed

Nachbar, Markus; El Deeb, Sami; Mozafari, Mona; Alhazmi, Hassan A; Preu, Lutz; Redweik, Sabine; Lehmann, Wolf Dieter; Wätzig, Hermann

2016-03-01

Strong, sequence-specific gas-phase bindings between proline-rich peptides and alkaline earth metal ions in nanoESI-MS experiments were reported by Lehmann et al. (Rapid Commun. Mass Spectrom. 2006, 20, 2404-2410), however its relevance for physiological-like aqueous phase is uncertain. Therefore, the complexes should also be studied in aqueous solution and the relevance of the MS method for binding studies be evaluated. A mobility shift ACE method was used for determining the binding between the small peptide GAPAGPLIVPY and various metal ions in aqueous solution. The findings were compared to the MS results and further explained using computational methods. While the MS data showed a strong alkaline earth ion binding, the ACE results showed nonsignificant binding. The proposed vacuum state complex also decomposed during a molecular dynamic simulation in aqueous solution. This study shows that the formed stable peptide-metal ion adducts in the gas phase by ESI-MS does not imply the existence of analogous adducts in the aqueous phase. Comparing peptide-metal ion interaction under the gaseous MS and aqueous ACE conditions showed huge difference in binding behavior. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anthracene and pyrene photolysis kinetics in aqueous, organic, and mixed aqueous-organic phases

NASA Astrophysics Data System (ADS)

Grossman, Jarod N.; Stern, Adam P.; Kirich, Makena L.; Kahan, Tara F.

2016-03-01

Condensed phases in the atmosphere, such as cloud droplets and aerosols, often contain both water and organic matter (OM). Reactivity can differ significantly between aqueous and organic phases. We have measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene and pyrene in several organic solvents and in water, as well as in miscible and phase-separated aqueous-organic mixtures at atmospherically-relevant wavelengths. Photolysis rate constants generally increased with increasing solvent polarity; photolysis of both PAHs was more than ten times faster in water than in octanol. Local polarity had a much greater effect on PAH photolysis kinetics than changes in PAH absorptivity or singlet oxygen concentrations. Photolysis kinetics in homogeneous aqueous-organic mixtures varied monotonically with2 OM volume fraction. Kinetics in immiscible (phase-separated) solutions were more complex, with different dependences on OM content observed in stagnant and turbulent solutions. Our results suggest that OM could greatly affect the photochemical lifetimes of PAHs in atmospheric condensed phases such as aerosols, even if the OM does not itself absorb photons.

Coupling hydrothermal liquefaction and anaerobic digestion for energy valorization from model biomass feedstocks.

PubMed

Posmanik, Roy; Labatut, Rodrigo A; Kim, Andrew H; Usack, Joseph G; Tester, Jefferson W; Angenent, Largus T

2017-06-01

Hydrothermal liquefaction converts food waste into oil and a carbon-rich hydrothermal aqueous phase. The hydrothermal aqueous phase may be converted to biomethane via anaerobic digestion. Here, the feasibility of coupling hydrothermal liquefaction and anaerobic digestion for the conversion of food waste into energy products was examined. A mixture of polysaccharides, proteins, and lipids, representing food waste, underwent hydrothermal processing at temperatures ranging from 200 to 350°C. The anaerobic biodegradability of the hydrothermal aqueous phase was examined through conducting biochemical methane potential assays. The results demonstrate that the anaerobic biodegradability of the hydrothermal aqueous phase was lower when the temperature of hydrothermal processing increased. The chemical composition of the hydrothermal aqueous phase affected the anaerobic biodegradability. However, no inhibition of biodegradation was observed for most samples. Combining hydrothermal and anaerobic digestion may, therefore, yield a higher energetic return by converting the feedstock into oil and biomethane. Copyright © 2017 Elsevier Ltd. All rights reserved.

Insights into Aqueous-phase processing through Comparison of the Organic Chemical Composition of Atmospheric Particles and Cloud Water in the Southeast United States

NASA Astrophysics Data System (ADS)

Boone, E.; Laskin, J.; Laskin, A.; Wirth, C.; Shepson, P. B.; Stirm, B. H.; Pratt, K.

2014-12-01

Organic compounds comprise a significant mass fraction of submicron atmospheric particles with considerable contribution from secondary organic aerosol (SOA), a large fraction of which is formed from the oxidation of biogenic volatile organic compounds. Aqueous-phase reactions in particles and cloud droplets are suggested to increase SOA mass and change the chemical composition the particles following cloud evaporation. Aqueous-phase processing may also explain discrepancies between measurements and models. To gain a better understanding of these processes, cloud water and below-cloud atmospheric particles were collected onboard a research aircraft during the Southeast Oxidants and Aerosol Study (SOAS) over Alabama in June 2013. Nanospray desorption electrospray ionization (nano-DESI) and direct electrospray ionization (ESI) coupled with high resolution mass spectrometry were utilized to compare the organic molecular composition of the particle and cloud water samples, respectively. Several hundred unique compounds have been identified in the particle and cloud water samples, allowing possible aqueous-phase reactions to be examined. Hydrolysis of organosulfate compounds, aqueous-phase formation of nitrogen-containing compounds, and possible fragmentation of oligomeric compounds will be discussed, with comparisons to previous laboratory studies. This study provides insights into aqueous-phase reactions in ambient cloud droplets.

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

PubMed

Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

2016-03-10

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Qiuxia; Lopez-Ruiz, Juan A.; Cooper, Alan R.

The effect of aqueous phase on the acetic acid ketonization over monoclinic zirconia has been investigated using first-principles based density functional theory (DFT) calculations. To capture the aqueous phase chemistry over the solid zirconia catalyst surface, the aqueous phase is represented by 111 explicit water molecules with a liquid water density of 0.93 g/cm3 and the monoclinic zirconia is modeled by the most stable surface structure . The dynamic nature of aqueous phase/ interface was studied using ab initio molecular dynamics simulation, indicating that nearly half of the surface Zr sites are occupied by either adsorbed water molecules or hydroxylmore » groups at 550 K. DFT calculations show that the adsorption process of acetic acid from the liquid water phase to the surface is nearly thermodynamically neutral with a Gibbs free energy of -2.3 kJ/mol although the adsorption strength of acetic acid on the surface in aqueous phase is much stronger than in vapor phase. Therefore it is expected that the adsorption of acetic acid will dramatically affects aqueous phase ketonization reactivity over the monoclinic zirconia catalyst. Using the same ketonization mechanism via the β-keto acid intermediate, we have compared acetic acid ketonization to acetone in both vapor and aqueous phases. Our DFT calculation results show although the rate-determining step of the β-keto acid formation via the C-C coupling is not pronouncedly affected, the presence of liquid water molecules will dramatically affect dehydrogenation and hydrogenation steps via proton transfer mechanism. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL.« less

Environmentally benign processing of YAG transparent wafers

NASA Astrophysics Data System (ADS)

Yang, Yan; Wu, Yiquan

2015-12-01

Transparent yttrium aluminum garnet (YAG) wafers were successfully produced via aqueous tape casting and vacuum sintering techniques using a new environmentally friendly binder, a copolymer of isobutylene and maleic anhydride with the commercial name ISOBAM (noted as ISOBAM). Aqueous YAG slurries were mixed by ball-milling, which was followed by de-gassing and tape casting of wafers. The final YAG green tapes were homogenous and flexible, and could be bent freely without cracking. After the drying and sintering processes, transparent YAG wafers were achieved. The microstructures of both the green tape and vacuum-sintered YAG ceramic were observed by scanning electronic microscopy (SEM). Phase compositions were examined by X-ray diffraction (XRD). Optical transmittance was measured in UV-VIS regions with the result that the transmittance is 82.6% at a wavelength of 800 nm.

REMOVAL OF CHLORIDE FROM AQUEOUS SOLUTIONS

DOEpatents

Schulz, W.W.

1959-08-01

The removal of chlorides from aqueons solutions is described. The process involves contacting the aqueous chloride containing solution with a benzene solution about 0.005 M in phenyl mercuric acetate whereby the chloride anions are taken up by the organic phase and separating the organic phase from the aqueous solutions.

Humidity influence on gas-particle phase partitioning of α-pinene + O3 secondary organic aerosol

NASA Astrophysics Data System (ADS)

Prisle, N. L.; Engelhart, G. J.; Bilde, M.; Donahue, N. M.

2010-01-01

Water vapor uptake to particles could potentially affect organic-aerosol mass in three ways: first, water in the organic phase could reduce organic (equilibrium) partial pressures according to Raoult's law; second, an aqueous phase could attract water soluble organics according to Henry's law; finally, deliquescence of inorganic particle cores could mix the organic and inorganic particle phases, significantly diluting the organics and again reducing organic partial pressures according to Raoult's law. We present experiments using initially dry α-pinene + ozone secondary organic aerosol (SOA) on ammonium sulfate (AS) seeds at atmospheric concentrations in a smog chamber. After SOA formation, the chamber relative humidity is increased steadily by addition of steam to near 100%. Little subsequent SOA mass growth is observed, suggesting that none of these potential effects play a strong role in this system.

Arsenic interactions with a fullerene-like BN cage in the vacuum and aqueous phase.

PubMed

Beheshtian, Javad; Peyghan, Ali Ahmadi; Bagheri, Zargham

2013-02-01

Adsorption of arsenic ions, As (III and V), on the surface of fullerene-like B(12)N(12) cage has been explored in vacuum and aqueous phase using density functional theory in terms of Gibbs free energies, enthalpies, geometry, and density of state analysis. It was found that these ions can be strongly chemisorbed on the surface of the cluster in both vacuum and aqueous phase, resulting in significant changes in its electronic properties so that the cluster transforms from a semi-insulator to a semiconductor. The solvent significantly affects the geometry parameters and electronic properties of the As/B(12)N(12) complexes and the interaction between components is considerably weaker in the aqueous phase than that in the vacuum.

Photochemistry of aqueous pyruvic acid

PubMed Central

Griffith, Elizabeth C.; Carpenter, Barry K.; Shoemaker, Richard K.; Vaida, Veronica

2013-01-01

The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH3COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH3CHOHCOCH3), lactic acid (CH3CHOHCOOH), acetic acid (CH3COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols. PMID:23821751

Aqueous phase hydrodeoxygenation of polyols over Pd/WO3-ZrO2: Role of Pd-WO3 interaction and hydrodeoxygenation pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Changjun; Sun, Junming; Brown, Heather M.

Aqueous-phase hydrodeoxygenation of sugar and sugar-derived molecules can be used to produce a range of alkanes and oxygenates. In this paper, we have identified the reaction intermediates and reaction chemistry for the aqueous-phase hydrodeoxygenation of sorbitol over a bifunctional catalyst (Pt/SiO2–Al2O3) that contains both metal (Pt) and acid (SiO2–Al2O3) sites. A wide variety of reactions occur in this process including Csingle bondC bond cleavage, Csingle bondO bond cleavage, and hydrogenation reactions. The key Csingle bondC bond cleavage reactions include: retro-aldol condensation and decarbonylation, which both occur on metal catalytic sites. Dehydration is the key Csingle bondO bond cleavage reaction andmore » occurs on acid catalytic sites. Sorbitol initially undergoes dehydration and ring closure to produce cyclic C6 molecules or retro-aldol condensation reactions to produce primarily C3 polyols. Isosorbide is the major final product from sorbitol dehydration. Isosorbide then undergoes ring opening hydrogenation reactions and a dehydration/hydrogenation step to form 1,2,6-hexanetriol. The hexanetriol is then converted into hexanol and hexane by dehydration/hydrogenation. Smaller oxygenates are produced by Csingle bondC bond cleavage. These smaller oxygenates undergo dehydration/hydrogenation reactions to produce alkanes from C1–C5. The results from this paper suggest that hydrodeoxygenation chemistry can be tuned to make a wide variety of products from biomass-derived oxygenates.« less

Direct NMR Monitoring of Phase Separation Behavior of Highly Supersaturated Nifedipine Solution Stabilized with Hypromellose Derivatives.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2017-07-03

We investigated the phase separation behavior and maintenance mechanism of the supersaturated state of poorly water-soluble nifedipine (NIF) in hypromellose (HPMC) derivative solutions. Highly supersaturated NIF formed NIF-rich nanodroplets through phase separation from aqueous solution containing HPMC derivative. Dissolvable NIF concentration in the bulk water phase was limited by the phase separation of NIF from the aqueous solution. HPMC derivatives stabilized the NIF-rich nanodroplets and maintained the NIF supersaturation with phase-separated NIF for several hours. The size of the NIF-rich phase was different depending on the HPMC derivatives dissolved in aqueous solution, although the droplet size had no correlation with the time for which NIF supersaturation was maintained without NIF crystallization. HPMC acetate and HPMC acetate succinate (HPMC-AS) effectively maintained the NIF supersaturation containing phase-separated NIF compared with HPMC. Furthermore, HPMC-AS stabilized NIF supersaturation more effectively in acidic conditions. Solution 1 H NMR measurements of NIF-supersaturated solution revealed that HPMC derivatives distributed into the NIF-rich phase during the phase separation of NIF from the aqueous solution. The hydrophobicity of HPMC derivative strongly affected its distribution into the NIF-rich phase. Moreover, the distribution of HPMC-AS into the NIF-rich phase was promoted at lower pH due to the lower aqueous solubility of HPMC-AS. The distribution of a large amount of HPMC derivatives into NIF-rich phase induced the strong inhibition of NIF crystallization from the NIF-rich phase. Polymer distribution into the drug-rich phase directly monitored by solution NMR technique can be a useful index for the stabilization efficiency of drug-supersaturated solution containing a drug-rich phase.

URANIUM SEPARATION PROCESS

DOEpatents

McVey, W.H.; Reas, W.H.

1959-03-10

The separation of uranium from an aqueous solution containing a water soluble uranyl salt is described. The process involves adding an alkali thiocyanate to the aqueous solution, contacting the resulting solution with methyl isobutyl ketons and separating the resulting aqueous and organic phase. The uranium is extracted in the organic phase as UO/sub 2/(SCN)/sub/.

Effect of lipophilization on the distribution and reactivity of ingredients in emulsions.

PubMed

Leong, Wai Fun; Berton-Carabin, Claire C; Elias, Ryan J; Lecomte, Jérôme; Villeneuve, Pierre; Zhao, Yu; Coupland, John N

2015-12-01

The reactivity of small molecules in emulsions is believed to depend on their partitioning between phases, yet this is hard to verify experimentally in situ. In the present work, we use electron paramagnetic resonance (EPR) spectroscopy to simultaneously measure the distribution and reactivity of a homologous series of lipophilized spin probes in an emulsion. 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPOL) was derivatized with saturated fatty acids to create a series of spin probes with increasing lipophilicity (C4-, C8-, C12-, and C16-TEMPO). The probes were added to a 10 wt.% tetradecane-in water emulsions (d32∼190 nm) stabilized with sodium caseinate (1 wt.% in the aqueous phase, pH 7). The distribution of the probes between phases was measured by electron paramagnetic resonance (EPR) spectroscopy. TEMPOL partitioned into the aqueous phase, C4-TEMPO distributed between the lipid and aqueous phases (69% and 31% respectively) while the more lipophilic probes dissolved exclusively within the lipid droplets. Interestingly, the more lipophilic probes initially precipitated upon their addition to the emulsion, and only slowly redistributed to the droplets over hours or days, the rate of which was dependent on their carbon chain length. The reactivity of the probes with aqueous an aqueous phase reductant (ascorbate) generally depended on the proportion in the aqueous phase (i.e., TEMPOL>C4-TEMPO>C8-TEMPO∼C12-TEMPO∼C16-TEMPO). Copyright © 2015 Elsevier Inc. All rights reserved.

Summary report for the FY-2015 SACSESS Collaboration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peterman, Dean Richard; Mincher, Bruce Jay

2015-09-01

During FY-2015, a collaborative research program was established by the Department of Energy-Nuclear Energy (DOE-NE) Material Recovery and Waste Form Development program and the European Union (EU) Safety of Actinide Separation Processes (SACSESS) program. One component of this collaboration was the evaluation of the radiolytic stability of a Selective ActiNide Extraction (SANEX) separation which utilized a TODGA-based organic solvent and an aqueous phase containing the hydrophilic complexing reagent, SO3-Ph-BTP. To best simulate process conditions, this experiment was irradiated in the radiolysis/hydrolysis test loop located at the Idaho National Laboratory. The effect of irradiation on a SACSESS program iSANEX formulation containingmore » a TODGA-based organic phase and a BTP-based aqueous phase was investigated using irradiations at INL in static and test loop modes. When irradiated in contact with only the acidic aqueous phase, the TODGA organic solution maintained excellent extraction performance of americium, cerium and europium to a maximum absorbed dose of nearly 0.9 MGy. When the aqueous phase was changed to that containing the aqueous soluble BTP, the irradiated aqueous phase showed a dramatic color change, but this does not appear to have adverse effects on solvent extraction performance. Only minor increases in distribution ratios for both the lanthanides and actinide were measured, and the separation factors were essentially unchanged to a maximum absorbed dose of 174 kGy. The determination of the americium, cerium, and europium distribution ratios for the remaining SACSESS test loop samples will be completed in the near future. The analysis of stable metals concentration in the the irradiated aqueous and organic phases will be completed shortly.« less

A method for the preparation of curcumin by ultrasonic-assisted ammonium sulfate/ethanol aqueous two phase extraction.

PubMed

Xu, Guangkuan; Hao, Changchun; Tian, Suyang; Gao, Feng; Sun, Wenyuan; Sun, Runguang

2017-01-15

This study investigated a new and easy-to-industrialized extracting method for curcumin from Curcuma longa rhizomes using ultrasonic extraction technology combined with ammonium sulfate/ethanol aqueous two-phase system (ATPS), and the preparation of curcumin using the semi-preparative HPLC. The single-factor experiments and response surface methodology (RSM) were utilized to determine the optimal material-solvent ratio, ultrasonic intensity (UI) and ultrasonic time. The optimum extraction conditions were finally determined to be material-solvent rate of 3.29:100, ultrasonic intensity of 33.63W/cm 2 and ultrasonic time of 17min. At these optimum conditions, the extraction yield could reach 46.91mg/g. And the extraction yields of curcumin remained stable in the case of amplification, which indicated that scale-up extraction was feasible and efficient. Afterwards, the semi-preparative HPLC experiment was carried out, in which optimal preparation conditions were elected according to the single factor experiment. The prepared curcumin was obtained and the purity could up to 85.58% by the semi-preparative HPLC. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of processing on the release profiles of matrix systems containing 5-aminosalicylic acid.

PubMed

Korbely, Anita; Kelemen, András; Kása, Péter; Pintye-Hódi, Klára

2012-12-01

The aim of this study was to investigate the influence of different processing methods on the profiles of 5-aminosalicylic acid dissolution from controlled-release matrix systems based on Eudragit® RL and Eudragit® RS water-insoluble polymers. The pure polymers and their mixtures were studied as matrix formers using different processing methods, i.e., direct compression, wet granulation of the active ingredient with the addition of polymer(s) to the external phase, wet granulation with water, and wet granulation with aqueous dispersions. In comparison with the directly compressed tablets, tablets made by wet granulation with water demonstrated a 6-19% increase in final drug dissolution, whereas when polymers were applied in the external phase during compression, a 0-13% decrease was observed in the amount of drug released. Wet granulation with aqueous polymer dispersions delayed the release of the drug; this was especially marked (a 54-56% decrease in drug release) in compositions, which contained a high amount of Eudragit RL 30D. The release profiles were mostly described by the Korsmeyer-Peppas model or the Hopfenberg model.

Ionic liquid phase microextraction combined with fluorescence spectrometry for preconcentration and quantitation of carvedilol in pharmaceutical preparations and biological media.

PubMed

Zeeb, Mohsen; Mirza, Behrooz

2015-04-30

Carvedilol belongs to a group of medicines termed non-selective beta-adrenergic blocking agents. In the presented approach, a practical and environmentally friendly microextraction method based on the application of ionic liquids (ILs) was followed by fluorescence spectrometry for trace determination of carvedilol in pharmaceutical and biological media. A rapid and simple ionic liquid phase microextraction was utilized for preconcentration and extraction of carvedilol. A hydrophobic ionic liquid (IL) was applied as a microextraction solvent. In order to disperse the IL through the aqueous media and extract the analyte of interest, IL was injected into the sample solution and a proper temperature was applied and then for aggregating the IL-phase, the sample was cooled in an ice water-bath. The aqueous media was centrifuged and IL-phase collected at the bottom of the test tube was introduced to the micro-cell of spectrofluorimeter, in order to determine the concentration of the enriched analyte. Main parameters affecting the accuracy and precision of the proposed approach were investigated and optimized values were obtained. A linear response range of 10-250 μg I(-1) and a limit of detection (LOD) of 1.7 μg I(-1) were obtained. Finally, the presented method was utilized for trace determination of carvedilol in commercial pharmaceutical preparations and biological media.

Determination of tramadol by dispersive liquid-liquid microextraction combined with GC-MS.

PubMed

Habibollahi, Saeed; Tavakkoli, Nahid; Nasirian, Vahid; Khani, Hossein

2015-01-01

Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) has been developed for preconcentration and determination of tramadol, ((±)-cis-2-[(dimethylamino)methyl]-1-(3-methoxyphenyl)cyclohexanol-HCl), in aqueous and biological samples (urine, blood). DLLME is a simple, rapid and efficient method for determination of drugs in aqueous samples. Efficient factors on the DLLME process has defined and optimized for extraction of tramadol including type of extraction and disperser solvents and their volumes, pH of donor phase, time of extraction and ionic strength of donor phase. Based on the results of this study, under optimal conditions and by using 2-nitro phenol as internal standard, tramadol was determined by GC-MS, and the figures of merit of this work were evaluated. The enrichment factor, relative recovery and limit of detection were obtained 420, 99.2% and 0.08 µg L(-1), respectively. The linear range was between 0.26 and 220.00 µg L(-1) (R(2) = 0.9970). The relative standard deviation for 50.00 µg L(-1) of tramadol in aqueous samples by using 2-nitro phenol as IS was 3.6% (n = 7). Finally, the performance of DLLME was evaluated for analysis of tramadol in urine and blood. Published by Oxford University Press 2014. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Synthesis of aqueous suspensions of magnetic nanoparticles with the co-precipitation of iron ions in the presence of aspartic acid

NASA Astrophysics Data System (ADS)

Pušnik, Klementina; Goršak, Tanja; Drofenik, Miha; Makovec, Darko

2016-09-01

There is increasing demand for the production of large quantities of aqueous suspensions of magnetic iron-oxide nanoparticles. Amino acids are one possible type of inexpensive, nontoxic, and biocompatible molecules that can be used as the surfactants for the preparation of stable suspensions. This preparation can be conducted in a simple, one-step process based on the co-precipitation of Fe3+/Fe2+ ions in the presence of the amino acid. However, the presence of this amino acid changes the mechanism of the magnetic nanoparticles' formation. In this investigation we analyzed the influence of aspartic amino acid (Asp) on the formation of magnetic iron-oxide nanoparticles during the co-precipitation. The process of the nanoparticles' formation was followed using a combination of TEM, x-ray diffractometry, magnetic measurements, in-situ FT-IR spectroscopy, and chemical analysis, and compared with the formation of nanoparticles without the Asp. The Asp forms a coordination complex with the Fe3+ ions, which impedes the formation of the intermediate iron oxyhydroxide phase and suppresses the growth of the final magnetic iron-oxide nanoparticles. Slower reaction kinetics can lead to the formation of nonmagnetic secondary phases. The aspartic-acid-absorbed nanoparticles can be dispersed to form relatively concentrated aqueous suspensions displaying a good colloidal stability at an increased pH.

Investigations of the local environment and macroscopic alignment behavior of novel polymerizeable lyotropic liquid crystals using nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Juang, Elizabeth

In this dissertation, a variety of NMR techniques were used to explore the local environment of novel polymerizeable lyotropic liquid crystals (LLC). The LLC monomers examined in this study self-assemble in the presence of a small amount of water to form uniform, nanometer-scale tubes with aqueous interiors. The phase architecture is retained upon photopolymerization to yield the resulting nanoporous material. By dissolving reactive precursors into the aqueous phase, well- structured nancomposite materials have also been formed. Proposed uses for these novel polymerizeable LLCs are as porous water filtration membranes, as heterogeneous organic catalysts, and as nanocomposite materials for load bearing and optical applications. In order to better exploit these polymerizeable LLCs for materials development, the local environment must be examined. In addition, the macroscopic orientation of these materials remains an important step in their advancement. Various NMR studies were conducted on these novel LLCs. NMR T1 relaxation measurements were conducted to elucidate the local environment and dynamics of the 23Na counterions located inside the aqueous channels. 2H NMR line shape analyses were used to characterize the local structure and dynamics near the hydrophilic headgroup. 29 Si NMR studies were performed on silica nanocomposites formed with these LLC structures. Finally, the macroscopic alignment behavior of these novel LLCs using shear and magnetic fields was examined.

Phase-separable aqueous amide solutions as a thermal history indicator.

PubMed

Kitsunai, Makoto; Miyajima, Kentaro; Mikami, Yuzuru; Kim, Shokaku; Hirasawa, Akira; Chiba, Kazuhiro

2008-12-01

Aqueous solutions of several new amide compounds for use as simple thermal history indicators in the low-temperature transport of food and other products were synthesized. The phase transition temperatures of the aqueous solutions can be freely adjusted by changing the amide-water ratio in solution, the sodium chloride concentration of the water, and the type of amide compound. It is expected that these aqueous solutions can be applied as new thermal history indicators.

A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in wastewater treatment process models.

PubMed

Flores-Alsina, Xavier; Kazadi Mbamba, Christian; Solon, Kimberly; Vrecko, Darko; Tait, Stephan; Batstone, Damien J; Jeppsson, Ulf; Gernaey, Krist V

2015-11-15

There is a growing interest within the Wastewater Treatment Plant (WWTP) modelling community to correctly describe physico-chemical processes after many years of mainly focusing on biokinetics. Indeed, future modelling needs, such as a plant-wide phosphorus (P) description, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems. In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation/pairing is presented and interfaced with industry standard models. The module accounts for extensive consideration of non-ideality, including ion activities instead of molar concentrations and complex ion pairing. The general equilibria are formulated as a set of Differential Algebraic Equations (DAEs) instead of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies. The latter is reinforced with the Simulated Annealing method to increase the robustness of the solver making the system not so dependent of the initial conditions. Simulation results show pH predictions when describing Biological Nutrient Removal (BNR) by the activated sludge models (ASM) 1, 2d and 3 comparing the performance of a nitrogen removal (WWTP1) and a combined nitrogen and phosphorus removal (WWTP2) treatment plant configuration under different anaerobic/anoxic/aerobic conditions. The same framework is implemented in the Benchmark Simulation Model No. 2 (BSM2) version of the Anaerobic Digestion Model No. 1 (ADM1) (WWTP3) as well, predicting pH values at different cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated, by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling studies can be complemented with a rigorous description of aqueous phase and ion chemistry (pH, speciation, complexation). Copyright © 2015 Elsevier Ltd. All rights reserved.

Key Role of Nitrate in Phase Transitions of Urban Particles: Implications of Important Reactive Surfaces for Secondary Aerosol Formation

NASA Astrophysics Data System (ADS)

Sun, Jiaxing; Liu, Lei; Xu, Liang; Wang, Yuanyuan; Wu, Zhijun; Hu, Min; Shi, Zongbo; Li, Yongjie; Zhang, Xiaoye; Chen, Jianmin; Li, Weijun

2018-01-01

Ammonium sulfate (AS) and ammonium nitrate (AN) are key components of urban fine particles. Both field and model studies showed that heterogeneous reactions of SO2, NO2, and NH3 on wet aerosols accelerated the haze formation in northern China. However, little is known on phase transitions of AS-AN containing haze particles. Here hygroscopic properties of laboratory-generated AS-AN particles and individual particles collected during haze events in an urban site were investigated using an individual particle hygroscopicity system. AS-AN particles showed a two-stage deliquescence at mutual deliquescence relative humidity (MDRH) and full deliquescence relative humidity (DRH) and three physical states: solid before MDRH, solid-aqueous between MDRH and DRH, and aqueous after DRH. During hydration, urban haze particles displayed a solid core and aqueous shell at RH = 60-80% and aqueous phase at RH > 80%. Most particles were in aqueous phase at RH > 50% during dehydration. Our results show that AS content in individual particles determines their DRH and AN content determines their MDRH. AN content increase can reduce MDRH, which indicates occurrence of aqueous shell at lower RH. The humidity-dependent phase transitions of nitrate-abundant urban particles are important to provide reactive surfaces of secondary aerosol formation in the polluted air.

The free radical chemistry of cloud droplets and its impact upon the composition of rain

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.

1982-01-01

Calculations are presented that simulate the free radical chemistries of the gas phase and aqueous phase within a warm cloud during midday. It is demonstrated that in the presence of midday solar fluxes, the heterogeneous scavenging of OH and HO2 from the gas phase by cloud droplets can represent a major source of free radicals to cloud water, provided the accommodation or sticking coefficient for these species impinging upon water droplets is not less than 0.0001. The aqueous-phase of HO2 radicals are found to be converted to H2O2 by aqueous-phase chemical reactions at a rate that suggests that this mechanism could produce a significant fraction of the H2O2 found in cloud droplets. The rapid oxidation of sulfur species dissolved in cloudwater by this free-radical-produced H2O2 as well as by aqueous-phase OH radicals could conceivably have a significant impact upon the chemical composition of rain.

Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

EPA Science Inventory

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for...

Efflorescence of ammonium sulfate and coated ammonium sulfate particles: evidence for surface nucleation.

PubMed

Ciobanu, V Gabriela; Marcolli, Claudia; Krieger, Ulrich K; Zuend, Andreas; Peter, Thomas

2010-09-09

Using optical microscopy, we investigated the efflorescence of ammonium sulfate (AS) in aqueous AS and in aqueous 1:1 and 8:1 (by dry weight) poly(ethylene glycol)-400 (PEG-400)/AS particles deposited on a hydrophobically coated slide. Aqueous PEG-400/AS particles exposed to decreasing relative humidity (RH) exhibit a liquid-liquid phase separation below approximately 90% RH with the PEG-400-rich phase surrounding the aqueous AS inner phase. Pure aqueous AS particles effloresced in the RH range from 36.3% to 43.7%, in agreement with literature data (31-48% RH). In contrast, aqueous 1:1 (by dry weight) PEG-400/AS particles with diameters of the AS phase from 7.2 to 19.2 mum effloresced between 26.8% and 33.9% RH and aqueous 8:1 (by dry weight) PEG-400/AS particles with diameters of the AS phase from 1.8 to 7.3 mum between 24.3% and 29.3% RH. Such low efflorescence relative humidity (ERH) values have never been reached before for AS particles of this size range. We show that these unprecedented low ERHs of AS in PEG-400/AS particles could not possibly be explained by the presence of low amounts of PEG-400 in the aqueous AS phase, by a potential inhibition of water evaporation via anomalously slow diffusion through the PEG coating, or by different time scales between various experimental techniques. High-speed photography of the efflorescence process allowed the development of the AS crystallization fronts within the particles to be monitored with millisecond time resolution. The nucleation sites were inferred from the initial crystal growth sites. Analysis of the probability distribution of initial sites of 31 and 19 efflorescence events for pure AS and 1:1 (by dry weight) PEG-400/AS particles, respectively, showed that the particle volume can be excluded as the preferred nucleation site in the case of pure AS particles. For aqueous 1:1 (by dry weight) PEG-400/AS particles preferential AS nucleation in the PEG phase and at the PEG/AS/substrate contact line can be excluded. On the basis of this probability analysis of efflorescence events together with the AS ERH values of pure aqueous AS and aqueous PEG-400/AS particles aforementioned, we suggest that in pure aqueous AS particles nucleation starts at the surface of the particles and attribute the lower ERH values observed for aqueous PEG-400/AS particles to the suppression of the surface-induced nucleation process. Our results suggest that surface-induced nucleation is likely to also occur during the efflorescence of atmospheric AS aerosol particles, possibly constituting the dominating nucleation pathway.

Methods for removing contaminants from algal oil

DOEpatents

Lupton, Francis Stephen

2016-09-27

Methods for removing contaminants from algal oil are provided. In an embodiment, a method comprises the steps of combining a sulfuric acid-aqueous solution that has a pH of about 1 or less with a contaminant-containing algal oil at treatment conditions effective to form an effluent. The effluent comprises a treated algal oil phase and contaminants in an acidic aqueous phase. The contaminants comprise metals, phosphorus, or combinations thereof. The acidic aqueous phase is removed from the effluent to form a contaminant-depleted algal oil.

SEPARATION OF HAFNIUM FROM ZIRCONIUM

DOEpatents

Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

1960-05-31

The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

Preparative crystallization of a single chain antibody using an aqueous two-phase system.

PubMed

Huettmann, Hauke; Berkemeyer, Matthias; Buchinger, Wolfgang; Jungbauer, Alois

2014-11-01

A simultaneous crystallization and aqueous two-phase extraction of a single chain antibody was developed, demonstrating process integration. The process conditions were designed to form an aqueous two-phase system, and to favor crystallization, using sodium sulfate and PEG-2000. At sufficiently high concentrations of PEG, a second phase was generated in which the protein crystallization occurred simultaneously. The single chain antibody crystals were partitioned to the top, polyethylene glycol-rich phase. The crystal nucleation took place in the sodium sulfate-rich phase and at the phase boundary, whereas crystal growth was progressing mainly in the polyethylene glycol-rich phase. The crystals in the polyethylene glycol-rich phase grew to a size of >50 µm. Additionally, polyethylene glycol acted as an anti-solvent, thus, it influenced the crystallization yield. A phase diagram with an undersaturation zone, crystallization area, and amorphous precipitation zone was established. Only small differences in polyethylene glycol concentration caused significant shifts of the crystallization yield. An increase of the polyethylene glycol content from 2% (w/v) to 4% (w/v) increased the yield from approximately 63-87%, respectively. Our results show that crystallization in aqueous two-phase systems is an opportunity to foster process integration. © 2014 Wiley Periodicals, Inc.

Human plasma-derived immunoglobulin G fractionated by an aqueous two-phase system, caprylic acid precipitation, and membrane chromatography has a high purity level and is free of detectable in vitro thrombogenic activity.

PubMed

Vargas, M; Segura, Á; Wu, Y-W; Herrera, M; Chou, M-L; Villalta, M; León, G; Burnouf, T

2015-02-01

Instituto Clodomiro Picado has developed an immunoglobulin G (IgG) plasma fractionation process combining a polyethylene glycol/phosphate aqueous two-phase system (ATPS), caprylic acid precipitation and anion-exchange membrane chromatography. We evaluated the purity and in vitro thrombogenicity of such IgG, in line with current international requirements. Contributions of the different production steps to reduce thrombogenicity were assessed at 0·2 l-scale, and then the methodology was scaled-up to a 10 l-scale and final products (n = 3) were analysed. Purity, immunoglobulin composition, and subclass distribution were determined by electrophoretic and immunochemical methods. The in vitro thrombogenic potential was determined by a thrombin generation assay (TGA) using a Technothrombin fluorogenic substrate. Prekallikrein activator (PKA), plasmin, factor Xa, thrombin and thrombin-like activities were assessed using S-2302, S-2251, S-2222, S-2238 and S-2288 chromogenic substrates, respectively, and FXI by an ELISA. The thrombogenicity markers were reduced mostly during the ATPS step and were found to segregate mostly into the discarded liquid upper phase. The caprylic acid precipitation eliminated the residual procoagulant activity. The IgG preparations made from the 10 l-batches contained 100% gamma proteins, low residual IgA and undetectable IgM. The IgG subclass distribution was not substantially affected by the process. TGA and amidolytic activities revealed an undetectable in vitro thrombogenic risk and the absence of proteolytic enzymes in the final product. Fractionating human plasma by an ATPS combined with caprylic acid and membrane chromatography resulted in an IgG preparation of high purity and free of a detectable in vitro thrombogenic risk. © 2014 International Society of Blood Transfusion.

Solid-phase extraction sorbent consisting of alkyltrimethylammonium surfactants immobilized onto strong cation-exchange polystyrene resin.

PubMed

Reid, Kendra R; Kennedy, Lonnie J; Crick, Eric W; Conte, Eric D

2002-10-25

Presented is a solid-phase extraction sorbent material composed of cationic alkyltrimethylammonium surfactants attached to a strong cation-exchange resin via ion-exchange. The original hydrophilic cation-exchange resin is made hydrophobic by covering the surface with alkyl chains from the hydrophobic portion of the surfactant. The sorbent material now has a better ability to extract hydrophobic molecules from aqueous samples. The entire stationary phase (alkyltrimethylammonium surfactant) is removed along with the analyte during the elution step. The elution step requires a mild elution solvent consisting of 0.25 M Mg2+ in a 50% 2-propanol solution. The main advantage of using a removable stationary phase is that traditionally utilized toxic elution solvents such as methylene chloride, which are necessary to efficiently release strongly hydrophobic species from SPE stationary phases, may now be avoided. Also, the final extract is directly compatible with reversed-phase liquid chromatography. The performance of this procedure is presented using pyrene as a test molecule.

Vibrational Studies of Saccharide-Induced Lipid Film Reorganization at Aqueous/Air Interfaces

DOE PAGES

Link, Katie A.; Hsieh, Chia -Yun; Tuladhar, Aashish; ...

2018-02-09

Vibrational sum frequency generation (VSFG) and surface tension experiments were used to examine the effects of aqueous phase soluble saccharides on the structure and organization of insoluble lipid monolayers adsorbed to aqueous-air interfaces. Changes in dipalmitoylphosphocholine (DPPC) chain structure as a function of aqueous phase saccharide concentration and pH are reported. Complementary differential scanning calorimetry (DSC) measurements performed on solutions containing soluble saccharides and DPPC vesicles measured the effects of the saccharides on the lipid membrane phase behavior. Here, data show that the saccharides glucosamine and glucuronic acid induce a higher degree of organization in compressed DPPC monolayers regardless ofmore » the saccharide’s charge.« less

Vibrational Studies of Saccharide-Induced Lipid Film Reorganization at Aqueous/Air Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Link, Katie A.; Hsieh, Chia -Yun; Tuladhar, Aashish

Vibrational sum frequency generation (VSFG) and surface tension experiments were used to examine the effects of aqueous phase soluble saccharides on the structure and organization of insoluble lipid monolayers adsorbed to aqueous-air interfaces. Changes in dipalmitoylphosphocholine (DPPC) chain structure as a function of aqueous phase saccharide concentration and pH are reported. Complementary differential scanning calorimetry (DSC) measurements performed on solutions containing soluble saccharides and DPPC vesicles measured the effects of the saccharides on the lipid membrane phase behavior. Here, data show that the saccharides glucosamine and glucuronic acid induce a higher degree of organization in compressed DPPC monolayers regardless ofmore » the saccharide’s charge.« less

Studies of Physicochemical Processes in Atmospheric Particles and Acid Deposition.

NASA Astrophysics Data System (ADS)

Pandis, Spyros N.

A comprehensive chemical mechanism for aqueous -phase atmospheric chemistry was developed and its detailed sensitivity analysis was performed. The main aqueous-phase reaction pathways for the system are the oxidation of S(IV) to S(VI) by H_2O_2 , OH, O_2 (catalysed by Fe ^{3+} and Mn^ {2+}), O_3 and HSO_sp{5}{-}. The gas-phase concentrations of SO_2, H_2O_2, HO _2, OH, O_3 HCHO, NH_3, HNO_3 and HCl and the liquid water content of the cloud are of primary importance. The Lagrangian model predictions for temperature profile, fog development, liquid water content, gas-phase concentrations of SO_2 , HNO_3, and NH_3 , pH, aqueous-phase concentrations of SO _sp{4}{2-}, NH _sp{4}{+} and NO _sp{3}{-}, and finally deposition rates of the above ions match well the observed values. A third model was developed to study the distribution of acidity and solute concentration among the various droplet sizes in a fog or a cloud. Significant solute concentration differences can occur in aqueous droplets inside a fog or a cloud. Fogs in polluted environments have the potential to increase aerosol sulfate concentrations, but at the same time to cause reductions in the aerosol concentration of nitrate, chloride, ammonium and sodium as well as in the total aerosol mass concentration. The sulfate producd during fog episodes favors the aerosol particles that have access to most of the fog liquid water. Aerosol scavenging efficiencies of around 80% were calculated for urban fogs. Sampling and subsequent mixing of fog droplets of different sizes may result in measured concentrations that are not fully representative of the fogwater chemical composition. Isoprene and beta-pinene, at concentration levels ranging from a few ppb to a few ppm were reacted photochemically with NO_ {x} in the Caltech outdoor smog chamber facility. Aerosol formation from the isoprene photooxidation was found to be negligible even under extreme ambient conditions due to the relatively high vapor pressure of its condensable products. Aerosol carbon yield from the beta -pinene photooxidation is as high as 8% and depends strongly on the initial HC/NO_{x} ratio. Monoterpene photooxidation can be a significant source of secondary aerosol in rural environments and in urban areas with extended natural vegetation. (Abstract shortened with permission of author.).

Influence of propylene glycol on aqueous silica dispersions and particle-stabilized emulsions.

PubMed

Binks, Bernard P; Fletcher, Paul D I; Thompson, Michael A; Elliott, Russell P

2013-05-14

We have studied the influence of adding propylene glycol to both aqueous dispersions of fumed silica nanoparticles and emulsions of paraffin liquid and water stabilized by the same particles. In the absence of oil, aerating mixtures of aqueous propylene glycol and particles yields either stable dispersions, aqueous foams, climbing particle films, or liquid marbles depending on the glycol content and particle hydrophobicity. The presence of glycol in water promotes particles to behave as if they are more hydrophilic. Calculations of their contact angle at the air-aqueous propylene glycol surface are in agreement with these findings. In the presence of oil, particle-stabilized emulsions invert from water-in-oil to oil-in-water upon increasing either the inherent hydrophilicity of the particles or the glycol content in the aqueous phase. Stable multiple emulsions occur around phase inversion in systems of low glycol content, and completely stable, waterless oil-in-propylene glycol emulsions can also be prepared. Accounting for the surface energies at the respective interfaces allows estimation of the contact angle at the oil-polar phase interface; reasonable agreement between measured and calculated phase inversion conditions is found assuming no glycol adsorption on particle surfaces.

Cloud Point and Liquid-Liquid Equilibrium Behavior of Thermosensitive Polymer L61 and Salt Aqueous Two-Phase System.

PubMed

Rao, Wenwei; Wang, Yun; Han, Juan; Wang, Lei; Chen, Tong; Liu, Yan; Ni, Liang

2015-06-25

The cloud point of thermosensitive triblock polymer L61, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO), was determined in the presence of various electrolytes (K2HPO4, (NH4)3C6H5O7, and K3C6H5O7). The cloud point of L61 was lowered by the addition of electrolytes, and the cloud point of L61 decreased linearly with increasing electrolyte concentration. The efficacy of electrolytes on reducing cloud point followed the order: K3C6H5O7 > (NH4)3C6H5O7 > K2HPO4. With the increase in salt concentration, aqueous two-phase systems exhibited a phase inversion. In addition, increasing the temperature reduced the concentration of salt needed that could promote phase inversion. The phase diagrams and liquid-liquid equilibrium data of the L61-K2HPO4/(NH4)3C6H5O7/K3C6H5O7 aqueous two-phase systems (before the phase inversion but also after phase inversion) were determined at T = (25, 30, and 35) °C. Phase diagrams of aqueous two-phase systems were fitted to a four-parameter empirical nonlinear expression. Moreover, the slopes of the tie-lines and the area of two-phase region in the diagram have a tendency to rise with increasing temperature. The capacity of different salts to induce aqueous two-phase system formation was the same order as the ability of salts to reduce the cloud point.

Aqueous two-phase partition applied to the isolation of plasma membranes and Golgi apparatus from cultured mammalian cells.

PubMed

Morré, D M; Morre, D J

2000-06-23

Partitioning in dextran-poly(ethylene)glycol (PEG) aqueous-aqueous phase systems represents a mature technology with many applications to separations of cells and to the preparation of membranes from mammalian cells. Most applications to membrane isolation and purification have focused on plasma membranes, plasma membrane domains and separation of right side-out and inside-out plasma membrane vesicles. The method exploits a combination of membrane properties, including charge and hydrophobicity. Purification is based upon differential distributions of the constituents in a sample between the two principal compartments of the two phases (upper and lower) and at the interface. The order of affinity of animal cell membranes for the upper phase is: endoplasmic reticulum

Aqueous two-phase partition applied to the isolation of plasma membranes and Golgi apparatus from cultured mammalian cells

NASA Technical Reports Server (NTRS)

Morre, D. M.; Morre, D. J.

2000-01-01

Partitioning in dextran-poly(ethylene)glycol (PEG) aqueous-aqueous phase systems represents a mature technology with many applications to separations of cells and to the preparation of membranes from mammalian cells. Most applications to membrane isolation and purification have focused on plasma membranes, plasma membrane domains and separation of right side-out and inside-out plasma membrane vesicles. The method exploits a combination of membrane properties, including charge and hydrophobicity. Purification is based upon differential distributions of the constituents in a sample between the two principal compartments of the two phases (upper and lower) and at the interface. The order of affinity of animal cell membranes for the upper phase is: endoplasmic reticulum

Synthesis and application of selective adsorbent for pirimicarb pesticides in aqueous media using allyl-β-cyclodextrin based binary functional monomers.

PubMed

He, Chengzijing; Lay, Sovichea; Yu, Haining; Shen, Shengrong

2018-04-01

Binary functional monomers, allyl-β-cyclodextrin (allyl-β-CD) and methacrylic acid (MAA) or allyl-β-CD and acrylonitrile (AN), were exploited in a fabrication of molecularly imprinted polymers (MIPs) for selective recognition and large enrichment of pirimicarb from aqueous media. Special attention was paid to the computational simulation of the imprinting molecular and functional monomers. The morphological characteristics of MIPs made of allyl-β-CD and MAA (M-MAA) were characterised by scanning electron microscopy. The effect of binding capacity of MAA-linked allyl-β-CD MIPs (M-MAA) demonstrated higher efficiency than that of AN-linked allyl-β-CD MIPs (M-AN) when tested in binding specificity. Finally, M-MAA was chosen to run through molecularly imprinted solid-phase extraction (MISPE) to analyse the spiked fresh leafy vegetables of pirimicarb. The present proposed technique is a promising tool for the preparation of the receptors which could recognise pirimicarb pesticide in aqueous media. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

End-Member Formulation of Solid Solutions and Reactive Transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

Aqueous biphasic extraction of uranium and thorium from contaminated soils. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaiko, D.J.; Gartelmann, J.; Henriksen, J.L.

1995-07-01

The aqueous biphasic extraction (ABE) process for soil decontamination involves the selective partitioning of solutes and fine particulates between two immiscible aqueous phases. The biphase system is generated by the appropriate combination of a water-soluble polymer (e.g., polyethlene glycol) with an inorganic salt (e.g., sodium carbonate). Selective partitioning results in 99 to 99.5% of the soil being recovered in the cleaned-soil fraction, while only 0.5 to 1% is recovered in the contaminant concentrate. The ABE process is best suited to the recovery of ultrafine, refractory material from the silt and clay fractions of soils. During continuous countercurrent extraction tests withmore » soil samples from the Fernald Environmental Management Project site (Fernald, OH), particulate thorium was extracted and concentrated between 6- and 16-fold, while the uranium concentration was reduced from about 500 mg/kg to about 77 mg/kg. Carbonate leaching alone was able to reduce the uranium concentration only to 146 mg/kg. Preliminary estimates for treatment costs are approximately $160 per ton of dry soil. A detailed flowsheet of the ABE process is provided.« less

Closantel nano-encapsulated polyvinyl alcohol (PVA) solutions.

PubMed

Vega, Abraham Faustino; Medina-Torres, Luis; Calderas, Fausto; Gracia-Mora, Jesus; Bernad-Bernad, MaJosefa

2016-08-01

The influence of closantel on the rheological and physicochemical properties (particle size and by UV-Vis absorption spectroscopy) of PVA aqueous solutions is studied here. About 1% PVA aqueous solutions were prepared by varying the closantel content. The increase of closantel content led to a reduction in the particle size of final solutions. All the solutions were buffered at pH 7.4 and exhibited shear-thinning behavior. Furthermore, in oscillatory flow, a "solid-like" type behavior was observed for the sample containing 30 μg/mL closantel. Indicating a strong interaction between the dispersed and continuous phases and evidencing an interconnected network between the nanoparticle and PVA, this sample also showed the highest shear viscosity and higher shear thinning slope, indicating a more intrincate structure disrupted by shear. In conclusion, PVA interacts with closantel in aqueous solution and the critical concentration for closantel encapsulation by PVA was about 30 μg/mL; above this concentration, the average particle size decreased notoriously which was associated to closantel interacting with the surface of the PVA aggregates and thus avoiding to some extent direct polymer-polymer interaction.

Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

NASA Astrophysics Data System (ADS)

Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

2016-11-01

Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus, formation of pyruvate/oxalate suggests the potential for aqueous processing of these ambient mixtures to form SOAAQ.

Aqueous two-phase assisted by ultrasound for the extraction of anthocyanins from Lycium ruthenicum Murr.

PubMed

Qin, Benlin; Liu, Xuecong; Cui, Haiming; Ma, Yue; Wang, Zimin; Han, Jing

2017-10-21

In this study, an efficient ultrasound-assisted aqueous two-phase extraction method was used for the extraction of anthocyanins from Lycium ruthenicum Murr. An ethanol/ammonium sulfate system was chosen for the aqueous two-phase system due to its fine partitioning and recycling behaviors. Single-factor experiments were conducted to determine the optimized composition of the system, and the response surface methodology was used for the further optimization of the ultrasound-assisted aqueous two-phase extraction. The optimal conditions were as follows: a salt concentration of 20%, an ethanol concentration of 25%, an extraction time of 33.7 min, an extraction temperature of 25°C, a liquid/solid ratio of 50:1 w/w, pH value of 3.98, and an ultrasound power of 600 W. Under the above conditions, the yields of anthocyanins reached 4.71 mg/g dry sample. For the further purification, D-101 resin was used, and the purity of anthocyanins reached 25.3%. In conclusion, ultrasound-assisted aqueous two-phase extraction was an efficient, ecofriendly, and economical method, and it may be a promising technique for extracting bioactive components from plants.

A novel TFC forward osmosis (FO) membrane supported by polyimide (PI) microporous nanofiber membrane

NASA Astrophysics Data System (ADS)

Chi, Xiang-Yu; Zhang, Ping-Yun; Guo, Xue-Jiao; Xu, Zhen-Liang

2018-01-01

A novel interfacial polymerization (IP) procedure on polyimide (PI) microporous nanofiber membrane support with mean pore size 1.27 μm was reported. Using m-phenylenediamine (MPD) as aqueous phase monomer, trimesoyl chloride (TMC) as organic phase monomer, ethanol as aqueous phase co-solvent, thin-film composite (TFC) forward osmosis (FO) membrane was fabricated by two IP procedures. The first IP procedure with the unconventional order (ie, the membrane was immersed in the TMC organic phase first, then in the co-solvent ethanol-water MPD aqueous phase) was used to diminish the pore size of PI microporous nanofiber membrane support for the formation of the polyamide layer. The secondary IP procedure was employed to form the relatively dense polyamide layer with conventional order (ie, the membrane was immersed in the co-solvent ethanol-water MPD aqueous phase first, then in the TMC organic phase). The experimental results showed that higher ethanol concentration led to the relatively higher pure water permeability in RO process and osmotic water flux in FO process, whereas NaCl rejection in RO process decreased and reverse salt flux increased. The specific salt flux (Js/Jv) of TFC FO PI nanofiber membrane (PIN-2-4) could be as low as 0.095 g/L in FO mode. These results could be attributed to influence of the addition of ethanol into aqueous phase on the surface morphology, hydrophilicity and polyamide layer structure.

Chemical composition of an aqueous oxalato-/citrato-VO(2+) solution as determinant for vanadium oxide phase formation.

PubMed

Peys, Nick; Maurelli, Sara; Reekmans, Gunter; Adriaensens, Peter; De Gendt, Stefan; Hardy, An; Van Doorslaer, Sabine; Van Bael, Marlies K

2015-01-05

Aqueous solutions of oxalato- and citrato-VO(2+) complexes are prepared, and their ligand exchange reaction is investigated as a function of the amount of citrate present in the aqueous solution via continuous-wave electron paramagnetic resonance (CW EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopy. With a low amount of citrate, monomeric cis-oxalato-VO(2+) complexes occur with a distorted square-pyramidal geometry. As the amount of citrate increases, oxalate is gradually exchanged for citrate. This leads to (i) an intermediate situation of monomeric VO(2+) complexes with a mix of oxalate/citrate ligands and (ii) a final situation of both monomeric and dimeric complexes with exclusively citrato ligands. The monomeric citrato-VO(2+) complexes dominate (abundance > 80%) and are characterized by a 6-fold chelation of the vanadium(IV) ion by 4 RCO2(-) ligands at the equatorial positions and a H2O/R-OH ligand at the axial position. The different redox stabilities of these complexes, relative to that of dissolved O2 in the aqueous solution, is analyzed via (51)V NMR. It is shown that the oxidation rate is the highest for the oxalato-VO(2+) complexes. In addition, the stability of the VO(2+) complexes can be drastically improved by evacuation of the dissolved O2 from the solution and subsequent storage in a N2 ambient atmosphere. The vanadium oxide phase formation process, starting with the chemical solution deposition of the aqueous solutions and continuing with subsequent processing in an ambient 0.1% O2 atmosphere, differs for the two complexes. The oxalato-VO(2+) complexes turn into the oxygen-deficient crystalline VO2 B at 400 °C, which then turns into crystalline V6O13 at 500 °C. In contrast, the citrato-VO(2+) complexes form an amorphous film at 400 °C that crystallizes into VO2 M1 and V6O13 at 500 °C.

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

Water-Soluble Nonconjugated Polymer Nanoparticles with Strong Fluorescence Emission for Selective and Sensitive Detection of Nitro-Explosive Picric Acid in Aqueous Medium.

PubMed

Liu, Shi Gang; Luo, Dan; Li, Na; Zhang, Wei; Lei, Jing Lei; Li, Nian Bing; Luo, Hong Qun

2016-08-24

Water-soluble nonconjugated polymer nanoparticles (PNPs) with strong fluorescence emission were prepared from hyperbranched poly(ethylenimine) (PEI) and d-glucose via Schiff base reaction and self-assembly in aqueous phase. Preparation of the PEI-d-glucose (PEI-G) PNPs was facile (one-pot reaction) and environmentally friendly under mild conditions. Also, PEI-G PNPs showed a high fluorescence quantum yield in aqueous solution, and the fluorescence properties (such as concentration- and solvent-dependent fluorescence) and origin of intrinsic fluorescence were investigated and discussed. PEI-G PNPs were then used to develop a fluorescent probe for fast, selective, and sensitive detection of nitro-explosive picric acid (PA) in aqueous medium, because the fluorescence can be easily quenched by PA whereas other nitro-explosives and structurally similar compounds only caused negligible quenching. A wide linear range (0.05-70 μM) and a low detection limit (26 nM) were obtained. The fluorescence quenching mechanism was carefully explored, and it was due to a combined effect of electron transfer, resonance energy transfer, and inner filter effect between PA and PEI-G PNPs, which resulted in good selectivity and sensitivity for PA. Finally, the developed sensor was successfully applied to detection of PA in environmental water samples.

PCE DNAPL degradation using ferrous iron solid mixture (ISM).

PubMed

Lee, Hong-Kyun; Do, Si-Hyun; Batchelor, Bill; Jo, Young-Hoon; Kong, Sung-Ho

2009-08-01

Ferrous iron solid mixture (ISM) containing Fe(II), Fe(III), and Cl was synthesized for degradation of tetrachloroethene (PCE) as a dense non-aqueous phase liquid (DNAPL), and an extraction procedure was developed to measure concentrations of PCE in both the aqueous and non-aqueous phases. This procedure included adding methanol along with hexane in order to achieve the high extraction efficiency, particularly when solids were present. When PCE was present as DNAPL, dechlorination of PCE was observed to decrease linearly with respect to the total PCE concentration (aqueous and non-aqueous phases) and the concentration of PCE in the aqueous phase was observed to be approximately constant. In the absence of DNAPL, the rate of PCE degradation was observed to be the first-order with respect to the concentration in the aqueous phase. A kinetic model was developed to describe these observations and it was able to fit experimental data well. Increasing the concentration of Fe(II) in ISM increased the values of rate constants, while increasing the concentration of PCE DNAPL did not affect the value of the rate constant. The reactivity of ISM for PCE dechlorination might be close to that of Friedel's salt, and the accumulation of trichloroethylene (TCE) might imply the lower reactivity of ISM for degradation of TCE or the necessity of large amount of Fe(II) in ISM. TCE (the major chlorinated intermediate), ethene (the major non-chlorinated compound), acetylene and ethane were detected, which implied that both hydrogenolysis and beta-elimination were pathways of PCE DNAPL degradation on ISM.

Triton X-114 based cloud point extraction: a thermoreversible approach for separation/concentration and dispersion of nanomaterials in the aqueous phase.

PubMed

Liu, Jing-fu; Liu, Rui; Yin, Yong-guang; Jiang, Gui-bin

2009-03-28

Capable of preserving the sizes and shapes of nanomaterials during the phase transferring, Triton X-114 based cloud point extraction provides a general, simple, and cost-effective route for reversible concentration/separation or dispersion of various nanomaterials in the aqueous phase.

Anomalistic Self-Assembled Phase Behavior of Block Copolymer Blended with Organic Derivative Depending on Temperature

DOE PAGES

Kim, Tae-Hwan; Kim, Eunhye; Do, Changwoo; ...

2016-08-16

Amphiphilic Pluronic block copolymers have attracted great attention in a broad spectrum of potential applications due to the excellent phase behaviors in an aqueous solution, and many efforts have been made to investigate their phase behaviors under various external conditions. With a variety of external conditions, however, the closed looplike phase behaviors of a Pluronic block copolymer in an aqueous solution have not been reported yet. Herein, we report the closed looplike (CLL) phase behavior of a Pluronic P65 triblock copolymer blended with an organic derivative, 5-methylsalicylic acid (5mS), in aqueous solution, which is very unique for block copolymers. Asmore » the 5mS concentration increases, the isotropic to ordered phase or back to isotropic phase transition temperature is decreased while the number of closed loops is increased to two. To the best of our knowledge, this is the first demonstration of a CLL phase transition of a Pluronic block copolymer in an aqueous solution, which is readily applicable to optical devices such as optical sensors or optoelectronics, and nanotemplates for a highly ordered superlattice. Additionally, this provides new insight into the understanding on the phase behavior of a Pluronic block copolymer blended with additives.« less

Anomalistic Self-Assembled Phase Behavior of Block Copolymer Blended with Organic Derivative Depending on Temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Tae-Hwan; Kim, Eunhye; Do, Changwoo

Amphiphilic Pluronic block copolymers have attracted great attention in a broad spectrum of potential applications due to the excellent phase behaviors in an aqueous solution, and many efforts have been made to investigate their phase behaviors under various external conditions. With a variety of external conditions, however, the closed looplike phase behaviors of a Pluronic block copolymer in an aqueous solution have not been reported yet. Herein, we report the closed looplike (CLL) phase behavior of a Pluronic P65 triblock copolymer blended with an organic derivative, 5-methylsalicylic acid (5mS), in aqueous solution, which is very unique for block copolymers. Asmore » the 5mS concentration increases, the isotropic to ordered phase or back to isotropic phase transition temperature is decreased while the number of closed loops is increased to two. To the best of our knowledge, this is the first demonstration of a CLL phase transition of a Pluronic block copolymer in an aqueous solution, which is readily applicable to optical devices such as optical sensors or optoelectronics, and nanotemplates for a highly ordered superlattice. Additionally, this provides new insight into the understanding on the phase behavior of a Pluronic block copolymer blended with additives.« less

SEPARATION OF POLONIUM, PROTACTINIUM OR MIXTURES THEREOF IN AQUEOUS SOLUTION FROM BISMUTH, LEAD, ZIRCONIUM AND/OR COLUMBIUM VALUES

DOEpatents

Van Winkle, Q.; Kraus, K.A.

1959-10-27

A process is presented for separating polonium, protactinium, or mixtures thereof in aqueous solution from bismuth, zirconium, lead, and niobium values contained in the solution. The method comprises providing hydrochloric acid in the solution in a concentration of at least 5N. contacting the aqueous solution with a substantially waterimmiscible organic solvent such as diisopropyl ketone, and separating the aqueous phase containing the bismuth, zirconium, lead, and niobium from the organic extract phase containing the polonium, protactinium, or mixture thereof.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1999-01-01

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1999-03-30

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

Adsorptive removal of phthalate ester (Di-ethyl phthalate) from aqueous phase by activated carbon: a kinetic study.

PubMed

Venkata Mohan, S; Shailaja, S; Rama Krishna, M; Sarma, P N

2007-07-19

Adsorptive studies were carried out on Di-ethyl phthalate (DEP) removal from aqueous phase onto activated carbon. Batch sorption studies were performed and the results revealed that activated carbon demonstrated ability to adsorb DEP. Influence of varying experimental conditions such as DEP concentration, pH of aqueous solution, and dosage of adsorbent were investigated on the adsorption process. Sorption interaction of DEP onto activated carbon obeyed the pseudo second order rate equation. Experimental data showed good fit with both the Langmuir and Freundlich adsorption isotherm models. DEP sorption was found to be dependent on the aqueous phase pH and the uptake was observed to be greater at acidic pH.

SE-72/AS-72 generator system based on Se extraction/ As reextraction

DOEpatents

Fassbender, Michael Ernst; Ballard, Beau D

2013-09-10

The preparation of a .sup.72Se/.sup.72As radioisotope generator involves forming an acidic aqueous solution of an irradiated alkali bromide target such as a NaBr target, oxidizing soluble bromide in the solution to elemental bromine, removing the elemental bromine, evaporating the resulting solution to a residue, removing hydrogen chloride from the residue, forming an acidic aqueous solution of the residue, adding a chelator that selectively forms a chelation complex with selenium, and extracting the chelation complex from the acidic aqueous solution into an organic phase. As the .sup.72Se generates .sup.72As in the organic phase, the .sup.72As may be extracted repeatedly from the organic phase with an aqueous acid solution.

Ice growth from supercooled aqueous solutions of benzene, naphthalene, and phenanthrene.

PubMed

Liyana-Arachchi, Thilanga P; Valsaraj, Kalliat T; Hung, Francisco R

2012-08-23

Classical molecular dynamics (MD) were performed to investigate the growth of ice from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene. The main objective of this study is to explore the fate of those aromatic molecules after freezing of the supercooled aqueous solutions, i.e., if these molecules become trapped inside the ice lattice or if they are displaced to the QLL or to the interface with air. Ice growth from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene result in the formation of quasi-liquid layers (QLLs) at the air/ice interface that are thicker than those observed when pure supercooled water freezes. Naphthalene and phenanthrene molecules in the supercooled aqueous solutions are displaced to the air/ice interface during the freezing process at both 270 and 260 K; no incorporation of these aromatics into the ice lattice is observed throughout the freezing process. Similar trends were observed during freezing of supercooled aqueous solutions of benzene at 270 K. In contrast, a fraction of the benzene molecules become trapped inside the ice lattice during the freezing process at 260 K, with the rest of the benzene molecules being displaced to the air/ice interface. These results suggest that the size of the aromatic molecule in the supercooled aqueous solution is an important parameter in determining whether these molecules become trapped inside the ice crystals. Finally, we also report potential of mean force (PMF) calculations aimed at studying the adsorption of gas-phase benzene and phenanthrene on atmospheric air/ice interfaces. Our PMF calculations indicate the presence of deep free energy minima for both benzene and phenanthrene at the air/ice interface, with these molecules adopting a flat orientation at the air/ice interface.

Small molecules as tracers in atmospheric secondary organic aerosol

NASA Astrophysics Data System (ADS)

Yu, Ge

Secondary organic aerosol (SOA), formed from in-air oxidation of volatile organic compounds, greatly affects human health and climate. Although substantial research has been devoted to SOA formation and evolution, the modeled and lab-generated SOA are still low in mass and degree of oxidation compared to ambient measurements. In order to compensate for these discrepancies, the aqueous processing pathway has been brought to attention. The atmospheric waters serve as aqueous reaction media for dissolved organics to undergo further oxidation, oligomerization, or other functionalization reactions, which decreases the vapor pressure while increasing the oxidation state of carbon atoms. Field evidence for aqueous processing requires the identification of tracer products such as organosulfates. We synthesized the standards for two organosulfates, glycolic acid sulfate and lactic acid sulfate, in order to measure their aerosol-state concentration from five distinct locations via filter samples. The water-extracted filter samples were analyzed by LC-MS. Lactic acid sulfate and glycolic acid sulfate were detected in urban locations in the United States, Mexico City, and Pakistan with varied concentrations, indicating their potential as tracers. We studied the aqueous processing reaction between glyoxal and nitrogen-containing species such as ammonium and amines exclusively by NMR spectrometry. The reaction products formic acid and several imidazoles along with the quantified kinetics were reported. The brown carbon generated from these reactions were quantified optically by UV-Vis spectroscopy. The organic-phase reaction between oxygen molecule and alkenes photosensitized by alpha-dicarbonyls were studied in the same manner. We observed the fast kinetics transferring alkenes to epoxides under simulated sunlight. Statistical estimations indicate a very effective conversion of aerosol-phase alkenes to epoxides, potentially forming organosulfates in a deliquescence event and increasing aerosol mass. Finally, we built a containerless apparatus to study aqueous processing reactions using an acoustic levitator paired with a mass spectrometer. The levitator is capable of trapping droplets with the size of 80-500 mum in diameter for over eight hours. The apparatus is also capable of drying and wetting the droplet in a controllable manner. We performed am example reaction between glyoxal and ammonium sulfate using this instrument, and showed that it could qualitatively monitor aqueous processing reactions.

Development of Recombinant Human Growth Hormone (rhGH) sustained-release microspheres by a low temperature aqueous phase/aqueous phase emulsion method.

PubMed

Kang, Jian; Wu, Fei; Cai, Yunpeng; Xu, Mingxin; He, Mu; Yuan, Weien

2014-10-01

A novel method has been developed to protect Recombinant Human Growth Hormone (rhGH) in poly (lactic-co-glycolic acid) (PLGA) microspheres using an aqueous phase/aqueous phase emulsion and S/O/W multi-emulsion method. This method develops a novel rhGH sustained-release system, which is based on the combination of rhGH-loaded dextran microparticles and PLGA microspheres. The process to fabricate rhGH-loaded dextran microparticles involves an aqueous phase/aqueous phase emulsion system formed at the reduced temperature. RhGH was first dissolved in water together with dextran and polyethylene glycol, followed by stirring at the speed of 2000 rpm for 20-30s at 0°C, and then a freezing process could enable the dextran phase to separate from the continuous PEG phase and rhGH could preferentially be loaded with dextran. The sample after freezing and phase separation was then lyophilized to powder and washed with dichloromethane to remove the PEG. Once loaded in the dextran microparticles (1-4 μm in diameter), rhGH gained resistance to interface tensions and was encapsulated into PLGA microspheres without aggregation thereafter. RhGH released from PLGA microspheres was in a sustained manner with minimal burst and maximally reduced incomplete release in vitro. Single subcutaneous injection of rhGH-loaded PLGA microspheres to rats resulted in a stable plasma concentration for 30 days avoiding the drug concentration fluctuations after multiple injections of protein solutions. In a hypophysectomized rat model, the IGF-1 and bodyweight results showed that there were higher than the levels obtained for the sustained release formulation by W/O/W for 40 days. These results suggest that the microsphere delivery system had the potential to be an injectable depot for sustained-release of the biocompatible protein of rhGH. Copyright © 2014 Elsevier B.V. All rights reserved.

Droplet microfluidics with a nanoemulsion continuous phase.

PubMed

Gu, Tonghan; Yeap, Eunice W Q; Somasundar, Ambika; Chen, Ran; Hatton, T Alan; Khan, Saif A

2016-07-05

We present the first study of a novel, generalizable method that uses a water-in-oil nanoemulsion as the continuous phase to generate uniform aqueous micro-droplets in a capillary-based microfluidic system. We first study the droplet generation mechanism in this system and compare it to the more conventional case where a simple oil/solvent (with surfactant) is used as the continuous phase. Next, we present two versatile methods - adding demulsifying chemicals and heat treatment - to allow active online chemical interaction between the continuous and dispersed phases. These methods allow each generated micro-droplet to act as a well-mixed micro-reactor with walls that are 'permeable' to the nanoemulsion droplets and their contents. Finally, we demonstrate an application of this system in the fabrication of uniform hydrogel (alginate) micro-beads with control over particle properties such as size and swelling. Our work expands the toolbox of droplet-based microfluidics, enabling new opportunities and applications involving active colloidal continuous phases carrying chemical payloads, both in advanced materials synthesis and droplet-based screening and diagnostic methods.

Magnetic ionic liquid aqueous two-phase system coupled with high performance liquid chromatography: A rapid approach for determination of chloramphenicol in water environment.

PubMed

Yao, Tian; Yao, Shun

2017-01-20

A novel organic magnetic ionic liquid based on guanidinium cation was synthesized and characterized. A new method of magnetic ionic liquid aqueous two-phase system (MILATPs) coupled with high-performance liquid chromatography (HPLC) was established to preconcentrate and determine trace amount of chloramphenicol (CAP) in water environment for the first time. In the absence of volatile organic solvents, MILATPs not only has the excellent properties of rapid extraction, but also exhibits a response to an external magnetic field which can be applied to assist phase separation. The phase behavior of MILATPs was investigated and phase equilibrium data were correlated by Merchuk equation. Various influencing factors on CAP recovery were systematically investigated and optimized. Under the optimal conditions, the preconcentration factor was 147.2 with the precision values (RSD%) of 2.42% and 4.45% for intra-day (n=6) and inter-day (n=6), respectively. The limit of detection (LOD) and limit of quantitation (LOQ) were 0.14ngmL -1 and 0.42ngmL -1 , respectively. Fine linear range of 12.25ngmL -1 -2200ngmL -1 was obtained. Finally, the validated method was successfully applied for the analysis of CAP in some environmental waters with the recoveries for the spiked samples in the acceptable range of 94.6%-99.72%. Hopefully, MILATPs is showing great potential to promote new development in the field of extraction, separation and pretreatment of various biochemical samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of oil concentration and residence time on the biodegradation of α-pinene vapours in two-liquid phase suspended-growth bioreactors.

PubMed

Montes, María; Veiga, María C; Kennes, Christian

2012-02-20

Recently, research on the use of binary aqueous-organic liquid phase systems for the treatment of polluted air has significantly increased. This paper reports the removal of α-pinene from a waste air stream in a continuous stirred tank bioreactor (CSTB), using either a single-liquid aqueous phase or a mixed aqueous-organic liquid phase. The influence of gas flow rate, load and pollutant concentration was evaluated as well as the effect of the organic to aqueous phase ratio. Continuous experiments were carried out at different inlet α-pinene concentrations, ranging between 0.03 and 25.1 g m⁻³ and at four different flow rates, corresponding to residence times (RTs) of 120 s, 60 s, 36 s and 26 s. The maximum elimination capacities (ECs) reached in the CSTB were 382 g m⁻³ h⁻¹ (without silicone oil) and 608 g m⁻³ h⁻¹ (with 5%v/v silicone oil), corresponding to a 1.6-fold improvement using an aqueous-organic liquid phase. During shock-loads experiments, the performance and stability of the CSTB were enhanced with 5% silicone oil, quickly recovering almost 100% removal efficiency (RE), when pre-shock conditions were restored. The addition of silicone oil acted as a buffer for high α-pinene loads, showing a more stable behaviour in the case of two-liquid-phase systems. Copyright © 2011 Elsevier B.V. All rights reserved.

Formation of uniform carrot-like Cu31S16-CuInS2 heteronanostructures assisted by citric acid at the oil/aqueous interface.

PubMed

Li, Yongjie; Tang, Aiwei; Liu, Zhenyang; Peng, Lan; Yuan, Yi; Shi, Xifeng; Yang, Chunhe; Teng, Feng

2018-01-07

A simple two-phase strategy was developed to prepare Cu 31 S 16 -CuInS 2 heterostructures (HNS) at the oil/aqueous interface, in which the In(OH) 3 phase was often obtained in the products due to the reaction between indium ions and hydroxyl ions in the aqueous phase. To prevent the formation of the In(OH) 3 phase, citric acid was incorporated into the aqueous phase to assist in the synthesis of uniform carrot-like Cu 31 S 16 -CuInS 2 semiconductor HNS at the oil/aqueous interface for the first time. By manipulating the dosage of citric acid and Cu/In precursor ratios, the morphology of the Cu 31 S 16 -CuInS 2 HNS could be tailored from mushroom to carrot-like, and the presence of citric acid played a critical role in the synthesis of high-quality Cu 31 S 16 -CuInS 2 HNS, which inhibited the formation of the In(OH) 3 phase due to the formation of the indium(iii)-citric acid complex. The formation mechanism was studied by monitoring the morphology and phase evolution of the Cu 31 S 16 -CuInS 2 HNS with reaction time, which revealed that the Cu 31 S 16 seeds were first formed and then the cation-exchange reaction directed the subsequent anisotropic growth of the Cu 31 S 16 -CuInS 2 HNS.

Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment

DOE PAGES

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira; ...

2016-01-29

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

Retention of ionisable compounds on high-performance liquid chromatography XVII. Estimation of the pH variation of aqueous buffers with the change of the methanol fraction of the mobile phase.

PubMed

Subirats, Xavier; Bosch, Elisabeth; Rosés, Martí

2007-01-05

The use of methanol-aqueous buffer mobile phases in HPLC is a common election when performing chromatographic separations of ionisable analytes. The addition of methanol to the aqueous buffer to prepare such a mobile phase changes the buffer capacity and the pH of the solution. In the present work, the variation of these buffer properties is studied for acetic acid-acetate, phosphoric acid-dihydrogenphosphate-hydrogenphosphate, citric acid-dihydrogencitrate-hydrogencitrate-citrate, and ammonium-ammonia buffers. It is well established that the pH change of the buffers depends on the initial concentration and aqueous pH of the buffer, on the percentage of methanol added, and on the particular buffer used. The proposed equations allow the pH estimation of methanol-water buffered mobile phases up to 80% in volume of organic modifier from initial aqueous buffer pH and buffer concentration (before adding methanol) between 0.001 and 0.01 mol L(-1). From both the estimated pH values of the mobile phase and the estimated pKa of the ionisable analytes, it is possible to predict the degree of ionisation of the analytes and therefore, the interpretation of acid-base analytes behaviour in a particular methanol-water buffered mobile phase.

Non-aqueous phase cold vapor generation and determination of trace cadmium by atomic fluorescence spectrometry.

PubMed

Lei, Zirong; Chen, Luqiong; Hu, Kan; Yang, Shengchun; Wen, Xiaodong

2018-06-05

Cold vapor generation (CVG) of cadmium was firstly accomplished in non-aqueous media by using solid reductant of potassium borohydride (KBH 4 ) as a derivation reagent. The mixture of surfactant Triton X-114 micelle and octanol was innovatively used as the non-aqueous media for the CVG and atomic fluorescence spectrometry (AFS) was used for the elemental determination. The analyte ions were firstly extracted into the non-aqueous media from the bulk aqueous phase of analyte/sample solution via a novelly established ultrasound-assisted rapidly synergistic cloud point extraction (UARS-CPE) process and then directly mixed with the solid redcutant KBH 4 to generate volatile elemental state cadmium in a specially designed reactor, which was then rapidly transported to a commercial atomic fluorescence spectrometer for detection. Under the optimal conditions, the limit of detection (LOD) for cadmium was 0.004 μg L -1 . Compared to conventional hydride generation (HG)-AFS, the efficiency of non-aqueous phase CVG and the analytical performance of the developed system was considerably improved. Copyright © 2018 Elsevier B.V. All rights reserved.

Apparatus and method for the desulfurization of petroleum by bacteria

DOEpatents

Lizama, H.M.; Scott, T.C.; Scott, C.D.

1995-10-17

A method is described for treating petroleum with anaerobic microorganisms acting as biocatalysts that can remove sulfur atoms from hydrocarbon molecules, under anaerobic conditions, and then convert the sulfur atoms to hydrogen sulfide. The microorganisms utilized are from the family known as the ``Sulfate Reducing Bacteria``. These bacteria generate metabolic energy from the oxidation of organic compounds, but use oxidized forms of sulfur as an electron acceptor. Because the biocatalyst is present in the form of bacteria in an aqueous suspension, whereas the reacting substrate consists of hydrocarbon molecules in an organic phase, the actual desulfurization reaction takes place at the aqueous-organic interphase. To ensure adequate interfacial contacting and mass transfer, a biphasic electrostatic bioreactor system is utilized. The bioreactor is utilized to disperse and recoalesce a biocatalyst contained in the aqueous liquid phase into the organic liquid phase containing the sulfur. High-intensity electrical fields rupture the aqueous drops into a plurality of microdroplets and induce continuous coalescence and redispersion as the microdroplets travel through the organic phase, thus increasing surface area. As the aqueous microdroplets progress through the organic phase, the biocatalyst then reacts with the sulfur to produce hydrogen sulfide which is then removed from the bioreactor. The organic liquid, now free of the sulfur, is ready for immediate use or further processing. 5 figs.

Apparatus and method for the desulfurization of petroleum by bacteria

DOEpatents

Lizama, Hector M.; Scott, Timothy C.; Scott, Charles D.

1995-01-01

A method for treating petroleum with anaerobic microorganisms acting as biocatalysts that can remove sulfur atoms from hydrocarbon molecules, under anaerobic conditions, and then convert the sulfur atoms to hydrogen sulfide. The microorganisms utilized are from the family known as the "Sulfate Reducing Bacteria." These bacteria generate metabolic energy from the oxidation of organic compounds, but use oxidized forms of sulfur as an electron acceptor. Because the biocatalyst is present in the form of bacteria in an aqueous suspension, whereas the reacting substrate consists of hydrocarbon molecules in an organic phase, the actual desulfurization reaction takes place at the aqueous-organic interphase. To ensure adequate interfacial contacting and mass transfer, a biphasic electrostatic bioreactor system is utilized. The bioreactor is utilized to disperse and recoalesce a biocatalyst contained in the aqueous liquid phase into the organic liquid phase containing the sulfur. High-intensity electrical fields rupture the aqueous drops into a plurality of microdroplets and induce continuous coalescence and redispersion as the microdroplets travel through the organic phase, thus increasing surface area. As the aqueous microdroplets progress through the organic phase, the biocatalyst then reacts with the sulfur to produce hydrogen sulfide which is then removed from the bioreactor. The organic liquid, now free of the sulfur, is ready for immediate use or further processing.

Aqueous phase transfer of InP/ZnS nanocrystals conserving fluorescence and high colloidal stability.

PubMed

Tamang, Sudarsan; Beaune, Grégory; Texier, Isabelle; Reiss, Peter

2011-12-27

Small thiol-containing amino acids such as cysteine are appealing surface ligands for transferring semiconductor quantum dots (QDs) from organic solvents to the aqueous phase. They provide a compact hydrodynamic diameter and low nonspecific binding in biological environment. However, cysteine-capped QDs generally exhibit modest colloidal stability in water and their fluorescence quantum yield (QY) is significantly reduced as compared to organics. We demonstrate that during phase transfer the deprotonation of the thiol group by carefully adjusting the pH is of crucial importance for increasing the binding strength of cysteine to the QD surface. As a result, the colloidal stability of cysteine-capped InP/ZnS core/shell QDs is extended from less than one day to several months. The developed method is of very general character and can be used also with other hydrophilic thiols and various other types of QDs, e.g., CdSe/CdS/ZnS and CuInS(2)/ZnS QDs as well as CdSe and CdSe/CdS nanorods. We show that the observed decrease of QY upon phase transfer with cysteine is related to the generation of cysteine dimer, cystine. This side-reaction implies the formation of disulfide bonds, which efficiently trap photogenerated holes and inhibit radiative recombination. On the other hand, this process is not irreversible. By addition of an appropriate reducing agent, tris(2-carboxyethyl)phosphine hydrochloride (TCEP), the QY can be partially recovered. When TCEP is already added during the phase transfer, the QY of cysteine-capped InP/ZnS QDs can be maintained almost quantitatively. Finally, we show that penicillamine is a promising alternative to cysteine for the phase transfer of QDs, as it is much less prone to disulfide formation.

Aqueous-phase source of formic acid in clouds

NASA Technical Reports Server (NTRS)

Chameides, W. L.; Davis, D. D.

1983-01-01

The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

Soft X-ray spectroscopy of nanoparticles by velocity map imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kostko, O.; Xu, B.; Jacobs, M. I.

Velocity map imaging (VMI), a technique traditionally used to study chemical dynamics in the gas phase, is applied to study X-ray photoemission from aerosol nanoparticles. Soft X-rays from the Advanced Light Source synchrotron, probe a beam of nanoparticles, and the resulting photoelectrons are velocity mapped to obtain their kinetic energy distributions. A new design of the VMI spectrometer is described. The spectrometer is benchmarked by measuring vacuum ultraviolet photoemission from gas phase xenon and squalene nanoparticles followed by measurements using soft X-rays. It is demonstrated that the photoelectron distribution from X-ray irradiated squalene nanoparticles is dominated by secondary electrons. Bymore » scanning the photon energies and measuring the intensities of these secondary electrons, a near edge X-ray absorption fine structure (NEXAFS) spectrum is obtained. The NEXAFS technique is used to obtain spectra of aqueous nanoparticles at the oxygen K edge. By varying the position of the aqueous nanoparticle beam relative to the incident X-ray beam, evidence is presented such that the VMI technique allows for NEXAFS spectroscopy of water in different physical states. Finally, we discuss the possibility of applying VMI methods to probe liquids and solids via X-ray spectroscopy.« less

Hydrocarbon removal from bilgewater by a combination of air-stripping and photocatalysis.

PubMed

Cazoir, D; Fine, L; Ferronato, C; Chovelon, J-M

2012-10-15

In order to prevent hydrocarbon discharge at sea from the bilge of ships, the International Maritime Organization (IMO) enacted the MARPOL 73/78 convention in which effluents are now limited to those with maximum oil content of 15 ppmv. Thus, photocatalysis and air-stripping were combined for the hydrocarbon removal from a real oily bilgewater sample and an original monitoring of both aqueous and gaseous phases was performed by GC/MS to better understand the process. Our results show that the hydrocarbon oil index [HC] can be reduced to its maximum permissible value of 15 ppmv (MARPOL) in only 8.5h when photocatalysis and air-stripping are used together in a synergistic way, as against 17 h when photocatalysis is used alone. However, this air-assisted photocatalytic process emits a large quantity of volatile organic compounds (VOC) and, within the first four hours, ca. 10% of the hydrocarbon removal in the aqueous phase is actually just transferred into the gaseous one. Finally, we highlight that the n-alkanes with a number of carbon atoms higher than 15 (N(C)>15) are those which most decrease the rate of [HC] removal. Copyright © 2012 Elsevier B.V. All rights reserved.

Soft X-ray spectroscopy of nanoparticles by velocity map imaging

DOE PAGES

Kostko, O.; Xu, B.; Jacobs, M. I.; ...

2017-05-05

Velocity map imaging (VMI), a technique traditionally used to study chemical dynamics in the gas phase, is applied to study X-ray photoemission from aerosol nanoparticles. Soft X-rays from the Advanced Light Source synchrotron, probe a beam of nanoparticles, and the resulting photoelectrons are velocity mapped to obtain their kinetic energy distributions. A new design of the VMI spectrometer is described. The spectrometer is benchmarked by measuring vacuum ultraviolet photoemission from gas phase xenon and squalene nanoparticles followed by measurements using soft X-rays. It is demonstrated that the photoelectron distribution from X-ray irradiated squalene nanoparticles is dominated by secondary electrons. Bymore » scanning the photon energies and measuring the intensities of these secondary electrons, a near edge X-ray absorption fine structure (NEXAFS) spectrum is obtained. The NEXAFS technique is used to obtain spectra of aqueous nanoparticles at the oxygen K edge. By varying the position of the aqueous nanoparticle beam relative to the incident X-ray beam, evidence is presented such that the VMI technique allows for NEXAFS spectroscopy of water in different physical states. Finally, we discuss the possibility of applying VMI methods to probe liquids and solids via X-ray spectroscopy.« less

Translating Thermal Response of Triblock Copolymer Assemblies in Dilute Solution to Macroscopic Gelation and Phase Separation

DOE PAGES

Sun, Zhe; Tian, Ye; Hom, Wendy L.; ...

2016-12-28

The thermal response of semi-dilute solutions (5 w/w%) of two amphiphilic thermoresponsive poly(ethylene oxide)-b-poly(N,N-diethylacrylamide)-b-poly(N,N-dibutylacrylamide) (PEO 45-PDEAm x-PDBAm 12) triblock copolymers, which differ only in the size of the central responsive block, in water was examined in this paper. Aqueous PEO45-PDEAm41-PDBAm12 solutions, which undergo a thermally induced sphere-to-worm transition in dilute solution, were found to reversibly form soft (G'≈10 Pa) free-standing physical gels after 10 min at 55 °C. PEO 45-PDEAm 89-PDBAm 12 copolymer solutions, which undergo a thermally induced transition from spheres to large compound micelles (LCM) in dilute solution, underwent phase separation after heating at 55 °C for 10more » min owing to sedimentation of LCMs. The reversibility of LCM formation was investigated as a non-specific method for removal of a water-soluble dye from aqueous solution. Finally, the composition and size of the central responsive block in these polymers dictate the microscopic and macroscopic response of the polymer solutions as well as the rates of transition between assemblies.« less

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

NASA Astrophysics Data System (ADS)

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu; Boone, Eric; Chu, Rosalie K.; Dukett, James E.; Gunsch, Matthew J.; Zhang, Wuliang; Tolic, Nikola; Laskin, Alexander; Pratt, Kerri A.

2017-12-01

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds. Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds.more » Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.« less

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Travis S. Grimes; Richard D. Tillotson; Leigh R. Martin

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successfulmore » separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.« less

SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

DOEpatents

Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

1962-08-14

A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

Separation of uranium from technetium in recovery of spent nuclear fuel

DOEpatents

Pruett, D.J.; McTaggart, D.R.

1983-08-31

Uranium and technetium in the product stream of the Purex process for recovery of uranium in spent nuclear fuel are separated by (1) contacting the aqueous Purex product stream with hydrazine to reduce Tc/sup +7/ therein to a reduced species, and (2) contacting said aqueous stream with an organic phase containing tributyl phosphate and an organic diluent to extract uranium from said aqueous stream into said organic phase.

Separation of uranium from technetium in recovery of spent nuclear fuel

DOEpatents

Pruett, David J.; McTaggart, Donald R.

1984-01-01

Uranium and technetium in the product stream of the Purex process for recovery of uranium in spent nuclear fuel are separated by (1) contacting the aqueous Purex product stream with hydrazine to reduce Tc.sup.+7 therein to a reduced species, and (2) contacting said aqueous stream with an organic phase containing tributyl phosphate and an organic diluent to extract uranium from said aqueous stream into said organic phase.

EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

DOEpatents

Furman, N.H.; Mundy, R.J.

1957-12-10

An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

[Phase transfer catalyzed bioconversion of penicillin G to 6-APA by immobilized penicillin acylase in recyclable aqueous two-phase systems with light/pH sensitive copolymers].

PubMed

Jin, Ke-ming; Cao, Xue-jun; Su, Jin; Ma, Li; Zhuang, Ying-ping; Chu, Ju; Zhang, Si-liang

2008-03-01

Immobilized penicillin acylase was used for bioconversion of penicillin PG into 6-APA in aqueous two-phase systems consisting of a light-sensitive polymer PNBC and a pH-sensitive polymer PADB. Partition coefficients of 6-APA was found to be about 5.78 in the presence of 1% NaCl. Enzyme kinetics showed that the reaction reached equilibrium at roughly 7 h. The 6-APA mole yields were 85.3% (pH 7.8, 20 degrees C), with about 20% increment as compared with the reaction of single aqueous phase buffer. The partition coefficient of PG (Na) varied scarcely, while that of the product, 6-APA and phenylacetic acid (PA) significantly varied due to Donnan effect of the phase systems and hydrophobicity of the products. The variation of the partition coefficients of the products also affected the bioconversion yield of the products. In the aqueous two-phase systems, the substrate, PG, the products of 6-APA and PA were biased in the top phase, while immobilized penicillin acylase at completely partitioned at the bottom. The substrate and PG entered the bottom phase, where it was catalyzed into 6-APA and PA and entered the top phase. Inhibition of the substrate and products was removed to result in improvement of the product yield, and the immobilized enzyme showed higher efficiency than the immobilized cells and occupied smaller volume. Compared with the free enzyme, immobilized enzyme had greater stability, longer life-time, and was completely partitioned in the bottom phase and recycle. Bioconversion in two-phase systems using immobilized penicillin acylase showed outstanding advantage. The light-sensitive copolymer forming aqueous two-phase systems could be recovered by laser radiation at 488 nm or filtered 450 nm light, while pH-sensitive polymer PADB could be recovered at the isoelectric point (pH 4.1). The recovery of the two copolymers was between 95% and 99%.

An approach for upgrading biomass and pyrolysis product quality using a combination of aqueous phase bio-oil washing and torrefaction pretreatment.

PubMed

Chen, Dengyu; Cen, Kehui; Jing, Xichun; Gao, Jinghui; Li, Chen; Ma, Zhongqing

2017-06-01

Bio-oil undergoes phase separation because of poor stability. Practical application of aqueous phase bio-oil is challenging. In this study, a novel approach that combines aqueous phase bio-oil washing and torrefaction pretreatment was used to upgrade the biomass and pyrolysis product quality. The effects of individual and combined pretreatments on cotton stalk pyrolysis were studied using TG-FTIR and a fixed bed reactor. The results showed that the aqueous phase bio-oil washing pretreatment removed metals and resolved the two pyrolysis peaks in the DTG curve. Importantly, it increased the bio-oil yield and improved the pyrolysis product quality. For example, the water and acid content of bio-oil decreased significantly along with an increase in phenol formation, and the heating value of non-condensable gases improved, and these were more pronounced when combined with torrefaction pretreatment. Therefore, the combined pretreatment is a promising method, which would contribute to the development of polygeneration pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Management of the diffusion of 4-methylumbelliferone across phases in microdroplet-based systems for in vitro protein evolution.

PubMed

Wu, Nan; Courtois, Fabienne; Zhu, Yonggang; Oakeshott, John; Easton, Chris; Abell, Chris

2010-09-01

Fluorongenic reagents based on 4-methylumbelliferone (4-MU) have been widely used for the detection of phosphatase, sulfatase, esterase, lipase and glycosidase activities in conventionally formatted enzyme assay systems. However, the sensitivity of assays based on these substrates is also potentially very useful in the microdroplet formats now being developed for high throughput in vitro evolution experiments. In this article, we report the investigation of diffusion of 4-MU as a model dye from water-in-oil droplets and the internal aqueous phase of water-in-oil-in-water droplets in microfluidics. The effect of BSA in the aqueous phase on the diffusion of 4-MU is also discussed. Based on these results, we provided here proof-of-concept of the reaction of the enzyme OpdA with the substrate coumaphos in water-in-oil-in-water droplets. In this double-emulsion system, the reaction of OpdA and coumaphos was achieved by allowing coumaphos to diffuse from the continuous aqueous phase across the oil phase into the internal aqueous droplets.

Recovery of Picloram and 2,4-Dichlorophenoxyacetic Acid from Aqueous Samples by Reversed-Phase Solid-Phase Extraction

Treesearch

Martha J.M. Wells; Jerry L. Michael

1987-01-01

Extensive preparation of samples before chromatographic analysis is usually the most time-consuming process in the determination of many organic compounds in environmental matrices. In the past, removal of some organic from aqueous solution was commonly done by liquid/liquid extraction. However, the introduction of stable, covalently bonded reversed-phase sorbents now...

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1998-01-01

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

Diffusion-based process for carbon dioxide uptake and isoprene emission in gaseous/aqueous two-phase photobioreactors by photosynthetic microorganisms.

PubMed

Bentley, Fiona K; Melis, Anastasios

2012-01-01

Photosynthesis for the generation of fuels and chemicals from cyanobacteria and microalgae offers the promise of a single host organism acting both as photocatalyst and processor, performing sunlight absorption and utilization, as well as CO(2) assimilation and conversion into product. However, there is a need to develop methods for generating, sequestering, and trapping such bio-products in an efficient and cost-effective manner that is suitable for industrial scale-up and exploitation. A sealed gaseous/aqueous two-phase photobioreactor was designed and applied for the photosynthetic generation of volatile isoprene (C(5)H(8)) hydrocarbons, which operates on the principle of spontaneous diffusion of CO(2) from the gaseous headspace into the microalgal or cyanobacterial-containing aqueous phase, followed by photosynthetic CO(2) assimilation and isoprene production by the transgenic microorganisms. Volatile isoprene hydrocarbons were emitted from the aqueous phase and were sequestered into the gaseous headspace. Periodic replacement (flushing) of the isoprene (C(5)H(8)) and oxygen (O(2)) content of the gaseous headspace with CO(2) allowed for the simultaneous harvesting of the photoproducts and replenishment of the CO(2) supply in the gaseous headspace. Reduction in practice of the gaseous/aqueous two-phase photobioreactor is offered in this work with a fed-batch and a semi-continuous culturing system using Synechocystis sp. PCC 6803 heterologously expressing the Pueraria montana (kudzu) isoprene synthase (IspS) gene. Constitutive isoprene production was observed over 192 h of experimentation, coupled with cyanobacterial biomass accumulation. The diffusion-based process in gaseous/aqueous two-phase photobioreactors has the potential to be applied to other high-value photosynthetically derived volatile molecules, emanating from a variety of photosynthetic microorganisms. Copyright © 2011 Wiley Periodicals, Inc.

Sherwood correlation for dissolution of pooled NAPL in porous media

NASA Astrophysics Data System (ADS)

Aydin Sarikurt, Derya; Gokdemir, Cagri; Copty, Nadim K.

2017-11-01

The rate of interphase mass transfer from non-aqueous phase liquids (NAPLs) entrapped in the subsurface into the surrounding mobile aqueous phase is commonly expressed in terms of Sherwood (Sh) correlations that are expressed as a function of flow and porous media properties. Because of the lack of precise methods for the estimation of the interfacial area separating the NAPL and aqueous phases, most studies have opted to use modified Sherwood expressions that lump the interfacial area into the interphase mass transfer coefficient. To date, there are only two studies in the literature that have developed non-lumped Sherwood correlations; however, these correlations have undergone limited validation. In this paper controlled dissolution experiments from pooled NAPL were conducted. The immobile NAPL mass is placed at the bottom of a flow cell filled with porous media with water flowing horizontally on top. Effluent aqueous phase concentrations were measured for a wide range of aqueous phase velocities and for two different porous media. To interpret the experimental results, a two-dimensional pore network model of the NAPL dissolution kinetics and aqueous phase transport was developed. The observed effluent concentrations were then used to compute best-fit mass transfer coefficients. Comparison of the effluent concentrations computed with the two-dimensional pore network model to those estimated with one-dimensional analytical solutions indicates that the analytical model which ignores the transport in the lateral direction can lead to under-estimation of the mass transfer coefficient. Based on system parameters and the estimated mass transfer coefficients, non-lumped Sherwood correlations were developed and compared to previously published data. The developed correlations, which are a significant improvement over currently available correlations that are associated with large uncertainties, can be incorporated into future modeling studies requiring non-lumped Sh expressions.

Oxidation of Organic Compoundsin the Atmospheric Aqueous Phase: Development of a New Explicit Oxidation Mechanism

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bregonzio-Rozier, L.; Monod, A.; Leriche, M.; Doussin, J. F.; Chaumerliac, N. M.; Deguillaume, L.

2014-12-01

Current 3D models tend to underestimate the production of secondary organic aerosol (SOA) in the atmosphere (Volkamer et al., 2006). Recent studies argue that aqueous chemistry in clouds could be responsible for a significant production of SOA (Ervens et al., 2011; Carlton and Turpin, 2013) through oxidative and non-oxidative processes. Aqueous phase reactivity of organic compounds needs to be thoroughly described in models to identify organic molecules available to contribute to SOA mass. Recently, new empirical methods have been developed to allow the estimate of HO·reaction rates in the aqueous phase (Doussin and Monod, 2013, Minakata et al., 2009). These methods provide global rate constants together with branching ratios for HO·abstraction and addition on organic compounds of atmospheric interests. Current cloud chemistry mechanisms do not take the different possible pathways into account. Based on these structure-activity relationships, a new detailed aqueous phase mechanism describing the oxidation of hydrosoluble organic compounds resulting from isoprene oxidation is proposed. This new aqueous phase mechanism is coupled with the detailed gas phase mechanism MCM v3.2 (Jenkin et al., 1997; Saunders et al., 2003) through a kinetic of mass transfer parameterization for the exchange between gas phase and aqueous phase. The GROMHE SAR (Raventos-Duran et al., 2010) allows the evaluation of Henry's law constants for organic compounds. Variable photolysis in both phases using the TUV 4.5 radiative transfer model (Madronich and Flocke, 1997) is also calculated. The resulting multiphase mechanism has been implemented in a cloud chemistry model. Focusing on oxygenated compounds produced from the isoprene oxidation, sensitivity tests and comparisons with multiphase experiments performed in the framework of the CUMULUS project in the CESAM atmospheric simulation chamber (Wang et al., 2011) will be presented. Volkamer et al., GRL, 33, L17811, 2006. Carlton and Turpin, ACP, 13, 10203-10214, 2013. Ervens et al., ACP, 11069-11102, 2011. Doussin and Monod, ACP, 13, 11625-11641, 2013. Minakata et al., EST, 45, 3479-3486, 2009. Jenkin et al., AE, 31, 81, 1997. Saunders et al., ACP, 3, 161, 2003. Raventos-Duran et al., ACP, 10, 7643-7654, 2010. Madronich and Flocke, 1997. Wang et al., AMT, 4, 2465-2494,2011.

Secondary Organic Aerosol Produced from Aqueous Reactions of Phenols in Fog Drops and Deliquesced Particles

NASA Astrophysics Data System (ADS)

Smith, J.; Anastasio, C.

2014-12-01

The formation and evolution of secondary organic aerosol (SOA) in atmospheric condensed phases (i.e., aqueous SOA) can proceed rapidly, but relatively little is known of the important aqueous SOA precursors or their reaction pathways. In our work we are studying the aqueous SOA formed from reactions of phenols (phenol, guaiacol, and syringol), benzene-diols (catechol, resorcinol, and hydroquinone), and phenolic carbonyls (e.g., vanillin and syringaldehyde). These species are potentially important aqueous SOA precursors because they are released in large quantities from biomass burning, have high Henry's Law constants (KH = 103 -109 M-1 atm-1) and are rapidly oxidized. To evaluate the importance of aqueous reactions of phenols as a source of SOA, we first quantified the kinetics and SOA mass yields for 11 phenols reacting via direct photodegradation, hydroxyl radical (•OH), and with an excited organic triplet state (3C*). In the second step, which is the focus of this work, we use these laboratory results in a simple model of fog chemistry using conditions during a previously reported heavy biomass burning event in Bakersfield, CA. Our calculations indicate that under aqueous aerosol conditions (i.e., a liquid water content of 100 μg m-3) the rate of aqueous SOA production (RSOA(aq)) from phenols is similar to the rate in the gas phase. In contrast, under fog/cloud conditions the aqueous RSOA from phenols is 10 times higher than the rate in the gas phase. In both of these cases aqueous RSOA is dominated by the oxidation of phenols by 3C*, followed by direct photodegradation of phenolic carbonyls, and then •OH oxidation. Our results suggest that aqueous oxidation of phenols is a significant source of SOA during fog events and also during times when deliquesced aerosols are present.

Design of Phosphonium-Type Zwitterion as an Additive to Improve Saturated Water Content of Phase-Separated Ionic Liquid from Aqueous Phase toward Reversible Extraction of Proteins

PubMed Central

Ito, Yoritsugu; Kohno, Yuki; Nakamura, Nobuhumi; Ohno, Hiroyuki

2013-01-01

We designed phosphonium-type zwitterion (ZI) to control the saturated water content of separated ionic liquid (IL) phase in the hydrophobic IL/water biphasic systems. The saturated water content of separated IL phase, 1-butyl-3-methyimidazolium bis(trifluoromethanesulfonyl)imide, was considerably improved from 0.4 wt% to 62.8 wt% by adding N,N,N-tripentyl-4-sulfonyl-1-butanephosphonium-type ZI (P555C4S). In addition, the maximum water content decreased from 62.8 wt% to 34.1 wt% by increasing KH2PO4/K2HPO4 salt content in upper aqueous phosphate buffer phase. Horse heart cytochrome c (cyt.c) was dissolved selectively in IL phase by improving the water content of IL phase, and spectroscopic analysis revealed that the dissolved cyt.c retained its higher ordered structure. Furthermore, cyt. c dissolved in IL phase was re-extracted again from IL phase to aqueous phase by increasing the concentration of inorganic salts of the buffer solution. PMID:24013379

OPTIMIZING MODEL PERFORMANCE: VARIABLE SIZE RESOLUTION IN CLOUD CHEMISTRY MODELING. (R826371C005)

EPA Science Inventory

Under many conditions size-resolved aqueous-phase chemistry models predict higher sulfate production rates than comparable bulk aqueous-phase models. However, there are special circumstances under which bulk and size-resolved models offer similar predictions. These special con...

Jacob Kruger | NREL

Science.gov Websites

Jacob.Kruger@nrel.gov | 303-275-4081 Research Interests Algal growth systems targeting high-efficiency Hydrotalcite Catalysts," ACS Catalysis (2016) "Aqueous-Phase Fructose Dehydration Using Brønsted ) "Elucidating the Roles of Zeolite H-BEA in Aqueous-Phase Fructose Dehydration and HMF Rehydration

EVALUATION OF TECHNOLOGIES FOR IN SITU CLEANUP OF DNAPL CONTAMINATED SITES

EPA Science Inventory

Ground water contamination by non-aqueous phase liquids poses one of the greatest remedial challenges in the field of environmental engineering. Denser-than-water non-aqueous phase liquids (DNAPLs) are especially problematic due to their low water solubility, high density, an...

A Novel Aqueous Two Phase System Composed of Surfactant and Xylitol for the Purification of Lipase from Pumpkin (Cucurbita moschata) Seeds and Recycling of Phase Components.

PubMed

Amid, Mehrnoush; Manap, Mohd Yazid; Hussin, Muhaini; Mustafa, Shuhaimi

2015-06-17

Lipase is one of the more important enzymes used in various industries such as the food, detergent, pharmaceutical, textile, and pulp and paper sectors. A novel aqueous two-phase system composed of surfactant and xylitol was employed for the first time to purify lipase from Cucurbita moschata. The influence of different parameters such as type and concentration of surfactants, and the composition of the surfactant/xylitol mixtures on the partitioning behavior and recovery of lipase was investigated. Moreover, the effect of system pH and crude load on the degree of purification and yield of the purified lipase were studied. The results indicated that the lipase was partitioned into the top surfactant rich phase while the impurities partitioned into the bottom xylitol-rich phase using an aqueous two phase system composed of 24% (w/w) Triton X-100 and 20% (w/w) xylitol, at 56.2% of tie line length (TLL), (TTL is one of the important parameters in this study and it is determined from a bimodal curve in which the tie-line connects two nodes on the bimodal, that represent concentration of phase components in the top and bottom phases) and a crude load of 25% (w/w) at pH 8.0. Recovery and recycling of components was also measured in each successive step process. The enzyme was successfully recovered by the proposed method with a high purification factor of 16.4 and yield of 97.4% while over 97% of the phase components were also recovered and recycled. This study demonstrated that the proposed novel aqueous two phase system method is more efficient and economical than the traditional aqueous two phase system method for the purification and recovery of the valuable enzyme lipase.

Separation by solvent extraction

DOEpatents

Holt, Jr., Charles H.

1976-04-06

17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

Using design of experiments to optimize derivatization with methyl chloroformate for quantitative analysis of the aqueous phase from hydrothermal liquefaction of biomass.

PubMed

Madsen, René Bjerregaard; Jensen, Mads Mørk; Mørup, Anders Juul; Houlberg, Kasper; Christensen, Per Sigaard; Klemmer, Maika; Becker, Jacob; Iversen, Bo Brummerstedt; Glasius, Marianne

2016-03-01

Hydrothermal liquefaction is a promising technique for the production of bio-oil. The process produces an oil phase, a gas phase, a solid residue, and an aqueous phase. Gas chromatography coupled with mass spectrometry is used to analyze the complex aqueous phase. Especially small organic acids and nitrogen-containing compounds are of interest. The efficient derivatization reagent methyl chloroformate was used to make analysis of the complex aqueous phase from hydrothermal liquefaction of dried distillers grains with solubles possible. A circumscribed central composite design was used to optimize the responses of both derivatized and nonderivatized analytes, which included small organic acids, pyrazines, phenol, and cyclic ketones. Response surface methodology was used to visualize significant factors and identify optimized derivatization conditions (volumes of methyl chloroformate, NaOH solution, methanol, and pyridine). Twenty-nine analytes of small organic acids, pyrazines, phenol, and cyclic ketones were quantified. An additional three analytes were pseudoquantified with use of standards with similar mass spectra. Calibration curves with high correlation coefficients were obtained, in most cases R (2)  > 0.991. Method validation was evaluated with repeatability, and spike recoveries of all 29 analytes were obtained. The 32 analytes were quantified in samples from the commissioning of a continuous flow reactor and in samples from recirculation experiments involving the aqueous phase. The results indicated when the steady-state condition of the flow reactor was obtained and the effects of recirculation. The validated method will be especially useful for investigations of the effect of small organic acids on the hydrothermal liquefaction process.

Partitioning phase preference for secondary organic aerosol in an urban atmosphere

NASA Astrophysics Data System (ADS)

Chang, Wayne Li-Wen

Secondary organic aerosol (SOA) comprises a significant portion of atmospheric particular matter (PM). The impact of PM on both human health and global climate has long been recognized. Despite its importance, there are still many unanswered questions regarding the formation and evolution of SOA in the atmosphere. This study uses a modeling approach to understand the preferred partitioning behavior of SOA species into aqueous or organic condensed phases. More specifically, this work uses statistical analyses of approximately 24,000 data values for each variable from a state-of-the-art 3-D airshed model. Spatial and temporal distributions of fractions of SOA residing in the aqueous phase (fAQ) in the South Coast Air Basin of California are presented. Typical values of fAQ within the basin near the surface range from 5 to 80%. Results show that the distribution of fAQ values is inversely proportional to the total SOA loading. Further analysis accounting for various meteorological parameters indicates that large fAQ values are the results of aqueous-phase SOA insensitivity to the ambient conditions; while organic-phase SOA concentrations are dramatically reduced under unfavorable SOA formation conditions, aqueous-phase SOA level remains relatively unchanged, thus increasing fAQ at low SOA loading. Diurnal variations of fAQ near the surface are also observed: it tends to be larger during daytime hours than nighttime hours. When examining the vertical gradient of fAQ, largest values are found at heights above the surface layer. In summary, one must consider SOA in both organic and aqueous phases for proper regional and global SOA budget estimation.

A new set of K3Fe3(PO4)4·yH2O (0 ≤ y ≤ 1) layered phases obtained by topotactic reactions

NASA Astrophysics Data System (ADS)

Trad, Khiem; Wattiaux, Alain; Ben Amara, Mongi; Delmas, Claude; Carlier, Dany

2018-06-01

K3Fe3(PO4)4·H2O powder was synthesized by Na+/K+ exchange reaction from Na3Fe3(PO4)4 in aqueous medium. The replacement of the sodium cations by the potassium larger ones and water molecules causes a structural distortion leading to P2/n monoclinic K3Fe3(PO4)4·H2O. This new layered phase was characterized by XRD, Mössbauer spectroscopy and magnetic measurements. The study of its thermal stability reveals that other new layered K3Fe3(PO4)4·yH2O with (0 ≤ y ≤ 1) phases can be stabilized up to 600 °C and finally at higher temperature a new K3Fe3(PO4)4 polymorph with a different structural type is irreversibility formed.

SALICYLATE PROCESS FOR THORIUM SEPARATION FROM RARE EARTHS

DOEpatents

Cowan, G.A.

1959-08-25

The separation of thorium from rare earths is accomplished by forming an aqueous solution of salts of thorium and rare earths and sufficient acetate buffer to provide a pH of between 2 and 5, adding an ammonium salicylate to the aqueous buffered solution, contacting the resultant solution with a substantially water-immiscible organic solvent mixture of an ether and an ester, and separating the solvent extract phase containing thorium salicylate from the aqueous phase containing the rare earths.

The determination of nonylphenol and its precursors in a trickling filter wastewater treatment process.

PubMed

Petrie, Bruce; McAdam, Ewan J; Whelan, Mick J; Lester, John N; Cartmell, Elise

2013-04-01

An ultra performance liquid chromatography method coupled to a triple quadrupole mass spectrometer was developed to determine nonylphenol and 15 of its possible precursors (nonylphenol ethoxylates and nonylphenol carboxylates) in aqueous and particulate wastewater matrices. Final effluent method detection limits for all compounds ranged from 1.4 to 17.4 ng l(-1) in aqueous phases and from 1.4 to 39.4 ng g(-1) in particulate phases of samples. The method was used to measure the performance of a trickling filter wastewater treatment works, which are not routinely monitored despite their extensive usage. Relatively good removals of nonylphenol were observed over the biological secondary treatment process, accounting for a 53 % reduction. However, only an 8 % reduction in total nonylphenolic compound load was observed. This was explained by a shortening in ethoxylate chain length which initiated production of shorter polyethoxylates ranging from 1 to 4 ethoxylate units in length in final effluents. Modelling the possible impact of trickling filter discharge demonstrated that the nonylphenol environmental quality standard may be exceeded in receiving waters with low dilution ratios. In addition, there is a possibility that the EQS can be exceeded several kilometres downstream of the mixing zone due to the biotransformation of readily degradable short-chained precursors. This accentuates the need to monitor 'non-priority' parent compounds in wastewater treatment works since monitoring nonylphenol alone can give a false indication of process performance. It is thus recommended that future process performance monitoring and optimisation is undertaken using the full suite of nonylphenolic moieties which this method can facilitate.

Experimental measurements of U60 nanocluster stability in aqueous solution

NASA Astrophysics Data System (ADS)

Flynn, Shannon L.; Szymanowski, Jennifer E. S.; Gao, Yunyi; Liu, Tianbo; Burns, Peter C.; Fein, Jeremy B.

2015-05-01

In this study, the aqueous behavior of isolated U60 nanoclusters (K16Li25[UO2(O2)OH]60)-19 was studied under several pH conditions and nanocluster concentrations to determine if the nanoclusters exhibit solid phase buffering behavior or if they exhibit behavior more like aqueous complexes. U60 is a cage cluster consisting of 60 (UO2)(O2)2(OH)2 uranyl polyhedral which share OH and O2 groups with their neighboring uranyl polyhedral, resulting in negatively charged cage clusters whose charge is at least partially offset by K+ and Li+ in the aqueous phase. Batch experiments to monitor nanocluster stability were conducted for 16 days at pH 7.5, 8.0 and 8.5 at nanocluster suspension concentrations of 1.4, 2.8 and 6.0 g/L. The aqueous concentrations of U, Li, and K, determined after 10 kDa molecular weight filtration, achieved steady-state with the nanoclusters within 24 h. The steady-state aqueous U, Li, and K concentrations were independent of solution pH, however they increased with increasing nanocluster concentration, indicating that the nanoclusters do not buffer the aqueous activities as a bulk solid phase would, but exhibit behavior that is more characteristic of dissolved aqueous complexes. The ion activity product (I.A.P.) value was calculated using two approaches: (1) treating the nanoclusters as a solid phase with an activity of one, and (2) treating the nanoclusters as aqueous complexes with a non-unit activity equal to their concentration in solution. The I.A.P. values that were calculated with non-unit activity for the nanoclusters exhibited significantly less variation as a function of nanocluster concentration compared to the I.A.P. values calculated with a nanocluster activity of one. The results yield a calculated log dissociation constant for the U60 nanoclusters of 9.2 + 0.2/-0.3 (1σ). Our findings provide a better understanding of the thermodynamic stability and behavior of U60 nanoclusters in aqueous systems, and can be used to estimate the dissociation behavior of nanoclusters under a range of aqueous conditions.

Modeling the partitioning of organic chemical species in cloud phases with CLEPS (1.1)

NASA Astrophysics Data System (ADS)

Rose, Clémence; Chaumerliac, Nadine; Deguillaume, Laurent; Perroux, Hélène; Mouchel-Vallon, Camille; Leriche, Maud; Patryl, Luc; Armand, Patrick

2018-02-01

The new detailed aqueous-phase mechanism Cloud Explicit Physico-chemical Scheme (CLEPS 1.0), which describes the oxidation of isoprene-derived water-soluble organic compounds, is coupled with a warm microphysical module simulating the activation of aerosol particles into cloud droplets. CLEPS 1.0 was then extended to CLEPS 1.1 to include the chemistry of the newly added dicarboxylic acids dissolved from the particulate phase. The resulting coupled model allows the prediction of the aqueous-phase concentrations of chemical compounds originating from particle scavenging, mass transfer from the gas-phase and in-cloud aqueous chemical reactivity. The aim of the present study was more particularly to investigate the effect of particle scavenging on cloud chemistry. Several simulations were performed to assess the influence of various parameters on model predictions and to interpret long-term measurements conducted at the top of Puy de Dôme (PUY, France) in marine air masses. Specific attention was paid to carboxylic acids, whose predicted concentrations are on average in the lower range of the observations, with the exception of formic acid, which is rather overestimated in the model. The different sensitivity runs highlight the fact that formic and acetic acids mainly originate from the gas phase and have highly variable aqueous-phase reactivity depending on the cloud acidity, whereas C3-C4 carboxylic acids mainly originate from the particulate phase and are supersaturated in the cloud.

Bacterial RNA isolation.

PubMed

Ares, Manuel

2012-09-01

In this bacterial RNA isolation protocol, an "RNA-protective" treatment is followed by lysozyme digestion of the peptidoglycan component of the cell wall. EDTA promotes the loss of the outer membrane of Gram-negative bacteria and allows the lysozyme better access to the peptidoglycan. Cells begin to lyse during digestion in hypotonic lysozyme buffer and lysis is completed by sodium dodecyl sulfate (SDS) and hot phenol:chloroform:isoamyl alcohol (PCA) extraction. SDS and hot phenol disrupt membranes, denature protein (including RNase), and strip proteins from RNA. The separation of the organic phase from the aqueous phase is achieved using Phase Lock Gel, an inert material with a density intermediate between the organic and aqueous samples. The sample is split into three phases: from bottom to top, these are phenol and chloroform (organic phase), the inert gel with the interface material, and the aqueous phase with the RNA. The gel acts as a physical barrier between the sample and the organic phase plus interface. Following organic extraction, the RNA is concentrated by ethanol precipitation.

Carboxylic acid sorption regeneration process

DOEpatents

King, C. Judson; Poole, Loree J.

1995-01-01

Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine.

“Towards building better linkages between aqueous phase chemistry and microphysics in CMAQ”

EPA Science Inventory

Currently, CMAQ’s aqueous phase chemistry routine (AQCHEM-base) assumes Henry’s Law equilibrium and employs a forward Euler method to solve a small set of oxidation equations, considering the additional processes of aitken scavenging and wet deposition in series and e...

Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

PubMed

Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

2014-12-02

Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

Hydrogen donor solvent coal liquefaction process

DOEpatents

Plumlee, Karl W.

1978-01-01

An indigenous hydrocarbon product stream boiling within a range of from about C.sub.1 -700.degree. F., preferably C.sub.1 -400.degree. F., is treated to produce an upgraded hydrocarbon fuel component and a component which can be recycled, with a suitable donor solvent, to a coal liquefaction zone to catalyze the reaction. In accordance therewith, a liquid hydrocarbon fraction with a high end boiling point range up to about 700.degree. F., preferably up to about 400.degree. F., is separated from a coal liquefaction zone effluent, the separated fraction is contacted with an alkaline medium to provide a hydrocarbon phase and an aqueous extract phase, the aqueous phase is neutralized, and contacted with a peroxygen compound to convert indigenous components of the aqueous phase of said hydrocarbon fraction into catalytic components, such that the aqueous stream is suitable for recycle to the coal liquefaction zone. Naturally occurring phenols and alkyl substituted phenols, found in the aqueous phase, are converted, by the addition of hydroxyl constituents to phenols, to dihydroxy benzenes which, as disclosed in copending Application Ser. Nos. 686,813 now U.S. Pat. No. 4,049,536; 686,814 now U.S. Pat. No. 4,049,537; 686,827 now U.S. Pat. No. 4,051,012 and 686,828, K. W. Plumlee et al, filed May 17, 1976, are suitable hydrogen transfer catalysts.

Regional Air Quality Model Application of the Aqueous-Phase ...

EPA Pesticide Factsheets

In most ecosystems, atmospheric deposition is the primary input of mercury. The total wet deposition of mercury in atmospheric chemistry models is sensitive to parameterization of the aqueous-phase reduction of divalent oxidized mercury (Hg2+). However, most atmospheric chemistry models use a parameterization of the aqueous-phase reduction of Hg2+ that has been shown to be unlikely under normal ambient conditions or use a non mechanistic value derived to optimize wet deposition results. Recent laboratory experiments have shown that Hg2+ can be photochemically reduced to elemental mercury (Hg) in the aqueous-phase by dissolved organic matter and a mechanism and the rate for Hg2+ photochemical reduction by dicarboxylic acids (DCA) has been proposed. For the first time in a regional scale model, the DCA mechanism has been applied. The HO2-Hg2+ reduction mechanism, the proposed DCA reduction mechanism, and no aqueous-phase reduction (NAR) of Hg2+ are evaluated against weekly wet deposition totals, concentrations and precipitation observations from the Mercury Deposition Network (MDN) using the Community Multiscale Air Quality (CMAQ) model version 4.7.1. Regional scale simulations of mercury wet deposition using a DCA reduction mechanism evaluated well against observations, and reduced the bias in model evaluation by at least 13% over the other schemes evaluated, although summertime deposition estimates were still biased by −31.4% against observations. The use of t

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1998-01-13

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.

Aluminate effect on desilication product phase transformation

NASA Astrophysics Data System (ADS)

Peng, Hong; Vaughan, James

2018-06-01

It remains a grand challenge in the treatment of bauxite residue to physically separate zeolite (also known as the DeSilication Product, DSP) from other unleached mineral phases owing to their fine sizes, typically less than 2 μm in diameter. In this study, the effect of aluminate concentration on DSP phase transformation was investigated from synthetic NaOH-NaAl(OH)4-Na2SiO3-H2O solution at 90 °C. The results show how at relatively low aluminate concentrations of 0.125 and 0.25 M NaAl(OH)4(aq), larger zeolite crystals of up to 60 μm in diameter are formed during homogenous precipitation from aqueous solution. The precipitation process involves the conversion of zeolite LTA to sodalite via the formation of an intermediate phase, octahedral LTN. Initial amorphous solids precipitate as aggregates in which cubic zeolite LTA nucleation occurs. As the reaction proceeds, truncated octahedral LTN appears with the cubic zeolite LTA and finally sodalite crystallizes on the LTA-LTN aggregates resulting in coarsened particles.

Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

PubMed

Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

2015-03-03

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

Recovery of uranium values

DOEpatents

Brown, K. B.; Crouse, Jr., D. J.; Moore, J. G.

1959-03-10

A liquid-liquid extraction method is presented for recovering uranium values from an aqueous acidic solution by means of certain high molecular weight amine fn the amine classes of primary, secondary, heterocyclic secondary, tertiary, or heterocyclic tertiary. The uranium bearing aqueous acidic solution is contacted with the selected anine dissolved in a nonpolar waterimmiscible organfc solvent such as kerosene. The uranium which is substantially completely extracted by the organic phase may be stripped therefrom by water, and recovered from the aqueous phase by treatment into ammonia to precipitate ammonium diuranate.

RECOVERY OF URANIUM VALUES

DOEpatents

Brown, K.B.; Crouse, D.J. Jr.; Moore, J.G.

1959-03-10

A liquid-liquid extraction method is presented for recovering uranium values from an aqueous acidic solution by means of certain high molecular weight amine in the amine classes of primary, secondary, heterocyclic secondary, tertiary, or heterocyclic tertiary. The uranium bearing aqueous acidic solution is contacted with the selected amine dissolved in a nonpolar water-immiscible organic solvent such as kerosene. The uranium which is substantially completely exiracted by the organic phase may be stripped therefrom by waters and recovered from the aqueous phase by treatment into ammonia to precipitate ammonium diuranate.

Regional Air Quality Model Application of the Aqueous-Phase Photo Reduction of Atmospheric Oxidized Mercury by Dicarboxylic Acids

EPA Science Inventory

In most ecosystems, atmospheric deposition is the primary input of mercury. The total wet deposition of mercury in atmospheric chemistry models is sensitive to parameterization of the aqueous-phase reduction of divalent oxidized mercury (Hg2+). However, most atmospheric chemistry...

Carboxylic acid sorption regeneration process

DOEpatents

King, C.J.; Poole, L.J.

1995-05-02

Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine. 10 figs.

Precipitation of Co(2+) carbonates from aqueous solution: insights on the amorphous to crystalline transformation.

NASA Astrophysics Data System (ADS)

González-López, Jorge; Fernández-González, Ángeles; Jiménez, Amalia

2016-04-01

Cobalt is toxic metal that is present only as a trace in the Earth crust. However, Co might concentrate on specific areas due to both natural and anthropogenic factors and thus, soils and groundwater can be contaminated. It is from this perspective that we are interested in the precipitation of cobalt carbonates, since co-precipitation with minerals phases is a well-known method for metal immobilization in the environment. In particular, the carbonates are widely used due to its reactivity and natural abundance. In order to evaluate the cobalt carbonate precipitation at room temperature, a simple experimental work was carried out in this work. The precipitation occurred via reaction of two common salts: 0.05M of CoCl2 and 0.05M of Na2CO3 in aqueous solution. After reaction, the precipitated solid was kept in the remaining water at 25 oC and under constant stirring for different aging times of 5 min, 1 and 5 hours, 1, 2, 4, 7, 30 and 60 days. In addition to the aging and precipitation experiments, we carried out experiments to determine the solubility of the solids. In these experiments each precipitate was dissolved in Milli-Q water until equilibrium was reached and then the aqueous solution was analyzed regarding Co2+ and total alkalinity. Furthermore, acid solution calorimetry of the products were attained. Finally, we modeled the results using the PHREEQC code. Solid and aqueous phase identification and characterization have been extensively reported in a previous work (González-López et al., 2015). The main results of our investigation were the initial precipitation of an amorphous cobalt carbonate that evolve towards a poorly crystalline cobalt hydroxide carbonate with aging treatment. Solubility of both phases have been calculated under two different approaches: precipitation and dissolution. Values of solubility from each approach were obtained with a general error due to differences in experiment conditions, for instance, ionic strength, temperature and water content. It was surprising the low solubility product (Ksp) of the new phase Co2CO3(OH)2 in the order of 10-30 and this could explain its appearance only after 7 days of aging. On the other hand, the high solubility product of amorphous is consistent with its instantaneous precipitation at the beginning of the reaction. Solution calorimetry shows a higher value of exothermic solution enthalpy for crystalline cobalt hydroxide carbonate and hence, the solubility result are confirmed. Although geochemical models indicated that aqueous solution was supersaturated with respect both phases, the sequence of obtained phases (first amorphous and next crystalline) indicate that the evolution of the saturation index has to be dropped with respect to amorphous phase with time. These results points towards a simultaneous dissolution of the amorphous and the precipitation of crystalline phase Co2CO3(OH)2 at the first stages of the reaction. González-López, J. ; Fernández-González, Á. ; Jiménez, A. (2015) Prepublication: Crystallization of nanostructured cobalt hydroxide carbonate at ambient conditions: a key precursor of Co3O4. DOI: http://dx.doi.org/10.1180/minmag.2015.079.7.02

Preparation of Total RNA from Fission Yeast.

PubMed

Bähler, Jürg; Wise, Jo Ann

2017-04-03

Treatment with hot phenol breaks open fission yeast cells and begins to strip away bound proteins from RNA. Deproteinization is completed by multiple extractions with chloroform/isoamyl alcohol and separation of the aqueous and organic phases using MaXtract gel, an inert material that acts as a physical barrier between the phases. The final step is concentration of the RNA by ethanol precipitation. The protocol can be used to prepare RNA from several cultures grown in parallel, but it is important not to process too many samples at once because delays can be detrimental to RNA quality. A reasonable number of samples to process at once would be three to four for microarray or RNA sequencing analyses and six for preliminary investigations of mutants implicated in RNA metabolism. © 2017 Cold Spring Harbor Laboratory Press.

Improved Separations of Proteins and Sugar Derivatives Using the Small-Scale Cross-Axis Coil Planet Centrifuge with Locular Multilayer Coiled Columns.

PubMed

Shinomiya, Kazufusa; Umezawa, Motoki; Seki, Manami; Nitta, Jun; Zaima, Kazumasa; Harikai, Naoki; Ito, Yoichiro

2016-12-01

Countercurrent chromatography (CCC) is liquid-liquid partition chromatography without using a solid support matrix. This technique requires further improvement of partition efficiency and shortening theseparation time. The locular multilayer coils modified with and without mixer glass beads were developed for the separation of proteins and 4-methylumbelliferyl (MU) sugar derivatives using the small-scale cross-axis coil planet centrifuge. Proteins were well separated from each other and the separation was improved at a low flow rate of the mobile phase. On the other hand, 4-MU sugar derivatives were sufficiently resolved with short separation time at a highflow rate of the mobile phase under satisfactory stationary phase retention. Effective separations were achieved using the locular multilayer coil for proteins with aqueous-aqueous polymer phase systems and for 4-MU sugar derivatives with organic-aqueous two-phase solvent systems by inserting a glass bead into each locule.

A Chain of Modeling Tools For Gas and Aqueous Phase Chemstry

NASA Astrophysics Data System (ADS)

Audiffren, N.; Djouad, R.; Sportisse, B.

Atmospheric chemistry is characterized by the use of large set of chemical species and reactions. Handling with the set of data required for the definition of the model is a quite difficult task. We prsent in this short article a preprocessor for diphasic models (gas phase and aqueous phase in cloud droplets) named SPACK. The main interest of SPACK is the automatic generation of lumped species related to fast equilibria. We also developped a linear tangent model using the automatic differentiation tool named ODYSSEE in order to perform a sensitivity analysis of an atmospheric multi- phase mechanism based on RADM2 kinetic scheme.Local sensitivity coefficients are computed for two different scenarii. We focus in this study on the sensitivity of the ozone,NOx,HOx, system with respect to some aqueous phase reactions and we inves- tigate the influence of the reduction in the photolysis rates in the area below the cloud region.

Spiral counter-current chromatography of small molecules, peptides and proteins using the spiral tubing support rotor.

PubMed

Knight, Martha; Finn, Thomas M; Zehmer, John; Clayton, Adam; Pilon, Aprile

2011-09-09

An important advance in countercurrent chromatography (CCC) carried out in open flow-tubing coils, rotated in planetary centrifuges, is the new design to spread out the tubing in spirals. More spacing between the tubing was found to significantly increase the stationary phase retention, such that now all types of two-phase solvent systems can be used for liquid-liquid partition chromatography in the J-type planetary centrifuges. A spiral tubing support (STS) frame with circular channels was constructed by laser sintering technology into which FEP tubing was placed in 4 spiral loops per layer from the bottom to the top and a cover affixed allowing the tubing to connect to flow-tubing of the planetary centrifuge. The rotor was mounted and run in a P.C. Inc. type instrument. Examples of compounds of molecular weights ranging from <300 to approximately 15,000 were chromatographed in appropriate two-phase solvent systems to assess the capability for separation and purification. A mixture of small molecules including aspirin was completely separated in hexane-ethyl acetate-methanol-water. Synthetic peptides including a very hydrophobic peptide were each purified to a very high purity level in a sec-butanol solvent system. In the STS rotor high stationary phase retention was possible with the aqueous sec-butanol solvent system at a normal flow rate. Finally, the two-phase aqueous polyethylene glycol-potassium phosphate solvent system was applied to separate a protein from a lysate of an Escherichia coli expression system. These experiments demonstrate the versatility of spiral CCC using the STS rotor. Copyright © 2011 Elsevier B.V. All rights reserved.

Monodisperse hydrogel microspheres by forced droplet formation in aqueous two-phase systems.

PubMed

Ziemecka, Iwona; van Steijn, Volkert; Koper, Ger J M; Rosso, Michel; Brizard, Aurelie M; van Esch, Jan H; Kreutzer, Michiel T

2011-02-21

This paper presents a method to form micron-sized droplets in an aqueous two-phase system (ATPS) and to subsequently polymerize the droplets to produce hydrogel beads. Owing to the low interfacial tension in ATPS, droplets do not easily form spontaneously. We enforce the formation of drops by perturbing an otherwise stable jet that forms at the junction where the two aqueous streams meet. This is done by actuating a piezo-electric bending disc integrated in our device. The influence of forcing amplitude and frequency on jet breakup is described and related to the size of monodisperse droplets with a diameter in the range between 30 and 60 μm. Rapid on-chip polymerization of derivatized dextran inside the droplets created monodisperse hydrogel particles. This work shows how droplet-based microfluidics can be used in all-aqueous, surfactant-free, organic-solvent-free biocompatible two-phase environment.

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-interactive Chemicals Contained in Boundary Layer-targeted Emulsions

NASA Technical Reports Server (NTRS)

Richmond, Robert Chafee (Inventor); Schramm, Jr., Harry F. (Inventor); Defalco, Francis G. (Inventor)

2013-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Use of a parallel artificial membrane system to evaluate passive absorption and elimination in small fish.

PubMed

Kwon, Jung-Hwan; Katz, Lynn E; Liljestrand, Howard M

2006-12-01

A parallel artificial lipid membrane system was developed to mimic passive mass transfer of hydrophobic organic chemicals in fish. In this physical model system, a membrane filter-supported lipid bilayer separates two aqueous phases that represent the external and internal aqueous environments of fish. To predict bioconcentration kinetics in small fish with this system, literature absorption and elimination rates were analyzed with an allometric diffusion model to quantify the mass transfer resistances in the aqueous and lipid phases of fish. The effect of the aqueous phase mass transfer resistance was controlled by adjusting stirring intensity to mimic bioconcentration rates in small fish. Twenty-three simple aromatic hydrocarbons were chosen as model compounds for purposes of evaluation. For most of the selected chemicals, literature absorption/elimination rates fall into the range predicted from measured membrane permeabilities and elimination rates of the selected chemicals determined by the diffusion model system.

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

NASA Technical Reports Server (NTRS)

Defalco, Francis G. (Inventor); Richmond, Robert Chaffee (Inventor); Schramm, Jr., Harry F. (Inventor)

2017-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, water, or a water-based lubricant. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

NASA Technical Reports Server (NTRS)

Defalco, Francis G. (Inventor); Richmond, Robert Chaffee (Inventor); Schramm, Harry F., Jr. (Inventor)

2016-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

The effects of biomacromolecules on the physical stability of W/O/W emulsions.

PubMed

Li, Jinlong; Zhu, Yunping; Teng, Chao; Xiong, Ke; Yang, Ran; Li, Xiuting

2017-02-01

The effect of bovine serum albumin (BSA), whey protein isolate (WPI), whey protein hydrolysate (WPH), sodium caseinate (SC), carboxymethylcellulose sodium (CMC), fish gelatin (FG), high methoxyl apple pectin (HMAP), low methoxyl apple pectin (LMAP), gum Arabic (GA), ι-carrageenan (CGN), and hydroxypropyl chitosan (HPCTS) on physical stability of internal or external aqueous phase of water-in-oil-in-water (W/O/W) emulsions was evaluated. WPI and CGN in the internal aqueous phase, and GA, HPCTS, and CMC in the external phase reduced the size of emulsion droplets. BSA, WPI, SC, FG, CGN, and HPCTS improved the dilution stability of W/O/W emulsions, but HMAP had a negative effect. BSA, WPI, SC, FG, LMAP, GA, CGN, HPCTS, or CMC significantly improved the thermal stability of W/O/W emulsions. Results also indicated that the addition of CGN (1.0%), HMAP (1.0%), WPH (1.0%), or HPCTS (1.0%) in internal aqueous phase significantly increased the viscosity of emulsions, however, addition to the external aqueous phase had insignificant effects. A protein-knockout experiment confirmed that proteins as biomacromolecules, were the key factor in improving physical stability of emulsions.

Immobilization of enzymes using non-ionic colloidal liquid aphrons (CLAs): Surface and enzyme effects.

PubMed

Ward, Keeran; Xi, Jingshu; Stuckey, David C

2015-12-01

The use of non-ionic colloidal liquid aphrons (CLAs) as a support for enzyme immobilisation was investigated. Formulation required the mixing of an aqueous-surfactant solution with a relatively non-polar solvent-surfactant solution, forming a solvent droplet surrounded by a thin stabilised aqueous film (soapy shell). Studies utilising anionic surfactants have showed increased retention, however, very little have been understood about the forces governing immobilisation. This study seeks to determine the effects of enzyme properties on CLA immobilisation by examining a non-ionic/non-polar solvent system comprised of two non-ionic surfactants, Tween 20 and 80, mineral oil and the enzymes lipase, aprotinin and α-chymotrypsin. From these results it was deduced that hydrophobic interactions strongly governed immobilisation. Confocal Scanning Laser Microscopy (CSLM) revealed that immobilisation was predominantly achieved by surface adsorption attributed to hydrophobic interactions between the enzyme and the CLA surface. Enzyme surface affinity was found to increase when added directly to the formulation (pre-manufacture addition), as opposed to the bulk continuous phase (post-manufacture addition), with α-chymotrypsin and aprotinin being the most perturbed, while lipase was relatively unaffected. The effect of zeta potential on immobilisation showed that enzymes adsorbed better closer to their pI, indicating that charge minimisation was necessary for immobilisation. Finally, the effect of increasing enzyme concentration in the aqueous phase resulted in an increase in adsorption for all enzymes due to cooperativity between protein molecules, with saturation occurring faster at higher adsorption rates. Copyright © 2015 Elsevier B.V. All rights reserved.

pH recycling aqueous two-phase systems applied in extraction of Maitake β-Glucan and mechanism analysis using low-field nuclear magnetic resonance.

PubMed

Hou, Huiyun; Cao, Xuejun

2015-07-31

In this paper, a recycling aqueous two-phase systems (ATPS) based on two pH-response copolymers PADB and PMDM were used in purification of β-Glucan from Grifola frondosa. The main parameters, such as polymer concentration, type and concentration of salt, extraction temperature and pH, were investigated to optimize partition conditions. The results demonstrated that β-Glucan was extracted into PADB-rich phase, while impurities were extracted into PMDM-rich phase. In this 2.5% PADB/2.5% PMDM ATPS, 7.489 partition coefficient and 96.92% extraction recovery for β-Glucan were obtained in the presence of 30mmol/L KBr, at pH 8.20, 30°C. The phase-forming copolymers could be recycled by adjusting pH, with recoveries of over 96.0%. Furthermore, the partition mechanism of Maitake β-Glucan in PADB/PMDM aqueous two-phase systems was studied. Fourier transform infrared spectra, ForteBio Octet system and low-field nuclear magnetic resonance (LF-NMR) were introduced for elucidating the partition mechanism of β-Glucan. Especially, LF-NMR was firstly used in the mechanism analysis in partition of aqueous two-phase systems. The change of transverse relaxation time (T2) in ATPS could reflect the interaction between polymers and β-Glucan. Copyright © 2015 Elsevier B.V. All rights reserved.

Aqueous Cleaning and Validation for Space Shuttle Propulsion Hardware at the White Sands Test Facility

NASA Technical Reports Server (NTRS)

Hornung, Steven D.; Biesinger, Paul; Kirsch, Mike; Beeson, Harold; Leuders, Kathy

1999-01-01

The NASA White Sands Test Facility (WSTF) has developed an entirely aqueous final cleaning and verification process to replace the current chlorofluorocarbon (CFC) 113 based process. This process has been accepted for final cleaning and cleanliness verification of WSTF ground support equipment. The aqueous process relies on ultrapure water at 50 C (323 K) and ultrasonic agitation for removal of organic compounds and particulate. The cleanliness is verified bv determining the total organic carbon (TOC) content and filtration with particulate counting. The effectiveness of the aqueous methods for detecting hydrocarbon contamination and particulate was compared to the accepted CFC 113 sampling procedures. Testing with known contaminants, such as hydraulic fluid and cutting and lubricating oils, to establish a correlation between aqueous TOC and CFC 113 nonvolatile residue (NVR) was performed. Particulate sampling on cleaned batches of hardware that were randomly separated and sampled by the two methods was performed. This paper presents the approach and results, and discusses the issues in establishing the equivalence of aqueous sampling to CFC 113 sampling, while describing the approach for implementing aqueous techniques on Space Shuttle Propulsion hardware.

Multi-level Quantum Mechanics and Molecular Mechanics Study of Ring Opening Process of Guanine Damage by Hydroxyl Radical in Aqueous Solution.

PubMed

Liu, Peng; Wang, Qiong; Niu, Meixing; Wang, Dunyou

2017-08-10

Combining multi-level quantum mechanics theories and molecular mechanics with an explicit water model, we investigated the ring opening process of guanine damage by hydroxyl radical in aqueous solution. The detailed, atomic-level ring-opening mechanism along the reaction pathway was revealed in aqueous solution at the CCSD(T)/MM levels of theory. The potentials of mean force in aqueous solution were calculated at both the DFT/MM and CCSD(T)/MM levels of the theory. Our study found that the aqueous solution has a significant effect on this reaction in solution. In particular, by comparing the geometries of the stationary points between in gas phase and in aqueous solution, we found that the aqueous solution has a tremendous impact on the torsion angles much more than on the bond lengths and bending angles. Our calculated free-energy barrier height 31.6 kcal/mol at the CCSD(T)/MM level of theory agrees well with the one obtained based on gas-phase reaction profile and free energies of solvation. In addition, the reaction path in gas phase was also mapped using multi-level quantum mechanics theories, which shows a reaction barrier at 19.2 kcal/mol at the CCSD(T) level of theory, agreeing very well with a recent ab initio calculation result at 20.8 kcal/mol.

Non-conventional solvents in liquid phase microextraction and aqueous biphasic systems.

PubMed

An, Jiwoo; Trujillo-Rodríguez, María J; Pino, Verónica; Anderson, Jared L

2017-06-02

The development of rapid, convenient, and high throughput sample preparation approaches such as liquid phase microextraction techniques have been continuously developed over the last decade. More recently, significant attention has been given to the replacement of conventional organic solvents used in liquid phase microextraction techniques in order to reduce toxic waste and to improve selectivity and/or extraction efficiency. With these objectives, non-conventional solvents have been explored in liquid phase microextraction and aqueous biphasic systems. The utilized non-conventional solvents include ionic liquids, magnetic ionic liquids, and deep eutectic solvents. They have been widely used as extraction solvents or additives in various liquid phase microextraction modes including dispersive liquid-liquid microextraction, single-drop microextraction, hollow fiber-liquid phase microextraction, as well as in aqueous biphasic systems. This review provides an overview into the use of non-conventional solvents in these microextraction techniques in the past 5 years (2012-2016). Analytical applications of the techniques are also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Extraction of Biomolecules Using Phosphonium-Based Ionic Liquids + K3PO4 Aqueous Biphasic Systems

PubMed Central

Louros, Cláudia L. S.; Cláudio, Ana Filipa M.; Neves, Catarina M. S. S.; Freire, Mara G.; Marrucho, Isabel M.; Pauly, Jérôme; Coutinho, João A. P.

2010-01-01

Aqueous biphasic systems (ABS) provide an alternative and efficient approach for the extraction, recovery and purification of biomolecules through their partitioning between two liquid aqueous phases. In this work, the ability of hydrophilic phosphonium-based ionic liquids (ILs) to form ABS with aqueous K3PO4 solutions was evaluated for the first time. Ternary phase diagrams, and respective tie-lines and tie-lines length, formed by distinct phosphonium-based ILs, water, and K3PO4 at 298 K, were measured and are reported. The studied phosphonium-based ILs have shown to be more effective in promoting ABS compared to the imidazolium-based counterparts with similar anions. Moreover, the extractive capability of such systems was assessed for distinct biomolecules (including amino acids, food colourants and alkaloids). Densities and viscosities of both aqueous phases, at the mass fraction compositions used for the biomolecules extraction, were also determined. The evaluated IL-based ABS have been shown to be prospective extraction media, particularly for hydrophobic biomolecules, with several advantages over conventional polymer-inorganic salt ABS. PMID:20480041

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

DOE PAGES

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu; ...

2017-12-21

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds.more » Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.« less

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, Ryan D.; Lin, Ying-Hsuan; Peng, Zhuoyu

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds.more » Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10-12) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.« less

TOGA: A TOUGH code for modeling three-phase, multi-component, and non-isothermal processes involved in CO 2-based Enhanced Oil Recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Lehua; Oldenburg, Curtis M.

TOGA is a numerical reservoir simulator for modeling non-isothermal flow and transport of water, CO 2, multicomponent oil, and related gas components for applications including CO 2-enhanced oil recovery (CO 2-EOR) and geologic carbon sequestration in depleted oil and gas reservoirs. TOGA uses an approach based on the Peng-Robinson equation of state (PR-EOS) to calculate the thermophysical properties of the gas and oil phases including the gas/oil components dissolved in the aqueous phase, and uses a mixing model to estimate the thermophysical properties of the aqueous phase. The phase behavior (e.g., occurrence and disappearance of the three phases, gas +more » oil + aqueous) and the partitioning of non-aqueous components (e.g., CO 2, CH 4, and n-oil components) between coexisting phases are modeled using K-values derived from assumptions of equal-fugacity that have been demonstrated to be very accurate as shown by comparison to measured data. Models for saturated (water) vapor pressure and water solubility (in the oil phase) are used to calculate the partitioning of the water (H 2O) component between the gas and oil phases. All components (e.g., CO 2, H 2O, and n hydrocarbon components) are allowed to be present in all phases (aqueous, gaseous, and oil). TOGA uses a multiphase version of Darcy’s Law to model flow and transport through porous media of mixtures with up to three phases over a range of pressures and temperatures appropriate to hydrocarbon recovery and geologic carbon sequestration systems. Transport of the gaseous and dissolved components is by advection and Fickian molecular diffusion. New methods for phase partitioning and thermophysical property modeling in TOGA have been validated against experimental data published in the literature for describing phase partitioning and phase behavior. Flow and transport has been verified by testing against related TOUGH2 EOS modules and CMG. The code has also been validated against a CO 2-EOR experimental core flood involving flow of three phases and 12 components. Results of simulations of a hypothetical 3D CO 2-EOR problem involving three phases and multiple components are presented to demonstrate the field-scale capabilities of the new code. This user guide provides instructions for use and sample problems for verification and demonstration.« less

A Systematic Evaluation of the Extent of Photochemical Processing in Different Types of Secondary Organic Aerosols in the Aqueous Phase

NASA Astrophysics Data System (ADS)

Romonosky, D.; Lee, H.; Epstein, S. A.; Nizkorodov, S.; Laskin, J.; Laskin, A.

2013-12-01

A significant fraction of atmospheric organic compounds are predominantly found in condensed phases, such as organic phase in aerosol particles or aqueous phase in cloud droplets. The oxidation of VOCs followed by the condensation of products into particles was thought to be the main mechanism of organic aerosol (OA) formation. However, in the last several years, scientists have realized that a large fraction, if not the majority of organic particles, is produced through cloud and fog photochemical processes. Many of these organic compounds are photolabile, and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of droplets (hours) and particles (days). We previously reported that compounds in secondary organic aerosol (SOA) from ozonolysis of d-limonene efficiently photodegrade in both organic (Walser et al., 2007) and aqueous phases (Bateman et al., 2011). Significant photolysis was also observed in an aqueous extract of SOA from high-NOx photooxidation of isoprene (Nguyen et al., 2012). More recent experiments studying the response to irradiation of complex aqueous mixtures (as opposed to solutions of isolated compounds) found surprising resilience to photodegradation in aqueous extracts of SOA prepared by photooxidation of alpha-pinene (Romonosky et al., unpublished). We present a systematic investigation of the extent of photochemical processing in different types of SOA from various biogenic and anthropogenic precursors. Chamber- or flowtube-generated SOA is collected on an inert substrate, extracted in a methanol/water solution (70:30), photolyzed in the aqueous solution, and the extent of change in the molecular level composition of the material is assessed with high-resolution mass spectrometry (HR-MS). The outcome of this study will be improved understanding of the role of condensed-phase photochemistry in chemical aging of aerosol particles and cloud droplets. Bateman et al. Photolytic processing of secondary organic aerosols dissolved in cloud droplets. Phys. Chem. Chem. Phys. 2011, 13, 12199. Nguyen et al. Direct aqueous photochemistry of isoprene high-NOx secondary organic aerosol. Phys. Chem. Chem. Phys. 2012, 14, 9702. Walser et al. Photochemical aging of secondary organic aerosol particles generated from the oxidation of d-limonene. J. Phys. Chem. A 2007, 111, 1907.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1997-01-01

A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Patterns of intraocular pressure elevation after aqueous humor outflow obstruction in rats.

PubMed

Jia, L; Cepurna, W O; Johnson, E C; Morrison, J C

2000-05-01

To determine the diural intraocular pressure (IOP) response of Brown Norway rat eyes after sclerosis of the aqueous humor outflow pathways and its relationship to optic nerve damage. Hypertonic saline was injected into a single episcleral vein in 17 animals and awake IOP measured in both the light and dark phases of the circadian cycle for 34 days. Mean IOP for light and dark phases during the experimental period were compared with the respective pressures of the uninjected fellow eyes. Optic nerve cross sections from each nerve were graded for injury by five independent masked observers. For fellow eyes, mean light- and dark-phase IOP was 21 +/- 1 and 31 +/- 1 mm Hg, respectively. For four experimental eyes, mean IOPs for both phases were not altered. Six eyes demonstrated significant mean IOP elevations only during the dark phase. Of these, five showed persistent, large circadian oscillations, and four had partial optic nerve lesions. The remaining seven eyes experienced significant IOP elevations during both phases, and all had extensive optic nerve damage. Episcleral vein injection of hypertonic saline is more likely to increase IOP during the dark phase than the light. This is consistent with aqueous outflow obstruction superimposed on a circadian rhythm of aqueous humor production. Because these periodic IOP elevations produced optic nerve lesions, both light- and dark-phase IOP determinations are necessary for accurate correlation of IOP history to optic nerve damage in animals housed in a light- dark environment.

Ionic liquid-anionic surfactant based aqueous two-phase extraction for determination of antibiotics in honey by high-performance liquid chromatography.

PubMed

Yang, Xiao; Zhang, Shaohua; Yu, Wei; Liu, Zhongling; Lei, Lei; Li, Na; Zhang, Hanqi; Yu, Yong

2014-06-01

An ionic liquid-anionic surfactant based aqueous two-phase extraction was developed and applied for the extraction of tetracycline, oxytetracycline and chloramphenicol in honey. The honey sample was mixed with Na2EDTA aqueous solution. The sodium dodecyl sulfate, ionic liquid 1-octyl-3-methylimidazolium bromide and sodium chloride were added in the mixture. After the resulting mixture was ultrasonically shaken and centrifuged, the aqueous two phase system was formed and analytes were extracted into the upper phase. The parameters affecting the extraction efficiency, such as the volume of ionic liquid, the category and amount of salts, sample pH value, extraction time and temperature were investigated. The limits of detection of tetracycline, oxytetracycline and chloramphenicol were 5.8, 8.2 and 4.2 μg kg(-1), respectively. When the present method was applied to the analysis of real honey samples, the recoveries of analytes ranged from 85.5 to 110.9% and relative standard deviations were lower than 6.9%. Copyright © 2014 Elsevier B.V. All rights reserved.

Interactions in the aqueous phase and adsorption at the air-water interface of caseinoglycomacropeptide (GMP) and beta-lactoglobulin mixed systems.

PubMed

Martinez, María J; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Pilosof, Ana M R

2009-01-01

The aim of this work was to study the interactions and adsorption of caseinoglycomacropeptide (GMP) and GMP:beta-lactoglobulin (beta-lg) mixed system in the aqueous phase and at the air-water interface. The existence of associative interactions between GMP and beta-lg in the aqueous phase was investigated by dynamic light scattering, differential scanning calorimetry (DSC), fluorometry and native PAGE-electrophoresis. The surface pressure isotherm and the static and dynamic surface pressure were determined by tensiometry and surface dilatational properties. The results showed that GMP presented higher surface activity than beta-lg at a concentration of 4%wt but beta-lg showed higher film forming ability. In the mixed systems beta-lg dominated the static and dynamic surface pressure and the rheological properties of interfacial films suggesting that beta-lg hinders GMP adsorption because, in simple competition, GMP should dominate because of its higher surface activity. The surface predominance of beta-lg can be attributed to binding of GMP to beta-lg in the aqueous phase that prevents GMP adsorption on its own.

Aqueous-phase story of isoprene - A mini-review and reaction with HONO

NASA Astrophysics Data System (ADS)

Rudziński, Krzysztof J.; Szmigielski, Rafał; Kuznietsova, Inna; Wach, Paulina; Staszek, Dorota

2016-04-01

Isoprene is a major biogenic hydrocarbon emitted to the atmosphere and a well-recognized player in atmospheric chemistry, formation of secondary organic aerosol and air quality. Most of the scientific work on isoprene has focused on the gas-phase and smog chamber processing while direct aqueous chemistry has escaped the major attention because physical solubility of isoprene in water is low. Therefore, this work recollects the results of genuine research carried on atmospherically relevant aqueous-phase transformations of isoprene. It clearly shows that isoprene dissolves in water and reacts in aqueous solutions with common atmospheric oxidants such as hydrogen peroxide, ozone, hydroxyl radicals, sulfate radicals and sulfite radicals. The reactions take place in the bulk of solutions or on the gas-liquid interfaces and often are acid-catalyzed and/or enhanced by light. The review is appended by an experimental study of the aqueous-phase reaction of isoprene with nitrous acid (HONO). The decay of isoprene and formation of new products are demonstrated. The tentative chemical mechanism of the reaction is suggested, which starts with slow decomposition of HONO to NO2 and NO. The aqueous chemistry of isoprene explains the formation of a few tropospheric components identified by scientists yet considered of unknown origin. The reaction of isoprene with sulfate radicals explains formation of the MW 182 organosulfate found in ambient aerosol and rainwater while the reaction of isoprene with HONO explains formation of the MW 129 and MW 229 nitroorganic compounds identified in rainwater. Thus, aqueous transformations of isoprene should not be neglected without evidence but rather considered and evaluated in modeling of atmospheric chemical processes even if alternative and apparently dominant heterogeneous pathways of isoprene transformation, dry or wet, are demonstrated.

Three-phase hollow-fiber liquid-phase microextraction combined with HPLC-UV for the determination of isothiazolinone biocides in adhesives used for food packaging materials.

PubMed

Rosero-Moreano, Milton; Canellas, Elena; Nerín, Cristina

2014-02-01

The present study deals with the development of a liquid microextraction procedure for enhancing the sensitivity of the determination of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one in adhesives. The procedure involves a three-phase hollow-fiber liquid-phase microextraction using a semipermeable polypropylene membrane, which contained 1-octanol as the organic phase in the pores of the membrane. The donor and acceptor phases are aqueous acidic and alkaline media, respectively, and the final liquid phase (acceptor) is analyzed by HPLC coupled with diode array detection. The most appropriate conditions were extraction time 20 min, stirring speed 1400 rpm, extraction temperature 50°C. The quantification limits of the method were 0.123 and 0.490 μg/g for 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, respectively. Three different adhesive samples were successfully analyzed. The procedure was compared to direct analysis using ultra high pressure liquid chromatography coupled with TOF-MS, where the identification of the compounds and the quantification values were confirmed. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dense Non Aqueous Phase Liquid (DNAPL) Removal from Fractured Rock using Thermal Conductive Heating (TCH)

DTIC Science & Technology

2013-01-01

of 95% or greater in parent compounds . The data also show that most rock concentrations were lowered to around 0-5...INTRODUCTION 1.1 BACKGROUND The removal of dense non-aqueous phase liquids (DNAPL) and associated dissolved phase compounds is challenging in ...trend as presented in Figure 10. Figure 10. Vapor stream VOC concentrations for the dominant compounds . The more or less consistent level of

Process for recovering hydrocarbons from a diatomite-type ore

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davis, B.W.

1983-02-15

A process for recovering hydrocarbons from a diatomite-type ore which comprises contacting the diatomite ore with a C/sub 4/-C/sub 10/ alcohol and thereafter contacting the diatomite ore-alcohol mixture with an aqueous alkaline solution to separate a hydrocarbon-alcohol phase and an alkaline aqueous phase containing the stripped diatomite ore. Thereafter, the alcohol is distilled off from the hydrocarbon phase and recycled back into the initial process.

Preparation of novel alkaline pH-responsive copolymers for the formation of recyclable aqueous two-phase systems and their application in the extraction of lincomycin.

PubMed

Liu, Jiali; Cao, Xuejun

2016-02-01

Aqueous two-phase systems have potential industrial application in bioseparation and biocatalysis engineering; however, their practical application is limited primarily because the copolymers involved in the formation of aqueous two-phase systems cannot be recovered. In this study, two novel alkaline pH-responsive copolymers were synthesized and examined for the extraction of lincomycin. The two copolymers could form a novel alkaline aqueous two-phase systems when their concentrations were both 6% w/w and the pH was 8.4(±0.1)-8.7(±0.1). One copolymer was synthesized using acrylic acid, 2-(dimethylamino)ethyl methacrylate, and butyl methacrylate as monomers. Moreover, 98.8% of the copolymer could be recovered by adjusting the solution pH to its isoelectric point (pH 6.29). The other copolymer was synthesized using the monomers methacrylic acid, 2-(dimethylamino)ethyl methacrylate, and methyl methacrylate. In this case, 96.7% of the copolymer could be recovered by adjusting the solution pH to 7.19. The optimal partition coefficient of lincomycin was 0.17 at 30°C in the presence of 10 mM KBr and 5.5 at 40°C in the presence of 80 mM Ti(SO4)2 using the novel alkaline aqueous two-phase systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent Extraction of Rare Earth Elements from a Nitric Acid Leach Solution of Apatite by Mixtures of Tributyl Phosphate and Di-(2-ethylhexyl) Phosphoric Acid

NASA Astrophysics Data System (ADS)

Ferdowsi, Ali; Yoozbashizadeh, Hossein

2017-12-01

Solvent extraction of rare earths from nitrate leach liquor of apatite using mixtures of tributyl phosphate (TBP) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) was studied. The effects of nitrate and hydrogen ion concentration of the aqueous phase as well as the composition and concentration of extractants in the organic phase on the extraction behavior of lanthanum, cerium, neodymium, and yttrium were investigated. The distribution ratio of REEs increases by increasing the nitrate concentration in aqueous phase and concentration of extractants in organic phase, but the hydrogen ion concentration in aqueous phase has a decreasing effect. Yttrium as a heavy rare earth is more sensitive to these parameters than light rare earth elements. Although the composition of organic phase has a minor effect on the extraction of light rare earths, the percent of extraction of yttrium decreases dramatically by increasing the TBP content of organic phase. Mixtures of TBP and D2EHPA can show either synergism or antagonism extraction depending on the concentration and composition of extractants in organic phase. The best condition for separating rare earth elements in groups of heavy and light REEs can be achieved at high nitrate concentration, low H+ concentration, and high concentration of D2EHPA in organic phase. Separation of Ce and La by TBP and D2EHPA is practically impossible in the studied conditions; however, low nitrate concentration and high hydrogen ion concentration in aqueous phase and low concentration of extractants in organic phase favor the separation of Nd from other light rare earth elements.

GEOSURF: a computer program for modeling adsorption on mineral surfaces from aqueous solution

NASA Astrophysics Data System (ADS)

Sahai, Nita; Sverjensky, Dimitri A.

1998-11-01

A new program, GEOSURF, has been developed for calculating aqueous and surface speciation consistent with the triple-layer model of surface complexation. GEOSURF is an extension of the original programs MINEQL, MICROQL and HYDRAQL. We present, here, the basic algorithm of GEOSURF along with a description of the new features implemented. GEOSURF is linked to internally consistent data bases for surface species (SURFK.DAT) and for aqueous species (AQSOL.DAT). SURFK.DAT contains properties of minerals such as site densities, and equilibrium constants for adsorption of aqueous protons and electrolyte ions on a variety of oxides and hydroxides. The Helgeson, Kirkham and Flowers version of the extended Debye-Huckel Equation for 1:1 electrolytes is implemented for calculating aqueous activity coefficients. This permits the calculation of speciation at ionic strengths greater than 0.5 M. The activity of water is computed explicitly from the osmotic coefficient of the solution, and the total amount of electrolyte cation (or anion) is adjusted to satisfy the electroneutrality condition. Finally, the use of standard symbols for chemical species rather than species identification numbers is included to facilitate use of the program. One of the main limitations of GEOSURF is that aqueous and surface speciation can only be calculated at fixed pH and at fixed concentration of total adsorbate. Thus, the program cannot perform reaction-path calculations: it cannot determine whether or not a solution is over- or under-saturated with respect to one or more solid phases. To check the proper running of GEOSURF, we have compared results generated by GEOSURF with those from two other programs, HYDRAQL and EQ3. The Davies equation and the "bdot" equation, respectively, are used in the latter two programs for calculating aqueous activity coefficients. An example of the model fit to experimental data for rutile in 0.001 M-2.0 M NaNO 3 is included.

Partition Efficiency of High-Pitch Locular Multilayer Coil for Countercurrent Chromatographic Separation of Proteins Using Small-Scale Cross-Axis Coil Planet Centrifuge and Application to Purification of Various Collagenases with Aqueous-Aqueous Polymer Phase Systems

PubMed Central

Shinomiya, Kazufusa; Kobayashi, Hiroko; Inokuchi, Norio; Nakagomi, Kazuya; Ito, Yoichiro

2010-01-01

Partition efficiency of the high-pitch locular multilayer coil was evaluated in countercurrent chromatographic (CCC) separation of proteins with an aqueous-aqueous polymer phase system using the small-scale cross-axis coil planet centrifuge (X-axis CPC) fabricated in our laboratory. The separation column was specially made by high-pitch (ca 5 cm) winding of 1.0 mm I.D., 2.0 mm O.D. locular tubing compressed at 2 cm intervals with a total capacity of 29.5 mL. The protein separation was performed using a set of stable proteins including cytochrome C, myoglobin, and lysozyme with the 12.5% (w/w) polyethylene glycol (PEG) 1000 and 12.5% (w/w) dibasic potassium phosphate system (pH 9.2) under 1000 rpm of column revolution. This high-pitch locular tubing yielded substantially increased stationary phase retention than the normal locular tubing for both lower and upper mobile phases. In order to demonstrate the capability of the high-pitch locular tubing, the purification of collagenase from the crude commercial sample was carried out using an aqueous-aqueous polymer phase system. Using the 16.0% (w/w) PEG 1000 – 6.3% (w/w) dibasic potassium phosphate – 6.3% (w/w) monobasic potassium phosphate system (pH 6.6), collagenase I, II, V and X derived from Clostridium hystolyticum were separated from other proteins and colored small molecular weight compounds present in the crude commercial sample, while collagenase N-2 and S-1 from Streptomyces parvulus subsp. citrinus were eluted with impurities at the solvent front with the upper phase. The collagenase from C. hystolyticum retained its enzymatic activity in the purified fractions. The overall results demonstrated that the high-pitch locular multilayer coil is effectively used for the CCC purification of bioactive compounds without loss of their enzymatic activities. PMID:21869859

Coencapsulation of (-)-Epigallocatechin-3-gallate and Quercetin in Particle-Stabilized W/O/W Emulsion Gels: Controlled Release and Bioaccessibility.

PubMed

Chen, Xing; McClements, David Julian; Wang, Jian; Zou, Liqiang; Deng, Sumeng; Liu, Wei; Yan, Chi; Zhu, Yuqing; Cheng, Ce; Liu, Chengmei

2018-04-11

Particle-stabilized W 1 /O/W 2 emulsion gels were fabricated using a two-step procedure: ( i) a W 1 /O emulsion was formed containing saccharose (for osmotic stress balance) and gelatin (as a gelling agent) in the aqueous phase and polyglycerol polyricinoleate (a lipophilic surfactant) in the oil phase; ( ii) this W 1 /O emulsion was then homogenized with another water phase (W 2 ) containing wheat gliadin nanoparticles (hydrophilic emulsifier). The gliadin nanoparticles in the external aqueous phase aggregated at pH 5.5, which led to the formation of particle-stabilized W 1 /O/W 2 emulsion gels with good stability to phase separation. These emulsion gels were then used to coencapsulate a hydrophilic bioactive (epigallocatechin-3-gallate, EGCG) in the internal aqueous phase (encapsulation efficiency = 65.5%) and a hydrophobic bioactive (quercetin) in the oil phase (encapsulation efficiency = 97.2%). The emulsion gels improved EGCG chemical stability and quercetin solubility under simulated gastrointestinal conditions, which led to a 2- and 4-fold increase in their effective bioaccessibility, respectively.

Aqueous photooxidation of ambient Po Valley Italy air samples: Insights into secondary organic aerosol formation

NASA Astrophysics Data System (ADS)

Kirkland, J. R.; Lim, Y. B.; Sullivan, A. P.; Decesari, S.; Facchini, C.; Collett, J. L.; Keutsch, F. N.; Turpin, B. J.

2012-12-01

In this work, we conducted aqueous photooxidation experiments with ambient samples in order to develop insights concerning the formation of secondary organic aerosol through gas followed by aqueous chemistry (SOAaq). Water-soluble organics (e.g., glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone) are formed through gas phase oxidation of alkene and aromatic emissions of anthropogenic and biogenic origin. Their further oxidation in clouds, fogs and wet aerosols can form lower volatility products (e.g., oligomers, organic acids) that remain in the particle phase after water evaporation, thus producing SOA. The aqueous OH radical oxidation of several individual potentially important precursors has been studied in the laboratory. In this work, we used a mist-chamber apparatus to collect atmospheric mixtures of water-soluble gases from the ambient air at San Pietro Capofiume, Italy during the PEGASOS field campaign. We measured the concentration dynamics after addition of OH radicals, in order to develop new insights regarding formation of SOA through aqueous chemistry. Specifically, batch aqueous reactions were conducted with 33 ml mist-chamber samples (TOC ~ 50-100μM) and OH radicals (~10-12M) in a new low-volume aqueous reaction vessel. OH radicals were formed in-situ, continuously by H2O2 photolysis. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS +/-), and ESI-MS with IC pre-separation (IC/ESI-MS-). Reproducible formation of pyruvate and oxalate were observed both by IC and ESI-MS. These compounds are known to form from aldehyde oxidation in the aqueous phase. New insights regarding the aqueous chemistry of these "more atmospherically-realistic" experiments will be discussed.

PROCESS FOR DECONTAMINATING THORIUM AND URANIUM WITH RESPECT TO RUTHENIUM

DOEpatents

Meservey, A.A.; Rainey, R.H.

1959-10-20

The control of ruthenium extraction in solvent-extraction processing of neutron-irradiated thorium is presented. Ruthenium is rendered organic-insoluble by the provision of sulfite or bisulfite ions in the aqueous feed solution. As a result the ruthenium remains in the aqueous phase along with other fission product and protactinium values, thorium and uranium values being extracted into the organic phase. This process is particularly applicable to the use of a nitrate-ion-deficient aqueous feed solution and to the use of tributyl phosphate as the organic extractant.

Development of performance matrix for generic product equivalence of acyclovir topical creams.

PubMed

Krishnaiah, Yellela S R; Xu, Xiaoming; Rahman, Ziyaur; Yang, Yang; Katragadda, Usha; Lionberger, Robert; Peters, John R; Uhl, Kathleen; Khan, Mansoor A

2014-11-20

The effect of process variability on physicochemical characteristics and in vitro performance of qualitatively (Q1) and quantitatively (Q2) equivalent generic acyclovir topical dermatological creams was investigated to develop a matrix of standards for determining their in vitro bioequivalence with reference listed drug (RLD) product (Zovirax®). A fractional factorial design of experiment (DOE) with triplicate center point was used to create 11 acyclovir cream formulations with manufacturing variables such as pH of aqueous phase, emulsification time, homogenization speed, and emulsification temperature. Three more formulations (F-12-F-14) with drug particle size representing RLD were also prepared where the pH of the final product was adjusted. The formulations were subjected to physicochemical characterization (drug particle size, spreadability, viscosity, pH, and drug concentration in aqueous phase) and in vitro drug release studies against RLD. The results demonstrated that DOE formulations were structurally and functionally (e.g., drug release) similar (Q3) to RLD. Moreover, in vitro drug permeation studies showed that extent of drug bioavailability/retention in human epidermis from F-12-F-14 were similar to RLD, although differed in rate of permeation. The results suggested generic acyclovir creams can be manufactured to obtain identical performance as that of RLD with Q1/Q2/Q3. Published by Elsevier B.V.

Mechanistic Insights into Radical-Mediated Oxidation of Tryptophan from ab Initio Quantum Chemistry Calculations and QM/MM Molecular Dynamics Simulations.

PubMed

Wood, Geoffrey P F; Sreedhara, Alavattam; Moore, Jamie M; Wang, John; Trout, Bernhardt L

2016-05-12

An assessment of the mechanisms of (•)OH and (•)OOH radical-mediated oxidation of tryptophan was performed using density functional theory calculations and ab initio plane-wave Quantum Mechanics/Molecular Mechanics (QM/MM) molecular dynamics simulations. For the (•)OH reactions, addition to the pyrrole ring at position 2 is the most favored site with a barrierless reaction in the gas phase. The subsequent degradation of this adduct through a H atom transfer to water was intermittently observed in aqueous-phase molecular dynamics simulations. For the (•)OOH reactions, addition to the pyrrole ring at position 2 is the most favored pathway, in contrast to the situation in the model system ethylene, where concerted addition to the double bond is preferred. From the (•)OOH position 2 adduct QM/MM simulations show that formation of oxy-3-indolanaline occurs readily in an aqueous environment. The observed transformation starts from an initial rupture of the O-O bond followed by a H atom transfer with the accompanying loss of an (•)OH radical to solution. Finally, classical molecular dynamics simulations were performed to equate observed differential oxidation rates of various tryptophan residues in monoclonal antibody fragments. It was found that simple parameters derived from simulation correlate well with the experimental data.

Selective recovery of vanadium and scandium by ion exchange with D201 and solvent extraction using P507 from hydrochloric acid leaching solution of red mud.

PubMed

Zhu, Xiaobo; Li, Wang; Tang, Sen; Zeng, Majian; Bai, Pengyuan; Chen, Lunjian

2017-05-01

D201 resin and P507 extractant diluted with sulfonated kerosene were used to respectively separate vanadium and scandium, and impurity ions from hydrochloric acid leaching solution of red mud. More than 99% of vanadium was selectively adsorbed from the hydrochloric acid leaching solution under the conditions of pH value of 1.8, volume ratio of leaching solution to resin of 10, and flow rate of 3.33 mL/min. Maximum extraction and separation of scandium was observed from the acid leaching solution at an aqueous pH value of 0.2. More than 99% of scandium can be selectively extracted using 15% P507, 5% TBP at the aqueous solution/organic phase (A/O) ratio of 10:1 for 6 min. The loaded organic phase was washed with 0.3 mol/L sulfuric acid, wherein most impurities were removed. After the process of desorption or stripping, precipitation, and roasting, high-purity V 2 O 5 and Sc 2 O 3 were obtained. Finally, a conceptual flow sheet was established to separate and recover vanadium and scandium from red mud hydrochloric acid leaching solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Tailored Magnetic Nanoparticles for Optimizing Magnetic Fluid Hyperthermia

PubMed Central

Khandhar, Amit; Ferguson, R. Matthew; Simon, Julian A.; Krishnan, Kannan M.

2011-01-01

Magnetic Fluid Hyperthermia (MFH) is a promising approach towards adjuvant cancer therapy that is based on the localized heating of tumors using the relaxation losses of iron oxide magnetic nanoparticles (MNPs) in alternating magnetic fields (AMF). In this study, we demonstrate optimization of MFH by tailoring MNP size to an applied AMF frequency. Unlike conventional aqueous synthesis routes, we use organic synthesis routes that offer precise control over MNP size (diameter ~ 10–25 nm), size distribution and phase purity. Furthermore, the particles are successfully transferred to the aqueous phase using a biocompatible amphiphilic polymer, and demonstrate long-term shelf life. A rigorous characterization protocol ensures that the water-stable MNPs meet all the critical requirements: (1) uniform shape and monodispersity, (2) phase purity, (3) stable magnetic properties approaching that of the bulk, (4) colloidal stability, (5) substantial shelf life and (6) pose no significant in vitro toxicity. Using a dedicated hyperthermia system, we then identified that 16 nm monodisperse MNPs (σ ~ 0.175) respond optimally to our chosen AMF conditions (f = 373 kHz, Ho = 14 kA/m); however, with a broader size distribution (σ ~ 0.284) the Specific Loss Power (SLP) decreases by 30%. Finally, we show that these tailored MNPs demonstrate maximum hyperthermia efficiency by reducing viability of Jurkat cells in vitro, suggesting our optimization translates truthfully to cell populations. In summary, we present a way to intrinsically optimize MFH by tailoring the MNPs to any applied AMF, a required precursor to optimize dose and time of treatment. PMID:22213652

Phyllosilicate diversity and past aqueous activity revealed at Mawrth Vallis, Mars

USGS Publications Warehouse

Bishop, J.L.; Dobrea, E.Z.N.; McKeown, N.K.; Parente, M.; Ehlmann, B.L.; Michalski, J.R.; Milliken, R.E.; Poulet, F.; Swayze, G.A.; Mustard, J.F.; Murchie, S.L.; Bibring, J.-P.

2008-01-01

Observations by the Mars Reconnaissance Orbiter/Compact Reconnaissance Imaging Spectrometer for Mars in the Mawrth Vallis region show several phyllosilicate species, indicating a wide range of past aqueous activity. Iron/magnesium (Fe/Mg)-smectite is observed in light-toned outcrops that probably formed via aqueous alteration of basalt of the ancient cratered terrain. This unit is overlain by rocks rich in hydrated silica, montmorillonite, and kaolinite that may have formed via subsequent leaching of Fe and Mg through extended aqueous events or a change in aqueous chemistry. A spectral feature attributed to an Fe2+ phase is present in many locations in the Mawrth Vallis region at the transition from Fe/Mg-smectite to aluminum/silicon (Al/Si)-rich units. Fe2+-bearing materials in terrestrial sediments are typically associated with microorganisms or changes in pH or cations and could be explained here by hydrothermal activity. The stratigraphy of Fe/Mg-smectite overlain by a ferrous phase, hydrated silica, and then Al-phyllosilicates implies a complex aqueous history.

Aqueous Alteration of Carbonaceous Chondrites: New Insights from Comparative Studies of Two Unbrecciated CM2 Chondrites, Y 791198 and ALH 81002

NASA Technical Reports Server (NTRS)

Chizmadia, L. J.; Brearley, A. J.

2004-01-01

Carbonaceous chondrites are an important resource for understanding the physical and chemical conditions in the early solar system. In particular, a long-standing question concerns the role of water in the cosmochemical evolution of carbonaceous chondrites. It is well established that extensive hydration of primary nebular phases occurred in the CM and CI chondrites, but the location where this alteration occurred remains controversial. In the CM2 chondrites, hydration formed secondary phases such as serpentine, tochilinite, pentlandite, carbonate and PCP. There are several textural observations which suggest that alteration occurred before the accretion of the final CM parent asteroid, i.e. preaccretionary alteration. Conversely, there is a significant body of evidence that supports parent-body alteration. In order to test these two competing hypotheses further, we studied two CM chondrites, Y-791198 and ALH81002, two meteorites that exhibit widely differing degrees of aqueous alteration. In addition, both meteorites have primary accretionary textures, i.e. experienced minimal asteroidal brecciation. Brecciation significantly complicates the task of unraveling alteration histories, mixing components that have been altered to different degrees from different locations on the same asteroidal parent body. Alteration in Y-791198 is mostly confined to chondrule mesostases, FeNi metal and fine-grained matrix and rims. In comparison, the primary chondrule silicates in ALH81002 have undergone extensive replacement by secondary hydrous phases. This study focuses on compositional and textural relationships between chondrule mesostasis and the associated rim materials. Our hypothesis is: both these components are highly susceptible to aqueous alteration and should be sensitive recorders of the alteration process. For parent body alteration, we expect systematic coupled mineralogical and compositional changes in rims and altered mesostasis, as elemental exchange between these components occurs. Conversely, for preaccretionary alteration, there should be no clear relationships between the rims and mesostases.

Aqueous phase oligomerization of α,β-unsaturated carbonyls and acids investigated using ion mobility spectrometry coupled to mass spectrometry (IMS-MS)

NASA Astrophysics Data System (ADS)

Renard, Pascal; Tlili, Sabrine; Ravier, Sylvain; Quivet, Etienne; Monod, Anne

2016-04-01

One of the current essential issues to unravel our ability to forecast future climate change and air quality, implies a better understanding of natural processes leading to secondary organic aerosol (SOA) formation, and in particular the formation and fate of oligomers. The difficulty in characterizing macromolecules is to discern between large oxygenated molecules from series of oligomers containing repeated small monomers of diverse structures. In the present study, taking advantage from previously established radical vinyl oligomerization of methyl vinylketone (MVK) in the aqueous phase, where relatively simple oligomers containing up to 14 monomers were observed, we have investigated the same reactivity on several other unsaturated water soluble organic compounds (UWSOCs) and on a few mixtures of these precursor compounds. The technique used to characterize the formed oligomers was a traveling wave ion mobility spectrometry coupled to a hybrid quadrupole - time of flight mass spectrometer (IMS-MS) fitted with an electrospray source and ultra-high performance liquid chromatography (UPLC). The technique allows for an additional separation, especially for large ions, containing long carbon chains. We have shown the efficiency of the IMS-mass spectrometry technique to detect oligomers derived from MVK photooxidation in the aqueous phase. The results were then compared to other oligomers, derived from ten other individual biogenic UWSOCs. The technique allowed distinguishing between different oligomers arising from different precursors. It also clearly showed that compounds bearing a non-conjugated unsaturation did not provide oligomerization. Finally, it was shown that the IMS-mass spectrometry technique, applied to mixtures of unsaturated conjugated precursors, exhibited the ability of these precursors to co-oligomerize, i.e. forming only one complex oligomer system bearing monomers of different structures. The results are discussed in terms of atmospheric implications for the detection of oligomers in complex chamber and/or field samples.

Extraction of cesium, strontium and the platinium group metals from acidic high activity nuclear waste using a Purex process compatible organic extractant. Final report, December 15, 1980-August 15, 1983

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davis, M.W. Jr.; Van Brunt, V.

1984-09-14

Purex process compatible organic systems which selectively and reversibly extract cesium, strontium, and palladium from synthetic mixed fission product solutions containing 3M HNO/sub 3/ have been developed. This advance makes the development of continuous solvent extraction processes for their recovery more likely. The most favorable cesium and strontium complexing solutions have been tested for radiation stability to 10/sup 7/ rad using a 0.4 x 10/sup 7/ rad/h /sup 60/Co source. The distribution coefficients dropped somewhat but remained above unity. For cesium the complexing organic solution is 5 vol % (0.1M) NNS, 27 vol % TBP and 68 vol % kerosenemore » containing 0.05m Bis 4,4',(5')(1-hydroxy 2-ethylhexyl)-benzo 18-crown-6 (Crown XVII). The NNS is a sulfonic acid cation exchanger. With an aqueous phase containing 0.006M Cs/sup +1/ in contact with an equal volume of extractant the D org/aq = 1.6 at a temperature of 25 to 35/sup 0/C. For strontium the complexing organic solution is 5 vol % (0.1M) NNS, 27 vol % TBP and 68 vol % Kerosene containing 0.02M Bis 4,4'(5') (1-hydroxyheptyl)cyclohexo 18-crown-6 (Crown XVI). With an aqueous phase containing 0.003M Sr/sup +2/ in contact with an equal volume of extractant the D org/aq = 1.98 at a temperature of 25 to 35/sup 0/C. For palladium the complexing organic solution consisted of a ratio of TBP/kerosene of 0.667 containing 0.3M Alamine 336 which is a tertiary amine anion exchanger. With an aqueous phase containing 0.0045M Pd/sup +/ in contact with an equal volume of extractant the D org/aq = 1.95 at a temperature of 25 to 35/sup 0/C.« less

Analysis of organic compounds in aqueous samples of former ammunition plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levsen, K.; Preiss, A.; Berger-Preiss, E.

1995-12-31

In Germany, a large number of sites exist where ammunition was produced before and in particular during World War II. These former production sites represent a particular threat to the environment because these plants were constructed and operated under war conditions, where production was far more important than protection of the health of the (in general forced) workers and the environment. New approaches are presented for the extraction and analysis of explosives and related compounds in aqueous samples from former ammunition production sites. Quantitative extraction of nitro aromatics but also of the polar nitroamines such as RDX and HMX ismore » achieved by solid phase extraction with styrene-divinylbenzene polymers (Lichrolut EN). Proton nuclear magnetic resonance ({sup 1}H-NMR) has been used to identify and quantify unknowns in ammunition waste water. Finally, automated multiple development (AMD) high performance thin layer chromatography was applied for the first time to the analysis of this compound class.« less

EFFECT OF AQUEOUS PHASE PROPERTIES ON CLAY PARTICLE ZETA POTENTIAL AND ELECTRO-OSMOTIC PERMEABILITY: IMPLICATIONS FOR ELECTRO-KINETIC SOIL REMEDIATION PROCESSES

EPA Science Inventory

The influence of aqueous phase properties (pH, ionic strength and divalent metal ion concentration) on clay particle zeta potential and packed-bed electro-osmotic permeability was quantified. Although pH strongly altered the zeta potential of a Georgia kaolinite, it did not signi...

Photocatalytic Destruction of Nitrate Esters in Air

DTIC Science & Technology

2000-07-01

four technologies are thermal treatment (direct flame or incineration), absorption (scrubbing), biofiltration , and adsorption (activated carbon). The...recycling the water through an aqueous phase photocatalytic system. Both approaches eliminate the carbon and reduce the water consumption. The use...of an aqueous phase photocatalytic oxidation system increases the capital equipment cost but eliminates the chemical handling and wastewater issues

[Raman spectroscopic analysis of dissolution and phase transformation of chloropinnoite in the boric acid aqueous solution].

PubMed

Li, Xiao-Ping; Gao, Shi-Yang; Liu, Zhi-Hong; Hu, Man-Cheng; Xia, Shu-Ping

2005-01-01

Raman spectroscopy of dissolution and transformation of chloropinnoite in 4.5% (w.t.%) boric acid aqueous solution at 30 degrees C has been recorded. The Raman spectra of kinetics process have been obtained. The phase transformation product is kurnakovite (2MgO x 3B2O3 x 15H2O). The main polyborate anions and their interaction in aqueous solution have been proposed according to the Raman spectrum. Some assignments were tentatively given and the relations between the existing forms of polyborate anions and the crystallizing solid phases have been gained. A mechanisms of dissolution and crystallization reactions and the formation condition of kurnakovite in Qinghai-Tibet plateau were proposed and discussed.

Peptide Folding and Translocation Across the Water-Membrane Interface

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Chang, Sherwood (Technical Monitor)

1997-01-01

The ability of small peptides to organize at aqueous interfaces was examined by performing a series of large-scale, molecular dynamics computer simulations of several peptides composed of two amino acids, nonpolar leucine (L) and polar glutamine (Q). The peptides differed in size and sequence of the amino acids. Studies on dipeptides LL, LQ, QL and QQ were extended to two heptamers, LQQLLQL and LQLQLQL, designed to maximize interfacial stability of an alpha-helix and a beta-strand, respectively, by exposing polar side chains to water and nonpolar side chains to a nonpolar phase. Finally, a transition of an undecamer, composed entirely of leucine residues, from a disordered structure in water to an alpha-helix in a nonpolar phase representing the interior of the membrane was investigated. Complete folding of a peptide in solution was accomplished for the first time in computer simulations. The simulations revealed several basic principles governing the sequence-dependent organization of peptides at interfaces. Short peptides tend to accumulate at interfaces and acquire ordered structures, providing that they have a proper sequence of polar and nonpolar amino acids. The dominant factor determining the interfacial structure of peptides is the hydrophobic effect, which is manifested at aqueous interfaces as a tendency for polar and nonpolar groups of the solute to segregate into the aqueous and nonpolar phases, respectively. If peptides consist of nonpolar residue's only, they become inserted into the nonpolar phase. As demonstrated by the example of the leucine undecamer, such peptides fold into an alpha-helix as they partition into the nonpolar medium. The folding proceeds through an intermediate, called 3-10-helix, which remains in equilibrium with the alpha-helix. Once in the nonpolar environment, the peptides can readily change their orientation with respect to the interface from parallel to perpendicular, especially in response to local electric fields. The ability of nonpolar peptides to modify both the structure and orientation with respect to the interface from parallel to perpendicular, especially in response to local electric fields. The ability of nonpolar peptides to modify both the structure and orientation with changing external conditions may have provided a simple mechanism of transmitting signals from the environment to the interior of a cell.

Sorption of per- and polyfluoroalkyl substances (PFASs) on filter media: implications for phase partitioning studies.

PubMed

Chandramouli, Bharat; Benskin, Jonathan P; Hamilton, M Coreen; Cosgrove, John R

2015-01-01

Per- and polyfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are ubiquitous in the environment. Investigations into their fate and potential phase-partitioning behavior require separating solid from aqueous phases via filtration. However, sorption of aqueous-phase PFASs on filtration media may lead to underestimation of PFAS concentrations in the aqueous phase. The authors investigated the sorption of perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids (PFPiAs), polyfluoroalkyl phosphate monoesters, polyfluoroalkyl phosphate diesters (diPAPs), fluorotelomer sulfonates, and perfluorooctane sulfonamide on filtration media. The effects of concentration (3 spiking levels), filter media (4 types), matrix (4 matrices), and compound structure on sorption are reported. Glass fiber filtration resulted in the least sorption, whereas polytetrafluoroethylene filters resulted in the most sorption (up to 98%). Analyte concentration had no significant effect. Sorption was generally consistent across matrix types except for samples affected by aqueous film forming foam deployment, which displayed high sorption of PFOS on nylon filters. Sorption usually increased with an increasing number of carbon or fluorine atoms and was most pronounced for PFPiAs and diPAPs (30–75% sorption). Overall, glass fiber filters are more recommended than nylon filters in environmental samples when phase separation is required. Use of filtration media for PFAS must be preceded by matrix-specific testing to account for unpredictable effects. (C)2014 SETAC

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2012-09-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (<2%) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2013-01-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Development of magnetic dispersive solid phase extraction using toner powder as an efficient and economic sorbent in combination with dispersive liquid-liquid microextraction for extraction of some widely used pesticides in fruit juices.

PubMed

Farajzadeh, Mir Ali; Mohebbi, Ali

2018-01-12

In this study, for the first time, a magnetic dispersive solid phase extraction method using an easy-accessible, cheap, and efficient magnetic sorbent (toner powder) combined with dispersive liquid-liquid microextraction has been developed for the extraction and preconcentration of some widely used pesticides (diazinon, ametryn, chlorpyrifos, penconazole, oxadiazon, diniconazole, and fenazaquin) from fruit juices prior to their determination by gas chromatography-flame ionization detection. In this method, the magnetic sorbent is mixed with an appropriate dispersive solvent (methanol-water, 80:20, v/v) and then injected into an aqueous sample containing the analytes. By this action the analytes are rapidly adsorbed on the sorbent by binding to its carbon. The sorbent particles are isolated from the aqueous solution in the presence of an external magnetic field. Then an appropriate organic solvent (acetone) is used to desorb the analytes from the sorbent. Finally, the obtained supernatant is mixed with an extraction solvent and injected into deionized water in order to achieve high enrichment factors and sensitivity. Several significant factors affecting the performance of the introduced method were investigated and optimized. Under the optimum experimental conditions, the extraction recoveries of the proposed method for the selected analytes ranged from 49-75%. The relative standard deviations were ≤7% for intra- (n = 6) and inter-day (n = 4) precisions at a concentration of 10 μg L -1 of each analyte. The limits of detection were in the range of 0.15-0.36 μg L -1 . Finally, the applicability of the proposed method was evaluated by analysis of the selected analytes in some fruit juices. Copyright © 2017 Elsevier B.V. All rights reserved.

Diffusion-regulated phase-transfer catalysis for atom transfer radical polymerization of methyl methacrylate in an aqueous/organic biphasic system.

PubMed

Ding, Mingqiang; Jiang, Xiaowu; Peng, Jinying; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2015-03-01

A concept based on diffusion-regulated phase-transfer catalysis (DRPTC) in an aqueous-organic biphasic system with copper-mediated initiators for continuous activator regeneration is successfully developed for atom transfer radical polymerization (ICAR ATRP) (termed DRPTC-based ICAR ATRP here), using methyl methacrylate (MMA) as a model monomer, ethyl α-bromophenylacetate (EBrPA) as an initiator, and tris(2-pyridylmethyl)amine (TPMA) as a ligand. In this system, the monomer and initiating species in toluene (organic phase) and the catalyst complexes in water (aqueous phase) are simply mixed under stirring at room temperature. The trace catalyst complexes transfer into the organic phase via diffusion to trigger ICAR ATRP of MMA with ppm level catalyst content once the system is heated to the polymerization temperature (75 °C). It is found that well-defined PMMA with controlled molecular weights and narrow molecular weight distributions can be obtained easily. Furthermore, the polymerization can be conducted in the presence of limited amounts of air without using tedious degassed procedures. After cooling to room temperature, the upper organic phase is decanted and the lower aqueous phase is reused for another 10 recycling turnovers with ultra low loss of catalyst and ligand loading. At the same time, all the recycled catalyst complexes retain nearly perfect catalytic activity and controllability, indicating a facile and economical strategy for catalyst removal and recycling. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Concurrence of aqueous and gas phase contamination of groundwater in the Wattenberg oil and gas field of northern Colorado.

PubMed

Li, Huishu; Son, Ji-Hee; Carlson, Kenneth H

2016-01-01

The potential impact of rapid development of unconventional oil and natural gas resources using hydraulic fracturing and horizontal drilling on regional groundwater quality has received significant attention. Major concerns are methane or oil/gas related hydrocarbon (such as TPHs, BTEX including benzene, toluene, ethybenzene and xylene) leaks into the aquifer due to the failure of casing and/or stray gas migration. Previously, we investigated the relationship between oil and gas activity and dissolved methane concentration in a drinking water aquifer with the major finding being the presence of thermogenic methane contamination, but did not find detectable concentrations of TPHs or BTEX. To understand if aqueous and gas phases from the producing formation were transported concurrently to drinking water aquifers without the presence of oil/gas related hydrocarbons, the ionic composition of three water groups was studied: (1) uncontaminated deep confined aquifer, (2) suspected contaminated groundwater - deep confined aquifer containing thermogenic methane, and (3) produced water from nearby oil and gas wells that would represent aqueous phase contaminants. On the basis of quantitative and spatial analysis, we identified that the "thermogenic methane contaminated" groundwater did not have similarities to produced water in terms of ionic character (e.g. Cl/TDS ratio), but rather to the "uncontaminated" groundwater. The analysis indicates that aquifer wells with demonstrated gas phase contamination have not been contacted by an aqueous phase from oil and gas operations according to the methodology we use in this study and the current groundwater quality data from COGCC. However, the research does not prove conclusively that this the case. The results may provide insight on contamination mechanisms since improperly sealed well casing may result in stray gas but not aqueous phase transport. Copyright © 2015 Elsevier Ltd. All rights reserved.

A green separation strategy for neodymium (III) from cobalt (II) and nickel (II) using an ionic liquid-based aqueous two-phase system.

PubMed

Chen, Yuehua; Wang, Huiyong; Pei, Yuanchao; Wang, Jianji

2018-05-15

It is significant to develop sustainable strategies for the selective separation of rare earth from transition metals from fundamental and practical viewpoint. In this work, an environmentally friendly solvent extraction approach has been developed to selectively separate neodymium (III) from cobalt (II) and nickel (II) by using an ionic liquid-based aqueous two phase system (IL-ATPS). For this purpose, a hydrophilic ionic liquid (IL) tetrabutylphosphonate nitrate ([P 4444 ][NO 3 ]) was prepared and used for the formation of an ATPS with NaNO 3 . Binodal curves of the ATPSs have been determined for the design of extraction process. The extraction parameters such as contact time, aqueous phase pH, content of phase-formation components of NaNO 3 and the ionic liquid have been investigated systematically. It is shown that under optimal conditions, the extraction efficiency of neodymium (III) is as high as 99.7%, and neodymium (III) can be selectively separated from cobalt (II) and nickel (II) with a separation factor of 10 3 . After extraction, neodymium (III) can be stripped from the IL-rich phase by using dilute aqueous sodium oxalate, and the ILs can be quantitatively recovered and reused in the next extraction process. Since [P 4444 ][NO 3 ] works as one of the components of the ATPS and the extractant for the neodymium, no organic diluent, extra etractant and fluorinated ILs are used in the separation process. Thus, the strategy described here shows potential in green separation of neodymium from cobalt and nickel by using simple IL-based aqueous two-phase system. Copyright © 2018 Elsevier B.V. All rights reserved.

Aqueous-phase oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Product identification from methyl jasmonate and methyl salicylate oxidation

NASA Astrophysics Data System (ADS)

Hansel, Amie K.; Ehrenhauser, Franz S.; Richards-Henderson, Nicole K.; Anastasio, Cort; Valsaraj, Kalliat T.

2015-02-01

Green leaf volatiles (GLVs) are a group of biogenic volatile organic compounds (BVOCs) released into the atmosphere by vegetation. BVOCs produce secondary organic aerosol (SOA) via gas-phase reactions, but little is known of their aqueous-phase oxidation as a source of SOA. GLVs can partition into atmospheric water phases, e.g., fog, mist, dew or rain, and be oxidized by hydroxyl radicals (˙OH). These reactions in the liquid phase also lead to products that have higher molecular weights, increased polarity, and lower vapor pressures, ultimately forming SOA after evaporation of the droplet. To examine this process, we investigated the aqueous, ˙OH-mediated oxidation of methyl jasmonate (MeJa) and methyl salicylate (MeSa), two GLVs that produce aqueous-phase SOA. High performance liquid chromatography/electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to monitor product formation. The oxidation products identified exhibit higher molecular mass than their parent GLV due to either dimerization or the addition of oxygen and hydroxyl functional groups. The proposed structures of potential products are based on mechanistic considerations combined with the HPLC/ESI-MS data. Based on the structures, the vapor pressure and the Henry's law constant were estimated with multiple methods (SPARC, SIMPOL, MPBPVP, Bond and Group Estimations). The estimated vapor pressures of the products identified are significantly (up to 7 orders of magnitude) lower than those of the associated parent compounds, and therefore, the GLV oxidation products may remain as SOA after evaporation of the water droplet. The contribution of the identified oxidation products to SOA formation is estimated based on measured HPLC-ESI/MS responses relative to previous aqueous SOA mass yield measurements.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

NASA Astrophysics Data System (ADS)

Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

2012-01-01

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM-10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Callis, C.F.; Moore, R.L.

1959-09-01

>The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1997-02-18

A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

“Towards building better linkages between aqueous phase ...

EPA Pesticide Factsheets

Currently, CMAQ’s aqueous phase chemistry routine (AQCHEM-base) assumes Henry’s Law equilibrium and employs a forward Euler method to solve a small set of oxidation equations, considering the additional processes of aitken scavenging and wet deposition in series and employing a bisection method to calculate H+ concentrations. With potentially hundreds of reactions that may be important in cloud water and only seven reactions in the current model, expansion of the existing mechanism is an important area of investigation. However, with the current mechanism hardwired into the solver code, the module is difficult to expand with additional chemistry. It also ignores the impacts of mass transfer limitations on cloud chemistry which may be significant. Here, the Kinetic PreProcessor has been applied to generate a Rosenbrock solver for the CMAQ v5.0.1 aqueous phase chemistry mechanism. The module has been updated to simultaneously solve kinetic mass transfer between the phases, dissociation/association, chemical kinetics, Aitken scavenging, and wet deposition. This will allow for easier expansion of the chemical mechanism in the future and a better link between aqueous phase chemistry and droplet microphysics. The National Exposure Research Laboratory (NERL) Atmospheric Modeling and Analysis Division (AMAD) conducts research in support of EPA mission to protect human health and the environment. AMAD research program is engaged in developing and evaluating pre

Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.

2007-06-27

The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH ∙1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) revealed that microbial reductionmore » of solid phase U(VI) is a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity.« less

Preparation and evaluation of novel microemulsion-based hydrogels for dermal delivery of benzocaine.

PubMed

Üstündağ Okur, Neslihan; Çağlar, Emre Şefik; Arpa, Muhammet Davut; Karasulu, H Yeşim

2017-06-01

The purpose of the current research was to prepare and evaluate the potential use of microemulsion-based hydrogel (MBH) formulations for dermal delivery of benzocaine (BZN). The pseudoternary-phase diagrams were constructed for various microemulsions composed of isopropyl myristate (IPM) as oil phase, Span 20, Tween 20, Tween 80, cremophor EL and cremophor RH40 as surfactants, ethanol as cosurfactant and distilled water as aqueous phase. Finally, concentration of BZN in microemulsions was 2% (w/w). The physicochemical properties, such as conductivity, viscosity, pH, droplet size, polydispersity index and zeta potential of microemulsions, were measured. Carbopol 940 was used to convert BZN-loaded microemulsions into gel form without affecting their structure. Furthermore, excised rat abdominal skin was used to compare permeation and penetration properties of BZN loaded M3 and M3BHs with BZN solution. According to ex vivo study results, BZN-loaded M3BH1 showed highest flux values and high release rate values, and furthermore, this gel formulation had low surfactant content. Finally, in order to learn the localization of formulations within the dermal penetration, formulations and BZN solution were labeled with red oil O and subjected to fluorescence observation. In conclusion, BZN-loaded MBHs could be offered as a promising strategy for dermal drug delivery.

Improved Separations of Proteins and Sugar Derivatives Using the Small-Scale Cross-Axis Coil Planet Centrifuge with Locular Multilayer Coiled Columns

PubMed Central

Shinomiya, Kazufusa; Umezawa, Motoki; Seki, Manami; Nitta, Jun; Zaima, Kazumasa; Harikai, Naoki; Ito, Yoichiro

2016-01-01

1) Background Countercurrent chromatography (CCC) is liquid-liquid partition chromatography without using a solid support matrix. This technique requires further improvement of partition efficiency and shortening theseparation time. 2) Methods The locular multilayer coils modified with and without mixer glass beads were developed for the separation of proteins and 4-methylumbelliferyl (MU) sugar derivatives using the small-scale cross-axis coil planet centrifuge. 3) Results Proteins were well separated from each other and the separation was improved at a low flow rate of the mobile phase. On the other hand, 4-MU sugar derivatives were sufficiently resolved with short separation time at a highflow rate of the mobile phase under satisfactory stationary phase retention. 4) Conclusion Effective separations were achieved using the locular multilayer coil for proteins with aqueous-aqueous polymer phase systems and for 4-MU sugar derivatives with organic-aqueous two-phase solvent systems by inserting a glass bead into each locule. PMID:27891507

Actinium radioisotope products of enhanced purity

DOEpatents

Meikrantz, David Herbert; Todd, Terry Allen; Tranter, Troy Joseph; Horwitz, E. Philip

2010-06-15

A product includes actinium-225 (.sup.225Ac) and less than about 1 microgram (.mu.g) of iron (Fe) per millicurie (mCi) of actinium-225. The product may have a radioisotopic purity of greater than about 99.99 atomic percent (at %) actinium-225 and daughter isotopes of actinium-225, and may be formed by a method that includes providing a radioisotope mixture solution comprising at least one of uranium-233 (.sup.233U) and thorium-229 (.sup.229Th), extracting the at least one of uranium-233 and thorium-229 into an organic phase, substantially continuously contacting the organic phase with an aqueous phase, substantially continuously extracting actinium-225 into the aqueous phase, and purifying the actinium-225 from the aqueous phase. In some embodiments, the product may include less than about 1 nanogram (ng) of iron per millicurie (mCi) of actinium-225, and may include less than about 1 microgram (.mu.g) each of magnesium (Mg), Chromium (Cr), and manganese (Mn) per millicurie (mCi) of actinium-225.

Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate

NASA Technical Reports Server (NTRS)

Jacob, D. J.

1986-01-01

The chemistry of OH in nonprecipitating tropospheric clouds was studied using a coupled gas phase/aqueous phase chemical model. The simulation takes into account the radial dependence of the concentrations of short lived aqueous phase species, in particular, O3(aq) OH(aq). Formic acid is shown to be rapidly produced by the aqueous phase reaction between H2C(OH)2 and OH, but HCOO(-) and OH, but HCOO(-) is in turn rapidly oxidized by OH(aq). The HCOOH concentration in cloud is shown to be strongly dependent on the pH of the cloud water; clouds with pH greater than 5 are not efficient HCOOH sources. A novel mechanism is proposed for the oxidation of S(IV) by OH(aq), with the main product predicted to be peroxymonosulfate, HSO5(-). The latter could contribute significantly to total cloud water sulfur.

Effects of ammonium on uranium partitioning and kaolinite mineral dissolution.

PubMed

Emerson, Hilary P; Di Pietro, Silvina; Katsenovich, Yelena; Szecsody, Jim

2017-02-01

Ammonia gas injection is a promising technique for the remediation of uranium within the vadose zone. It can be used to manipulate the pH of a system and cause co-precipitation processes that are expected to remove uranium from the aqueous phase and decrease leaching from the solid phase. The work presented in this paper explores the effects of ammonium and sodium hydroxide on the partitioning of uranium and dissolution of the kaolinite mineral in simplified synthetic groundwaters using equilibrium batch sorption and sequential extraction experiments. It shows that there is a significant increase in uranium removal in systems with divalent cations present in the aqueous phase but not in sodium chloride synthetic groundwaters. Further, the initial conditions of the aqueous phase do not affect the dissolution of kaolinite. However, the type of base treatment does have an effect on mineral dissolution. Published by Elsevier Ltd.

Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water

PubMed Central

Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

2015-01-01

Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, . Here we report a universal water-content, , dependence of for aqueous solutions. Solutions with vitrify/devitrify at a constant temperature, , referring to freeze-concentrated phase with left behind ice crystallization. Those solutions with totally vitrify at under conventional cooling/heating process though, of the samples annealed at temperatures   to effectively evoke ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of by annealing is attributable to freeze-concentrated phase of solutions instead of ‘liquid II phase of water’. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution. PMID:26503911

Fractionation of poly(methacrylic acid) and poly(vinyl pyridine) in aqueous and organic mobile phases by multidetector thermal field-flow fractionation.

PubMed

Greyling, Guilaume; Pasch, Harald

2017-08-25

Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Hierarchical drug release of pH-sensitive liposomes encapsulating aqueous two phase system.

PubMed

Zhang, Xunan; Zong, Wei; Bi, Hongmei; Zhao, Kunming; Fuhs, Thomas; Hu, Ying; Cheng, Wenlong; Han, Xiaojun

2018-06-01

As promising drug delivery vehicles, previous investigations of liposomes as carriers are primarily focused on insertion and modification of lipid membrane interfaces. The utility of the inner core seems to be overlooked. Herein, we developed pH-sensitive liposomes (PSLs) containing an aqueous two phase system (ATPS), and intriguingly discovered their hierarchical release under acidic stimuli. ATPS containing two polymers (poly(ethylene glycol) (PEG) and dextran) is homogeneous above phase transition temperature when producing ATPS-liposomes, and separated into PEG-rich phase and dextran-rich phase after cooling down to room temperature. The overall release time of ATPS-liposomes is divided into two stages and prolonged compared to simple aqueous liposomes. The unique release profile is due to the disproportional distribution of drugs in two phases. Doxorubicin (DOX) is loaded in the ATPS-liposomes, and their half maximum inhibition concentration on HeLa cells is 0.018 μmol L -1 , which means 27.5 fold increase in inhibition efficiency over free DOX. Copyright © 2018 Elsevier B.V. All rights reserved.

Cross-phase separation of nanowires and nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qian, Fang; Duoss, Eric; Han, Jinkyu

In one embodiment, a process includes creating a mixture of an aqueous component, nanowires and nanoparticles, and a hydrophobic solvent and allowing migration of the nanowires to the hydrophobic solvent, where the nanoparticles remain in the aqueous component. Moreover, the nanowires and nanoparticles are in the aqueous component before the migration.

New lipid family that forms inverted cubic phases in equilibrium with excess water: molecular structure-aqueous phase structure relationship for lipids with 5,9,13,17-tetramethyloctadecyl and 5,9,13,17-tetramethyloctadecanoyl chains.

PubMed

Yamashita, Jun; Shiono, Manzo; Hato, Masakatsu

2008-10-02

With a view to discovering a new family of lipids that form inverted cubic phases, the aqueous phase behavior of a series of lipids with isoprenoid-type hydrophobic chains has been examined over a temperature range from -40 to 65 degrees C by using optical microscopy, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering) techniques. The lipids examined are those with 5,9,13,17-tetramethyloctadecyl and 5,9,13,17-tetramethyloctadecanoyl chains linked to a series of headgroups, that is, erythritol, pentaerythritol, xylose, and glucose. All of the lipid/water systems displayed a "water + liquid crystalline phase" two-phase coexistence state when sufficiently diluted. The aqueous phase structures of the most diluted liquid crystalline phases in equilibrium with excess water depend both on the lipid molecular structure and on the temperature. Given an isoprenoid chain, the preferred phase consistently follows a phase sequence of an H II (an inverted hexagonal phase) to a Q II (an inverted bicontinuous cubic phase) to an L alpha (a lamellar phase) as A* (cross-section area of the headgroup) increases. For a given lipid/water system, the phase sequence observed as the temperature increases is L alpha to Q II to H II. The present study allowed us to find four cubic phase-forming lipid species, PEOC 18+4 [mono- O-(5,9,13,17-tetramethyloctadecyl)pentaerythritol], beta-XylOC 18+4 [1- O-(5,9,13,17-tetramethyloctadecyl)-beta- d-xylopyranoside], EROCOC 17+4 [1- O-(5,9,13,17-tetramethyloctadecanoyl)erythritol], and PEOCOC 17+4 [mono- O-(5,9,13,17-tetramethyloctadecanoyl)pentaerythritol]. The values of T K (hydrated solid-liquid crystalline phase transition temperature) of the cubic phase-forming lipids are all below 0 degrees C. Quantitative analyses of the lipid molecular structure-aqueous phase structure relationship in terms of the experimentally evaluated "surfactant parameter" allow us to rationally select an optimum combination of hydrophilic/hydrophobic part of a lipid molecule that will form a desired phase in a desired temperature range.

Analytical methodologies based on LC-MS/MS for monitoring selected emerging compounds in liquid and solid phases of the sewage sludge.

PubMed

Boix, C; Ibáñez, M; Fabregat-Safont, D; Morales, E; Pastor, L; Sancho, J V; Sánchez-Ramírez, J E; Hernández, F

2016-01-01

In this work, two analytical methodologies based on liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) were developed for quantification of emerging pollutants identified in sewage sludge after a previous wide-scope screening. The target list included 13 emerging contaminants (EC): thiabendazole, acesulfame, fenofibric acid, valsartan, irbesartan, salicylic acid, diclofenac, carbamazepine, 4-aminoantipyrine (4-AA), 4-acetyl aminoantipyrine (4-AAA), 4-formyl aminoantipyrine (4-FAA), venlafaxine and benzoylecgonine. The aqueous and solid phases of the sewage sludge were analyzed making use of Solid-Phase Extraction (SPE) and UltraSonic Extraction (USE) for sample treatment, respectively. The methods were validated at three concentration levels: 0.2, 2 and 20 μg L(-1) for the aqueous phase, and 50, 500 and 2000 μg kg(-1) for the solid phase of the sludge. In general, the method was satisfactorily validated, showing good recoveries (70-120%) and precision (RSD < 20%). Regarding the limit of quantification (LOQ), it was below 0.1 μg L(-1) in the aqueous phase and below 50 μg kg(-1) in the solid phase for the majority of the analytes. The method applicability was tested by analysis of samples from a wider study on degradation of emerging pollutants in sewage sludge under anaerobic digestion. The key benefits of these methodologies are: • SPE and USE are appropriate sample procedures to extract selected emerging contaminants from the aqueous phase of the sewage sludge and the solid residue. • LC-MS/MS is highly suitable for determining emerging contaminants in both sludge phases. • Up to our knowledge, the main metabolites of dipyrone had not been studied before in sewage sludge.

Fast non-aqueous reversed-phase liquid chromatography separation of triacylglycerol regioisomers with isocratic mobile phase. Application to different oils and fats.

PubMed

Tamba Sompila, Arnaud W G; Héron, Sylvie; Hmida, Dorra; Tchapla, Alain

2017-01-15

The distribution of fatty acid species at the sn-1/3 position or the sn-2 position of triacylglycerols (TAGs) in natural fats and oils affects their physical and nutritional properties. In fats and oils, determining the presence of one or two regioisomers and the identification of structure, where they do have one, as well as their separation, became a problem of fundamental importance to solve. A variety of instrumental technics has been proposed, such as MS, chromatography-MS or pure chromatography. A number of studies deal with the optimization of the separation, but very often, they are expensive in time. In the present study, in order to decrease the analysis time while maintaining good chromatographic separation, we tested different monomeric and polymeric stationary phases and different chromatographic conditions (mobile phase composition and analysis temperature) using Non-Aqueous Reversed Phase Liquid Chromatography (NARP-LC). It was demonstrated that mixed polymeric stationary bonded silica with accessible terminal hydroxyl groups leads to very good separation for the pairs of TAGs regioisomers constituted by two saturated and one unsaturated fatty acid (with double bond number: from 1 to 6). A Nucleodur C18 ISIS percolated by isocratic mobile phase (acetonitrile/2-propanol) at 18°C leads to their separations in less than 15min. The difference of retention times between two regioisomers XYX and XXY are large enough to confirm, as application, the presence of POP, SOP, SOS and PLP and no PPO, SPO, SSO and PPL in Theobroma cacao butter. In the same way, this study respectively shows the presence of SOS, SOP and no SSO, PSO in Butyrospermum parkii butter, POP, SOP, SOS and no PPO, PSO and SSO in Carapa oil and finally POP and no PPO in Pistacia Lentiscus oil. Copyright © 2016 Elsevier B.V. All rights reserved.

Acidities of Water and Methanol in Aqueous Solution and DMSO

ERIC Educational Resources Information Center

Gao, Daqing

2009-01-01

The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

Cloud iron speciation: Experimental simulations

NASA Astrophysics Data System (ADS)

Sofikitis, A. M.; Colin, J. L.; Desboeufs, K. V.; Losno, R.

2003-04-01

The aim of our contribution is to identify major processes controlling iron speciation in the atmospheric aqueous phase. Fe is known to participate in a variety of redox reactions in cloud chemistry, as well as controlling free radical production in the troposphere. Iron cycling is slower than cycles with other catalytic transition metals (Cu, Mn). The residence time of each iron species is around ten minutes, this allows analytical separation and determination of each iron redox species and therefore its ratio. As the only source of trace metals in aqueous atmospheric phase is due to the solubilization of aerosols, we present here dissolution rate measurements obtained by laboratory experiments with an open flow reactor. This reactor enables us to reproduce the dissolution of a particle in aqueous atmospheric water. The dissolution rate and the speciation of iron are dependent on the mineralogy of the solid phase. Our experiments included Goethite, hematite and vermiculite, which are typical mineral constituents of dust particles. Comparisons were made with natural loess which is a blend of various crystalline and amorphous phases. We will present results of crustal origin particles dissolution experiments where kinetic parameters are determined, including iron speciation. Major functions of variation are pH and photochemistry in the aqueous weathering solution.

Sorption of carboxylic acid from carboxylic salt solutions at PHS close to or above the pK.sub.a of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

DOEpatents

King, C. Judson; Tung, Lisa A.

1992-01-01

Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH.sub.a into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. the acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carobxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia.

Effect of vacuum and of strong adsorbed water films on micropore formation in aluminum hydroxide xerogel powders.

PubMed

Beruto, Dario T; Botter, Rodolfo; Converti, Attilio

2009-02-01

Aluminum hydroxide gels were washed with water, ethanol, methanol and isopropanol to obtain new gels with different liquid phases that were dried either in air at 120 degrees C or under vacuum at 80 degrees C. Drying in air leads to alcoholic xerogels with BET surface areas larger than the aqueous ones. The effect of the alcoholic groups as substitutes of the hydroxyl ones has been discussed to account for the final size of xerogel crystallites. Drying under vacuum decreases the BET surface of the methanol xerogels, but no micropores are formed in all the alcoholic xerogel matrixes. On the contrary, the vacuum drying process changes significantly the microstructure of the aqueous xerogels. Their BET surface increases by 34 m(2)/g, and micropores are formed within their crystallite aggregates. It has been experimentally shown that these changes are due to a shear transformation that occurs in the boehmite xerogels obtained under vacuum. To discuss these data, the existence of chemical compounds such as AlOOHnH(2)O was postulated. On this ground, a neat analogy between vacuum drying process and vacuum interfacial decomposition reactions of inorganic salts can be drawn. This analogy explains how a state of stresses forms in aqueous xerogel matrix during vacuum drying process.

Suaveolic Acid: A Potent Phytotoxic Substance of Hyptis suaveolens

PubMed Central

Islam, A. K. M. Mominul; Ohno, Osamu; Suenaga, Kiyotake; Kato-Noguchi, Hisashi

2014-01-01

Hyptis suaveolens (Lamiaceae) is an exotic invasive plant in many countries. Earlier studies reported that the aqueous, methanol, and aqueous methanol extract of H. suaveolens and its residues have phytotoxic properties. However, to date, the phytotoxic substances of this plant have not been reported. Therefore, the objectives of this study were isolation and identification of phytotoxic substances of H. suaveolens. Aqueous methanol extract of this plant was purified by several chromatographic runs through bioassay guided fractionation using garden cress (Lepidium sativum) as a test plant. Final purification of a phytotoxic substance was achieved by reverse phase HPLC and characterized as 14α-hydroxy-13β-abiet-8-en-18-oic acid (suaveolic acid) by high-resolution ESI-MS, 1H-,13C-NMR, CD, and specific rotation. Suaveolic acid inhibited the shoot growth of garden cress, lettuce (Lactuca sativa), Italian ryegrass (Lolium multiflorum), and barnyard grass (Echinochloa crus-galli) at concentrations greater than 30 µM. Root growth of all but lettuce was also inhibited at concentrations greater than 30 µM. The inhibitory activities were concentration dependent. Concentrations required for 50% growth inhibition of suaveolic acid for those test plant species were ranged from 76 to 1155 µM. Therefore, suaveolic acid is phytotoxic and may be responsible for the phytotoxicity of H. suaveolens plant extracts. PMID:25405221

First-principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoon, Yeohoon; Rousseau, Roger J.; Weber, Robert S.

2014-07-23

The effects of aqueous phase on the reactivity of phenol hydrogenation over Pt and Ni catalysts were investigated using density functional theory based ab initio molecular dynamics (AIMD) calculations. The adsorption of phenol and the first hydrogenation steps via three carbon positions (ortho, meta and para) with respect to the phenolic OH group were studied in both vacuum and liquid phase conditions. To gain insight into how the aqueous phase affects the metal catalyst surface, increasing water environments including singly adsorbed water molecule, mono- (9 water molecules), double layers (24 water molecules), and the bulk liquid water which (52 watermore » molecules) on the Pt(111) and the Ni(111) surfaces were modeled. Compared to the vacuum/metal interfaces, AIMD simulation results suggest that the aqueous Pt(111) and Ni(111) interfaces have a lower metal work function in the order of 0.8 - 0.9 eV, thus, making the metals in aqueous phase stronger reducing agents and poorer oxidizing agents. Phenol adsorption from the aqueous phase is found to be slightly weaker that from the vapor phase. The first hydrogenation step of phenol at the ortho position of the phenolic ring is slightly favored over the other two positions. The polarization induced by the surrounding water molecules and the solvation effect play important roles in stabilizing the transition states associated with phenol hydrogenation by lowering the barriers of 0.1 - 0.4 eV. The detailed discussion on the basis of the interfacial electrostatics from the current study is very useful to understand the nature of a broader class of metal catalyzed reactions in liquid solution phase. This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and Office of Energy Efficiency and Renewable Energy. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.« less

Complexation Enhancement Drives Water-to-Oil Ion Transport: A Simulation Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiao, Baofu; Ferru, Geoffroy; Ellis, Ross J.

We address the structures and energetics of ion solvation in aqueous and organic solutions to understand liquid-liquid ion transport. Atomistic molecular dynamics (MD) simulations with polarizable force field are performed to study the coordination transformations driving lanthanide (Ln(III)) and nitrate ion transport between aqueous and an alkylamide-oil solution. An enhancement of the coordination behavior in the organic phase is achieved in contrast with the aqueous solution. In particular, the coordination number of Ce3+ increases from 8.9 in the aqueous to 9.9 in the organic solutions (from 8 in the aqueous to 8.8 in the organic systems for Yb3+). Moreover, themore » local coordination environ ment changes dramatically. Potential of mean force calculations show that the Ln(III)-ligand coordination interaction strengths follow the order of Ln(III-)nitrate> Ln(III)-water>Ln(III)-DMDBTDMA. They increase 2-fold in the lipophilic environment in comparison to the aqueous phase, and we attribute this to the shedding of the outer solvation shell. Our findings highlight the importance of outer sphere interactions on the competitive solvation energetics that cause ions to migrate between immiscible phases; an essential ingredient for advancing important applications such as rare earth metal separations. Some open questions in simulating the coordination behavior of heavy metals are also addressed.« less

Supercritical fluid chromatography for separation and preparation of tautomeric 7-epimeric spiro oxindole alkaloids from Uncaria macrophylla.

PubMed

Yang, Wenzhi; Zhang, Yibei; Pan, Huiqin; Yao, Changliang; Hou, Jinjun; Yao, Shuai; Cai, Luying; Feng, Ruihong; Wu, Wanying; Guo, Dean

2017-02-05

Increasing challenge arising from configurational interconversion in aqueous solvent renders it rather difficult to isolate high-purity tautomeric reference standards and thus largely hinders the holistic quality control of traditional Chinese medicine (TCM). Spiro oxindole alkaloids (SOAs), as the markers for the medicinal Uncaria herbs, can easily isomerize in polar or aqueous solvent via a retro-Mannich reaction. In the present study, supercritical fluid chromatography (SFC) is utilized to separate and isolate two pairs of 7-epimeric SOAs, including rhynchophylline (R) and isorhynchophylline (IR), corynoxine (C) and corynoxine B (CB), from Uncaria macrophylla. Initially, the solvent that can stabilize SOA epimers was systematically screened, and acetonitrile was used to dissolve and as the modifier in SFC. Then, key parameters of ultra-high performance SFC (ultra-performance convergence chromatography, UPC 2 ), comprising stationary phase, additive in modifier, column temperature, ABPR pressure, and flow rate, were optimized in sequence. Two isocratic UPC 2 methods were developed on the achiral Torus 1-AA and Torus Diol columns, suitable for UV and MS detection, respectively. MCI gel column chromatography fractionated the U. macrophylla extract into two mixtures (R/IR and C/CB). Preparative SFC, using a Viridis Prep Silica 2-EP OBD column and acetonitrile-0.2% diethylamine in CO 2 as the mobile phase, was finally employed for compound purification. As a result, the purity of four SOA compounds was all higher than 95%. Different from reversed-phase HPLC, SFC, by use of water-free mobile phase (inert CO 2 and aprotic modifier), provides a solution to rapid analysis and isolation of tautomeric reference standards for quality control of TCM. Copyright © 2016 Elsevier B.V. All rights reserved.

Recovery of sugars from ionic liquid biomass liquor by solvent extraction

DOEpatents

Brennan, Timothy Charles R.; Holmes, Bradley M.; Simmons, Blake A.; Blanch, Harvey W.

2015-10-13

The present invention provides for a composition comprising a solution comprising (a) an ionic liquid (IL) or ionic liquid-aqueous (ILA) phase and (b) an organic phase, wherein the solution comprises a sugar and a boronic acid. The present invention also provides for a method of removing a sugar from a solution, comprising: (a) providing a solution comprising (i) an IL or ILA phase and (ii) an organic phase, wherein the solution comprises an IL, a sugar and a boronic acid; (b) contacting the sugar with the boronic acid to form a sugar-boronic acid complex, (c) separating the organic phase and the aqueous phase, wherein the organic phase contains the sugar-boronic acid complex, and optionally (d) separating the sugar from the organic phase.

Room temperature chemical bath deposition of cadmium selenide, cadmium sulfide and cadmium sulfoselenide thin films with novel nanostructures

NASA Astrophysics Data System (ADS)

VanderHyde, Cephas A.; Sartale, S. D.; Patil, Jayant M.; Ghoderao, Karuna P.; Sawant, Jitendra P.; Kale, Rohidas B.

2015-10-01

A simple, convenient and low cost chemical synthesis route has been used to deposit nanostructured cadmium sulfide, selenide and sulfoselenide thin films at room temperature. The films were deposited on glass substrates, using cadmium acetate as cadmium ion and sodium selenosulfate/thiourea as a selenium/sulfur ion sources. Aqueous ammonia was used as a complex reagent and also to adjust the pH of the final solution. The as-deposited films were uniform, well adherent to the glass substrate, specularly reflective and red/yellow in color depending on selenium and sulfur composition. The X-ray diffraction pattern of deposited cadmium selenide thin film revealed the nanocrystalline nature with cubic phase; cadmium sulfide revealed mixture of cubic along with hexagonal phase and cadmium sulfoselenide thin film were grown with purely hexagonal phase. The morphological observations revealed the growth and formation of interesting one, two and three-dimensional nanostructures. The band gap of thin films was calculated and the results are reported.

Suitable conditions for liquid-phase microextraction using solidification of a floating drop for extraction of fat-soluble vitamins established using an orthogonal array experimental design.

PubMed

Sobhi, Hamid Reza; Yamini, Yadollah; Esrafili, Ali; Abadi, Reza Haji Hosseini Baghdad

2008-07-04

A simple, rapid and efficient microextraction method for the extraction and determination of some fat-soluble vitamins (A, D2, D3) in aqueous samples was developed. For the first time orthogonal array designs (OADs) were employed to screen the liquid-phase microextraction (LPME) method in which few microliters of 1-undecanol were delivered to the surface of the aqueous sample and it was agitated for a selected time. Then sample vial was cooled by inserting it into an ice bath for 5 min. The solidified solvent was transferred into a suitable vial and immediately melted. Then, the extract was directly injected into a high-performance liquid chromatography (HPLC) for analysis. Several factors affecting the microextraction efficiency such as sample solution temperature, stirring speed, volume of the organic solvent, ionic strength and extraction time were investigated and screened using an OA16 (4(5)) matrix. Under the best conditions (temperature, 55 degrees C; stirring speed, 1000 rpm; the volume of extracting solvent, 15.0 microL; no salt addition and extraction time, 60 min), detection limits of the method were in the range of 1.0-3.5 microgL(-1). The relative standard deviations (RSDs) to determine the vitamins at microg L(-1) levels by applying the proposed method varied in the range of 5.1-10.7%. Dynamic linear ranges of 5-500 mugL(-1) with good correlation coefficients (0.9984

Membrane Treatment of Aqueous Film Forming Foam (AFFF) Wastes for Recovery of Its Active Ingredients

DTIC Science & Technology

1980-10-01

T ME1MBRANE TREATMENT OF AQUEOUS FILM FORMING FOAM~ (AFFF) WASTES FOR RECOVERY OFI Fts ACTIVE INGREDIENTS FINAL REPORT October 1980 by Edward S. K...OF THIS PAGEOPMn Date AVntr* d)__ ---- Ultrafiltration (UF) and Reverse Osmosis (RO) treatment of Aqueous Film Forming Foam (AFFF) solutions was...of Aqueous Film Forming Foam (AFFF) solutions was investigated to determine the feasibility of employing membrane processes to separate and recover

Quantifying the equilibrium partitioning of substituted polycyclic aromatic hydrocarbons in aerosols and clouds using COSMOtherm.

PubMed

Awonaike, Boluwatife; Wang, Chen; Goss, Kai-Uwe; Wania, Frank

2017-03-22

Functional groups attached to polycyclic aromatic hydrocarbons (PAHs) can significantly modify the environmental fate of the parent compound. Equilibrium partition coefficients, which are essential for describing the environmental phase distribution of a compound, are largely unavailable for substituted PAHs (SPAHs). Here, COSMOtherm, a software based on quantum-chemical calculations is used to estimate the atmospherically relevant partition coefficients between the gas phase, the aqueous bulk phase, the water surface and the water insoluble organic matter phase, as well as the salting-out coefficients, for naphthalene, anthracene, phenanthrene, benz(a)anthracene, benzo(a)pyrene and dibenz(a,h)anthracene and 62 of their substituted counterparts. They serve as input parameters for the calculation of equilibrium phase distribution of these compounds in aerosols and clouds. Our results, which were compared with available experimental data, show that the effect of salts, the adsorption to the water surface and the dissolution in a bulk aqueous phase can be safely neglected when estimating the gas-particle partitioning of SPAHs in aerosols. However, for small PAHs with more than one polar functional group the aqueous phase can be the dominant reservoir in a cloud.

Integration of carboxyl modified magnetic particles and aqueous two-phase extraction for selective separation of proteins.

PubMed

Gai, Qingqing; Qu, Feng; Zhang, Tao; Zhang, Yukui

2011-07-15

Both of the magnetic particle adsorption and aqueous two-phase extraction (ATPE) were simple, fast and low-cost method for protein separation. Selective proteins adsorption by carboxyl modified magnetic particles was investigated according to protein isoelectric point, solution pH and ionic strength. Aqueous two-phase system of PEG/sulphate exhibited selective separation and extraction for proteins before and after magnetic adsorption. The two combination ways, magnetic adsorption followed by ATPE and ATPE followed by magnetic adsorption, for the separation of proteins mixture of lysozyme, bovine serum albumin, trypsin, cytochrome C and myloglobin were discussed and compared. The way of magnetic adsorption followed by ATPE was also applied to human serum separation. Copyright © 2011 Elsevier B.V. All rights reserved.

Predicting the Fluid-Phase Behavior of Aqueous Solutions of ELP (VPGVG) Sequences Using SAFT-VR.

PubMed

Zhao, Binwu; Lindeboom, Tom; Benner, Steven; Jackson, George; Galindo, Amparo; Hall, Carol K

2017-10-24

The statistical associating fluid theory for potentials of variable range (SAFT-VR) is used to predict the fluid phase behavior of elastin-like polypeptide (ELP) sequences in aqueous solution with special focus on the loci of lower critical solution temperatures (LCSTs). A SAFT-VR model for these solutions is developed following a coarse-graining approach combining information from atomistic simulations and from previous SAFT models for previously reported relevant systems. Constant-pressure temperature-composition phase diagrams are determined for solutions of (VPGVG) n sequences + water with n = 1 to 300. The SAFT-VR equation of state lends itself to the straightforward calculation of phase boundaries so that complete fluid-phase equilibria can be calculated efficiently. A broad range of thermodynamic conditions of temperature and pressure are considered, and regions of vapor-liquid and liquid-liquid coexistence, including LCSTs, are found. The calculated phase boundaries at low concentrations match those measured experimentally. The temperature-composition phase diagrams of the aqueous ELP solutions at low pressure (0.1 MPa) are similar to those of types V and VI phase behavior in the classification of Scott and van Konynenburg. An analysis of the high-pressure phase behavior confirms, however, that a closed-loop liquid-liquid immiscibility region, separate from the gas-liquid envelope, is present for aqueous solutions of (VPGVG) 30 ; such a phase diagram is typical of type VI phase behavior. ELPs with shorter lengths exhibit both liquid-liquid and gas-liquid regions, both of which become less extensive as the chain length of the ELP is decreased. The strength of the hydrogen-bonding interaction is also found to affect the phase diagram of the (VPGVG) 30 system in that the liquid-liquid and gas-liquid regions expand as the hydrogen-bonding strength is decreased and shrink as it is increased. The LCSTs of the mixtures are seen to decrease as the ELP chain length is increased.

Amorphous Metal Oxide Thin Films from Aqueous Precursors: New Routes to High-kappa Dielectrics, Impact of Annealing Atmosphere Humidity, and Elucidation of Non-Uniform Composition Profiles

NASA Astrophysics Data System (ADS)

Woods, Keenan N.

Metal oxide thin films serve as critical components in many modern technologies, including microelectronic devices. Industrial state-of-the-art production utilizes vapor-phase techniques to make high-quality (dense, smooth, uniform) thin film materials. However, vapor-phase techniques require large energy inputs and expensive equipment and precursors. Solution-phase routes to metal oxides have attracted great interest as cost-effective alternatives to vapor-phase methods and also offer the potential of large-area coverage, facile control of metal composition, and low-temperature processing. Solution deposition has previously been dominated by sol-gel routes, which utilize organic ligands, additives, and/or solvents. However, sol-gel films are often porous and contain residual carbon impurities, which can negatively impact device properties. All-inorganic aqueous routes produce dense, ultrasmooth films without carbon impurities, but the mechanisms involved in converting aqueous precursors to metal oxides are virtually unexplored. Understanding these mechanisms and the parameters that influence them is critical for widespread use of aqueous approaches to prepare microelectronic components. Additionally, understanding (and controlling) density and composition inhomogeneities is important for optimizing electronic properties. An overview of deposition approaches and the challenges facing aqueous routes are presented in Chapter I. A summary of thin film characterization techniques central to this work is given in Chapter II. This dissertation contributes to the field of solution-phase deposition by focusing on three areas. First, an all-inorganic aqueous route to high-kappa metal oxide dielectrics is developed for two ternary systems. Chapters III and IV detail the film formation chemistry and film properties of lanthanum zirconium oxide (LZO) and zirconium aluminum oxide (ZAO), respectively. The functionality of these dielectrics as device components is also demonstrated. Second, the impact of steam annealing on the evolution of aqueous-derived films is reported. Chapter V demonstrates that steam annealing lowers processing temperatures by effectively reducing residual counterion content, improving film stability with respect to water absorption, and enhancing dielectric properties of LZO films. Third, density and composition inhomogeneities in aqueous-derived films are investigated. Chapters VI and VII examine density inhomogeneities in single- and multi-metal component thin films, respectively, and show that these density inhomogeneities are related to inhomogeneous metal component distributions. This dissertation includes previously published coauthored material.

Hydrogen iodide decomposition

DOEpatents

O'Keefe, Dennis R.; Norman, John H.

1983-01-01

Liquid hydrogen iodide is decomposed to form hydrogen and iodine in the presence of water using a soluble catalyst. Decomposition is carried out at a temperature between about 350.degree. K. and about 525.degree. K. and at a corresponding pressure between about 25 and about 300 atmospheres in the presence of an aqueous solution which acts as a carrier for the homogeneous catalyst. Various halides of the platinum group metals, particularly Pd, Rh and Pt, are used, particularly the chlorides and iodides which exhibit good solubility. After separation of the H.sub.2, the stream from the decomposer is countercurrently extracted with nearly dry HI to remove I.sub.2. The wet phase contains most of the catalyst and is recycled directly to the decomposition step. The catalyst in the remaining almost dry HI-I.sub.2 phase is then extracted into a wet phase which is also recycled. The catalyst-free HI-I.sub.2 phase is finally distilled to separate the HI and I.sub.2. The HI is recycled to the reactor; the I.sub.2 is returned to a reactor operating in accordance with the Bunsen equation to create more HI.

Aqueous SOA formation from radical oligomerization of methyl vinyl ketone (MVK) and methacrolein (MACR)

NASA Astrophysics Data System (ADS)

Renard, P.; Siekmann, F.; Ravier, S.; Temime-Roussel, B.; Clément, J.; Ervens, B.; Monod, A.

2013-12-01

It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. We have investigated the aqueous phase photooxidation of MACR and MVK, which are biogenic organic compounds derived from isoprene. Aqueous phase photooxidation of MVK and MACR was investigated in a photoreactor using photolysis of H2O2 as OH radical source. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature (T = 298 K) and highest precursor initial concentrations ([MVK]0 = 20 mM). A radical mechanism of oligomerization is proposed to explain the formation of the high molecular weight products. Furthermore, we quantified the total amount of carbon present in oligomers. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the atmospheric multiphase system as compared to other aqueous phase as well as traditional SOA sources. MVK time profile (as measured by UV Spectroscopy) and mass spectra (obtained using UPLC-ESI-MS for the retention time range 0-5 min in the positive mode) at 5, 10 and 50 min of reaction (MVK 20 mM, 25° C, under supersaturated O2 initial conditions).

Extension of the CAPRAM mechanism with the improved mechanism generator GECKO-A

NASA Astrophysics Data System (ADS)

Bräuer, Peter; Mouchel-Vallon, Camille; Tilgner, Andreas; Wolke, Ralf; Aumont, Bernard; Herrmann, Hartmut

2013-04-01

Organic compounds are an ubiquitous constituent of the tropospheric multiphase system. With either biogenic or anthropogenic sources, they have a major influence on the atmospheric multiphase system and thus have become a main research topic within the last decades. Modelling can provide a useful tool to explore the tropospheric multiphase chemistry. While in the gas phase several comprehensive near-explicit mechanisms exist, in the aqueous phase those mechanisms are very limited. The current study aims to advance the currently most comprehensive aqueous phase mechanism CAPRAM 3.0 by means of automated mechanism construction. Therefore, the mechanism generator GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere; see Aumont et al., 2005) has been advanced to the aqueous phase. A protocol has been designed for automated mechanism construction based on reviewed experimental data and evaluated prediction methods. The generator is able to describe the oxidation of aliphatic organic compounds by OH and NO3. For the mechanism construction, mainly structure-activity relationships are used, which are completed by Evans-Polanyi-type correlations and further suitable estimates. GECKO-A has been used to create new CAPRAM versions, where branching ratios are introduced and new chemical subsystems with species with up to 4 carbon atoms are added. The currently most comprehensive version, CAPRAM 3.7, includes about 2000 aqueous phase species and more than 3300 reactions in the aqueous phase. Box model studies have been performed using a meteorological scenario with non-permanent clouds. Besides the investigation of the concentration-time profiles, detailed time-resolved flux analyses have been performed. Several aqueous phase subsystems have been investigated, such as the formation of oxidised mono- and diacids in the aqueous phase, as well as interactions to inorganic cycles and the influence on the gas phase chemistry and composition. Results have been compared to results of previous versions and show a significant improvement in the new mechanism versions, when comparing the modelled data to field data from literature. For example, in CAPRAM 3.7 there is a malonic acid production of about 80 ng m-3 compared to a few ng m-3 in CAPRAM 3.0. The results in CAPRAM 3.7 confirm recent measurements by Bao et al. (2012), who measure up to 137 ng m-3. Moreover, several attempts have been undertaken to validate the mechanisms created by GECKO-A with own field experiments, such as the HCCT-2010 campaign and chamber experiments in the LEAK chamber. References Aumont, B., Szopa, S., Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach. Atmos. Chem. Phys., 5, 2497-2517 (2005). Bao, L., Matsumoto, M., Kubota, T., Sekiguchi, K., Wang, Q., Sakamoto, K.: Gas/particle partitioning of low-molecular-weight dicarboxylic acids at a suburban site in Saitama, Japan. Atmos. Env., 47, 546 - 553 (2012).

Partitioning phase preference for secondary organic aerosol in an urban atmosphere.

PubMed

Chang, Wayne L; Griffin, Robert J; Dabdub, Donald

2010-04-13

Secondary organic aerosol (SOA) comprises a significant portion of atmospheric particular matter. The impact of particular matter on both human health and global climate has long been recognized. Despite its importance, there are still many unanswered questions regarding the formation and evolution of SOA in the atmosphere. This study uses a modeling approach to understand the preferred partitioning behavior of SOA species into aqueous or organic condensed phases. More specifically, this work uses statistical analyses of approximately 24,000 data values for each variable from a state of the art 3D airshed model. Spatial and temporal distributions of fractions of SOA residing in the aqueous phase (fAQ) in the South Coast Air Basin of California are presented. Typical values of fAQ within the basin near the surface range from 5 to 80%. Results show that the likelihood of large fAQ values is inversely proportional to the total SOA loading. Analysis of various meteorological parameters indicates that large fAQ values are predicted because modeled aqueous-phase SOA formation is less sensitive than that of organic-phase SOA to atmospheric conditions that are not conducive to SOA formation. There is a diurnal variation of fAQ near the surface: It tends to be larger during daytime hours than during nighttime hours. Results also indicate that the largest fAQ values are simulated in layers above ground level at night. In summary, one must consider SOA in both organic and aqueous phases for proper regional and global SOA budget estimation.

Influence of calcium on microbial reduction of solid phase uranium(VI).

PubMed

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M; Wang, Zheming

2007-08-15

The effect of calcium on the dissolution and microbial reduction of a representative solid phase uranyl [U(VI)], sodium boltwoodite (NaUO(2)SiO(3)OH . 1.5H(2)O), was investigated to evaluate the rate-limiting step of microbial reduction of the solid phase U(VI). Microbial reduction experiments were performed in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1, in a bicarbonate medium with lactate as electron donor at pH 6.8 buffered with PIPES. Calcium increased the rate of Na-boltwoodite dissolution and U(VI) bioavailability by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) collectively revealed that microbial reduction of solid phase U(VI) was a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. Under studied experimental conditions, the overall rate of microbial reduction of solid phase U(VI) was limited by U(VI) dissolution reactions in solutions without calcium and limited by microbial reduction in solutions with calcium. Generally, the overall rate of microbial reduction of solid phase U(VI) was determined by the coupling of solid phase U(VI) dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) that were all affected by calcium. (c) 2007 Wiley Periodicals, Inc.

The effect of alloy composition on the mechanism of stress corrosion cracking of titanium alloys in aqueous environments

NASA Technical Reports Server (NTRS)

Boyd, J. D.; Williams, D. N.; Wood, R. A.; Jaffee, R. I.

1972-01-01

The effects of alloy composition on the aqueous stress corrosion of titanium alloys were studied with emphasis on determining the interrelations among composition, phase structure, and deformation and fracture properties of the alpha phase in alpha-beta alloys. Accomplishments summarized include the effects of alloy composition on susceptibility, and metallurgical mechanisms of stress-corrosion cracking.

OZONATION BY-PRODUCTS 2. IMPROVEMENT OF AN AQUEOUS- PHASE DERIVITIZATION METHOD FOR THE DETECTION OF FORMALDEHYDE AND OTHER CARBONYL COMPOUNDS FORMED BY THE OZONATION OF DRINKING WATER

EPA Science Inventory

A method for the determination of low molecular weight aldehydes in water using aqueous-phase derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride has been improved by the use of high-resolution capillary GC. Detection limits with GC/ECD and GC/MS with ...

Microextraction in a tetrabutylammonium bromide/ammonium sulfate aqueous two-phase system and electrohydrodynamic generation of a micro-droplet.

PubMed

Song, Young Soo; Choi, Young Hoon; Kim, Do Hyun

2007-08-31

Microextraction of methyl orange in the aqueous two-phase system (ATPS) formed by dissolving tetrabutylammonium bromide (TBAB) and ammonium sulfate (AS) is reported. Methyl orange was transported from the AS-rich phase to TBAB-rich phase across the interface of the two immiscible phases. The electrohydrodynamic effect on the shape of the interface of two immiscible flows was also observed by applying dc voltage at the T-junction of the microchannel and the generation of a droplet of AS-rich phase was observed when the potential difference between positive and negative electrodes exceeds a threshold voltage. The minimum voltage necessary for the droplet generation depends on pH due to the degree of dissociation and charge accumulation.

Is there an aerosol signature of aqueous processing?

NASA Astrophysics Data System (ADS)

Ervens, B.; Sorooshian, A.

2017-12-01

The formation of aerosol mass in cloud water has been recognized as a substantial source of atmospheric aerosol mass. While sulfate formation can be relatively well constrained, the formation of secondary organic aerosol mass in the aqueous phase (aqSOA) is much more complex due to the multitude of precursors and variety in chemical processes. Aqueous phase processing adds aerosol mass to the droplet mode, which is formed due to mass addition to activated particles in clouds. In addition, it has been shown that aqSOA mass has specific characteristics in terms of oxidation state and hygroscopicity that might help to distinguish it from other SOA sources. Many models do not include detailed chemical mechanisms of sulfate and aqSOA formation and also lack details on the mass distribution of newly formed mass. Mass addition inside and outside clouds modifies different parts of an aerosol population and consequently affects predictions of properties and lifetime of particles. Using a combination of field data analysis and model studies for a variety of air masses, we will show which chemical and physical aerosol properties can be used, in order to identify an `aqueous phase signature' in processed aerosol populations. We will discuss differences in this signature in clean (e.g., background), moderately polluted (e.g., urban) and highly polluted (e.g., biomass burning) air masses and suggest air-mass-specific chemical and/or physical properties that will help to quantify the aqueous-phase derived aerosol mass.

Sorption-induced effects of humic substances on mass transfer of organic pollutants through aqueous diffusion boundary layers: the example of water/air exchange.

PubMed

Ramus, Ksenia; Kopinke, Frank-Dieter; Georgi, Anett

2012-02-21

This study examines the effect of dissolved humic substances (DHS) on the rate of water-gas exchange of organic compounds under conditions where diffusion through the aqueous boundary layer is rate-determining. A synthetic surfactant was applied for comparison. Mass-transfer coefficients were determined from the rate of depletion of the model compounds by means of an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution. In addition, experiments with continuous passive dosing of analytes into the water phase were conducted to simulate a system where thermodynamic activity of the chemical in the aqueous phase is identical in the presence and absence of DHS. The experimental results show that DHS and surfactants can affect water-gas exchange rates by the superposition of two mechanisms: (1) hydrodynamic effects due to surface film formation ("surface smoothing"), and (2) sorption-induced effects. Whether sorption accelerates or retards mass transfer depends on its effect on the thermodynamic activity of the pollutant in the aqueous phase. Mass transfer will be retarded if the activity (or freely dissolved concentration) of the pollutant is decreased due to sorption. If it remains unchanged (e.g., due to fast equilibration with a sediment acting as a large source phase), then DHS and surfactant micelles can act as an additional shuttle for the pollutants, enhancing the flux through the boundary layer.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A.; Simonetti, Dante A.; Kunkes, Edward L.

2015-12-08

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A [Verona, WI; Simonetti, Dante A [Middleton, WI; Kunkes, Edward L [Madison, WI

2011-12-13

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Supramolecular Phase-Selective Gelation by Peptides Bearing Side-Chain Azobenzenes: Effect of Ultrasound and Potential for Dye Removal and Oil Spill Remediation

PubMed Central

Bachl, Jürgen; Oehm, Stefan; Mayr, Judith; Cativiela, Carlos; Marrero-Tellado, José Juan; Díaz Díaz, David

2015-01-01

Phase selective gelation (PSG) of organic phases from their non-miscible mixtures with water was achieved using tetrapeptides bearing a side-chain azobenzene moiety. The presence of the chromophore allowed PSG at the same concentration as the minimum gelation concentration (MGC) necessary to obtain the gels in pure organic phases. Remarkably, the presence of the water phase during PSG did not impact the thermal, mechanical, and morphological properties of the corresponding organogels. In the case of miscible oil/water mixtures, the entire mixture was gelled, resulting in the formation of quasi-hydrogels. Importantly, PSG could be triggered at room temperature by ultrasound treatment of the mixture or by adding ultrasound-aided concentrated solution of the peptide in an oil-phase to a mixture of the same oil and water. Moreover, the PSG was not affected by the presence of salts or impurities existing in water from natural sources. The process could be scaled-up, and the oil phases (e.g., aromatic solvents, gasoline, diesel fuel) recovered almost quantitatively after a simple distillation process, which also allowed the recovery and reuse of the gelator. Finally, these peptidic gelators could be used to quantitatively remove toxic dyes from aqueous solutions. PMID:26006247

Sorption of carboxylic acid from carboxylic salt solutions at pHs close to or above the pK[sub a] of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

DOEpatents

King, C.J.; Tung, L.A.

1992-07-21

Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH[sub a] into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. The acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carboxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia. 8 figs.

Method for selectively reducing plutonium values by a photochemical process

DOEpatents

Friedman, Horace A.; Toth, Louis M.; Bell, Jimmy T.

1978-01-01

The rate of reduction of Pu(IV) to Pu(III) in nitric acid solution containing a reducing agent is enhanced by exposing the solution to 200-500 nm electromagnetic radiation. Pu values are recovered from an organic extractant solution containing Pu(IV) values and U(VI) values by the method of contacting the extractant solution with an aqueous nitric acid solution in the presence of a reducing agent and exposing the aqueous solution to electromagnetic radiation having a wavelength of 200-500 nm. Under these conditions, Pu values preferentially distribute to the aqueous phase and U values preferentially distribute to the organic phase.

Gas driven displacement in a Hele-Shaw cell with chemical reaction

NASA Astrophysics Data System (ADS)

White, Andrew; Ward, Thomas

2011-11-01

Injecting a less viscous fluid into a more viscous fluid produces instabilities in the form of fingering which grow radially from the less viscous injection point (Saffman & Taylor, Proc. R. Soc. Lon. A, 1958). For two non-reacting fluids in a radial Hele-Shaw cell the ability of the gas phase to penetrate the liquid phase is largely dependent on the gap height, liquid viscosity and gas pressure. In contrast combining two reactive fluids such as aqueous calcium hydroxide and carbon dioxide, which form a precipitate, presents a more complex but technically relevant system. As the two species react calcium carbonate precipitates and increases the aqueous phase visocosity. This change in viscosity may have a significant impact on how the gas phase penetrates the liquid phase. Experimental are performed in a radial Hele-Shaw cell with gap heights O(10-100) microns by loading a single drop of aqueous calcium hydroxide and injecting carbon dioxide into the drop. The calcium hydroxide concentration, carbon dioxide pressure and gap height are varied and images of the gas penetration are analyzed to determine residual film thickness and bursting times.

Recovery of high-purity silver directly from dilute effluents by an emulsion liquid membrane-crystallization process.

PubMed

Tang, Bing; Yu, Guojun; Fang, Jianzhang; Shi, Taihong

2010-05-15

An emulsion liquid membrane (ELM)-crystallization process, using hypophosphorous acid as a reducing agent in the internal aqueous phase, has been developed for the purpose of recovering high-purity silver directly from dilute industrial effluents (waste rinse water). After pretreatment with HNO(3), silver in waste rinse water can be reliably recovered with high efficiency through the established process. The main parameters in the process of ELM-crystallization include the concentration of carrier in the membrane phase, the concentration of reducing agent in the internal aqueous phase, and the treatment ratio, which influence the recovery efficiency to various extents and must be controlled carefully. The results indicated that more than 99.5% (wt.) of the silver ions in the external aqueous phase were extracted by the ELM-crystallization process, with an average efficiency of recovery of 99.24% (wt.) and a purity of 99.92% (wt.). The membrane phase can be used repeatedly without loss of the efficiency of recovery. Copyright (c) 2009 Elsevier B.V. All rights reserved.

Generalised syntheses of ordered mesoporous oxides: the atrane route

NASA Astrophysics Data System (ADS)

Cabrera, Saúl; El Haskouri, Jamal; Guillem, Carmen; Latorre, Julio; Beltrán-Porter, Aurelio; Beltrán-Porter, Daniel; Marcos, M. Dolores; Amorós *, Pedro

2000-06-01

A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant-inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructured intermediates and the final mesoporous materials are chemically homogeneous. The final ordered mesoporous materials are thermally stable and show unimodal porosity, as well as homogeneous microstructure and texture. Examples of materials synthesised on account of the versatility of this new method, including siliceous, non siliceous and mixed oxides, are presented and discussed.

Tailored magnetic nanoparticles for optimizing magnetic fluid hyperthermia.

PubMed

Khandhar, Amit P; Ferguson, R Matthew; Simon, Julian A; Krishnan, Kannan M

2012-03-01

Magnetic Fluid Hyperthermia (MFH) is a promising approach towards adjuvant cancer therapy that is based on the localized heating of tumors using the relaxation losses of iron oxide magnetic nanoparticles (MNPs) in alternating magnetic fields (AMF). In this study, we demonstrate optimization of MFH by tailoring MNP size to an applied AMF frequency. Unlike conventional aqueous synthesis routes, we use organic synthesis routes that offer precise control over MNP size (diameter ∼10 to 25 nm), size distribution, and phase purity. Furthermore, the particles are successfully transferred to the aqueous phase using a biocompatible amphiphilic polymer, and demonstrate long-term shelf life. A rigorous characterization protocol ensures that the water-stable MNPs meet all the critical requirements: (1) uniform shape and monodispersity, (2) phase purity, (3) stable magnetic properties approaching that of the bulk, (4) colloidal stability, (5) substantial shelf life, and (6) pose no significant in vitro toxicity. Using a dedicated hyperthermia system, we then identified that 16 nm monodisperse MNPs (σ-0.175) respond optimally to our chosen AMF conditions (f = 373 kHz, H₀ = 14 kA/m); however, with a broader size distribution (σ-0.284) the Specific Loss Power (SLP) decreases by 30%. Finally, we show that these tailored MNPs demonstrate maximum hyperthermia efficiency by reducing viability of Jurkat cells in vitro, suggesting our optimization translates truthfully to cell populations. In summary, we present a way to intrinsically optimize MFH by tailoring the MNPs to any applied AMF, a required precursor to optimize dose and time of treatment. Copyright © 2011 Wiley Periodicals, Inc.

Aqueous biphasic systems containing PEG-based deep eutectic solvents for high-performance partitioning of RNA.

PubMed

Zhang, Hongmei; Wang, Yuzhi; Zhou, Yigang; Xu, Kaijia; Li, Na; Wen, Qian; Yang, Qin

2017-08-01

In this work, 16 kinds of novel deep eutectic solvents (DESs) composed of polyethylene glycol (PEG) and quaternary ammonium salts, were coupled with Aqueous Biphasic Systems (ABSs) to extract RNA. The phase forming ability of ABSs were comprehensively evaluated, involving the effects of various proportions of DESs' components, carbon chain length and anions species of quaternary ammonium salts, average molecular weights of PEG and inorganic salts nature. Then the systems were applied in RNA extraction, and the results revealed that the extraction efficiency values were distinctly enhanced by relatively lower PEG content in DESs, smaller PEG molecular weights, longer carbon chain of quaternary ammonium salts and more hydrophobic inorganic salts. Then the systems composed of [TBAB][PEG600] and Na 2 SO 4 were utilized in the influence factor experiments, proving that the electrostatic interaction was the dominant force for RNA extraction. Therefore, back-extraction efficiency values ranging between 85.19% and 90.78% were obtained by adjusting the ionic strength. Besides, the selective separation of RNA and tryptophane (Trp) was successfully accomplished. It was found that 86.19% RNA was distributed in the bottom phase, while 72.02% Trp was enriched in the top phase in the novel ABSs. Finally, dynamic light scattering (DLS) and transmission electron microscope (TEM) were used to further investigate the extraction mechanism. The proposed method reveals the outstanding feasibility of the newly developed ABSs formed by PEG-based DESs and inorganic salts for the green extraction of RNA. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermochemistry analyses for transformation of C6 glucose compound into C9, C12 and C15 alkanes using density functional theory

NASA Astrophysics Data System (ADS)

Verma, Anand Mohan; Kishore, Nanda

2017-02-01

The hydrolysis of cellulose fraction of biomass yields C6 glucose which further can be transformed into long-chain hydrocarbons by C-C coupling. In this study, C6 glucose is transformed into three chain alkanes, namely, C9, C12 and C15 using C-C coupling reactions under the gas and aqueous phase milieus. The geometry optimisation and vibrational frequency calculations are carried out at well-known hybrid-GGA functional, B3LYP with the basis set of 6-31+g(d,p) under the density functional theory framework. The single point energetics are calculated at M05-2X/6-311+g(3df,2p) level of theory. All thermochemical properties are calculated over a wide range of temperature between 300 and 900 K at an interval of 100 K. The thermochemistry suggested that the aqueous phase behaviour is suitable for the hydrolysis of sugar into long-chain alkanes compared to gas-phase environment. The hydrodeoxygenation reactions under each reaction pathway are found as most favourable reactions in both phases; however, aqueous phase dominates over gas phase in all discussed thermodynamic parameters.

Temperature-Induced Protein Release from Water-in-Oil-in-Water Double Emulsions

PubMed Central

Rojas, Edith C.; Staton, Jennifer A.; John, Vijay T.; Papadopoulos, Kyriakos D.

2009-01-01

A model water-in-oil-in-water (W1/O/W2) double emulsion was prepared by a two-step emulsification procedure and subsequently subjected to temperature changes that caused the oil phase to freeze and thaw while the two aqueous phases remained liquid. Our previous work on individual double-emulsion globules1 demonstrated that crystallizing the oil phase (O) preserves stability, while subsequent thawing triggers coalescence of the droplets of the internal aqueous phase (W1) with the external aqueous phase (W2), termed external coalescence. Activation of this instability mechanism led to instant release of fluorescently tagged bovine serum albumin (fluorescein isothiocyanate (FITC)-BSA) from the W1 droplets and into W2. These results motivated us to apply the proposed temperature-induced globule-breakage mechanism to bulk double emulsions. As expected, no phase separation of the emulsion occurred if stored at temperatures below 18 °C (freezing point of the model oil n-hexadecane), whereas oil thawing readily caused instability. Crucial variables were identified during experimentation, and found to greatly influence the behavior of bulk double emulsions following freeze-thaw cycling. Adjustment of these variables accounted for a more efficient release of the encapsulated protein. PMID:18543998

Separation and recycling of nanoparticles using cloud point extraction with non-ionic surfactant mixtures.

PubMed

Nazar, Muhammad Faizan; Shah, Syed Sakhawat; Eastoe, Julian; Khan, Asad Muhammad; Shah, Afzal

2011-11-15

A viable cost-effective approach employing mixtures of non-ionic surfactants Triton X-114/Triton X-100 (TX-114/TX-100), and subsequent cloud point extraction (CPE), has been utilized to concentrate and recycle inorganic nanoparticles (NPs) in aqueous media. Gold Au- and palladium Pd-NPs have been pre-synthesized in aqueous phases and stabilized by sodium 2-mercaptoethanesulfonate (MES) ligands, then dispersed in aqueous non-ionic surfactant mixtures. Heating the NP-micellar systems induced cloud point phase separations, resulting in concentration of the NPs in lower phases after the transition. For the Au-NPs UV/vis absorption has been used to quantify the recovery and recycle efficiency after five repeated CPE cycles. Transmission electron microscopy (TEM) was used to investigate NP size, shape, and stability. The results showed that NPs are preserved after the recovery processes, but highlight a potential limitation, in that further particle growth can occur in the condensed phases. Copyright © 2011 Elsevier Inc. All rights reserved.

Drop mass transfer in a microfluidic chip compared to a centrifugal contactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nemer, Martin B.; Roberts, Christine C.; Hughes, Lindsey G.

2014-06-13

A model system was developed for enabling a multiscale understanding of centrifugal-contactor liquid–liquid extraction.The system consisted of Nd(III) + xylenol orange in the aqueous phase buffered to pH =5.5 by KHP, and dodecane + thenoyltrifluroroacetone (HTTA) + tributyphosphate (TBP) in the organic phase. Diffusion constants were measured for neodymium in both the organic and aqueous phases, and the Nd(III) partition coefficients were measured at various HTTA and TBP concentrations. A microfluidic channel was used as a high-shear model environment to observe mass-transfer on a droplet scale with xylenol orange as the aqueous-phase metal indicator; mass-transfer rates were measured quantitatively inmore » both diffusion and reaction limited regimes on the droplet scale. Lastly, the microfluidic results were comparable to observations made for the same system in a laboratory scale liquid–liquid centrifugal contactor, indicating that single drop microfluidic experiments can provide information on mass transfer in complicated flows and geometries.« less

Computer modeling of the mineralogy of the Martian surface, as modified by aqueous alteration

NASA Technical Reports Server (NTRS)

Zolensky, M. E.; Bourcier, W. L.; Gooding, J. L.

1988-01-01

Mineralogical constraints can be placed on the Martian surface by assuming chemical equilibria among the surface rocks, atmosphere and hypothesized percolating groundwater. A study was made of possible Martian surface mineralogy, as modified by the action of aqueous alteration, using the EQ3/6 computer codes. These codes calculate gas fugacities, aqueous speciation, ionic strength, pH, Eh and concentration and degree of mineral saturation for complex aqueous systems. Thus, these codes are also able to consider mineralogical solid solutions. These codes are able to predict the likely alteration phases which will occur as the result of weathering on the Martian surface. Knowledge of the stability conditions of these phases will then assist in the definition of the specifications for the sample canister of the proposed Martian sample return mission. The model and its results are discussed.

Screening of formulation variables for the preparation of poly(epsilon-caprolactone) nanocapsules containing the local anesthetic benzocaine.

PubMed

Moraes, Carolina Morales; de Matos, Angélica Prado; Grillo, Renato; de Melo, Nathalie F S; de Paula, Eneida; Dias Filho, Newton Luiz; Rosa, André Henrique; Fraceto, Leonardo Fernandes

2011-03-01

In this work we describe the screening of four parameters in the preparation, by nanoprecipitation, of poly(epsilon-caprolactone) nanocapsules, used as a drug carrier system for the local anesthetic, benzocaine. A 2(4-1) factorial experimental design was used to study the influence of four different independent variables (polymer, oily phase, Span 60 and Tween 80) on nanocapsule characteristics (size, polydispersion index, zeta potential) and drug loading capability. Best results were obtained using an aqueous formulation comprising 100 mg of polymer, 200 mg of oily phase, 40 mg of Span 60 and 60 mg of Tween 80 in a final volume of 10 mL which produced a colloidal system with particle size of 188 nm, zeta potential -32 mV, polydispersion index 0.07, and benzocaine association efficiency > 87%. These findings open the way for future clinical studies using such formulations.

Isolation and purification of lutein from the microalga Chlorella vulgaris by extraction after saponification.

PubMed

Li, Hua-Bin; Jiang, Yue; Chen, Feng

2002-02-27

A simple and efficient method for the isolation and purification of lutein from the microalga Chlorella vulgaris was developed. Crude lutein was obtained by extraction with dichloromethane from the microalga after saponification. Partition values of lutein in the two-phase system of ethanol-water-dichloromethane at different ratios were measured by HPLC so as to assist the determination of an appropriate condition for washing water-soluble impurities in the crude lutein. Partition values of lutein in another two-phase system of ethanol-water-hexane at different ratios were also measured by HPLC for determining the condition for removing fat-soluble impurities. The water-soluble impurities in the crude lutein were removed by washing with 30% aqueous ethanol, and the fat-soluble impurities were removed by extraction with hexane. The final purity of lutein obtained was 90-98%, and the yield was 85-91%.

Near infrared bioluminescence resonance energy transfer from firefly luciferase—quantum dot bionanoconjugates

NASA Astrophysics Data System (ADS)

Alam, Rabeka; Karam, Liliana M.; Doane, Tennyson L.; Zylstra, Joshua; Fontaine, Danielle M.; Branchini, Bruce R.; Maye, Mathew M.

2014-12-01

The bioluminescence resonance energy transfer (BRET) between firefly luciferase enzymes and semiconductive quantum dots (QDs) with near infrared emission is described. The QD were phase transferred to aqueous buffers using a histidine mediated phase transfer route, and incubated with a hexahistidine tagged, green emitting variant of firefly luciferase from Photinus pyralis (PPyGRTS). The PPyGRTS were bound to the QD interface via the hexahistidine tag, which effectively displaces the histidine layer and binds directly to the QD interfaces, allowing for short donor-acceptor distances (˜5.5 nm). Due to this, high BRET efficiency ratios of ˜5 were obtained. These PPyGRTS-QD bio-nano conjugates were characterized by transmission electron microscopy, thermal gravimetric analysis, Fourier transform infrared spectroscopy and BRET emission studies. The final optimized conjugate was easily observable by night vision imaging, demonstrating the potential of these materials in imaging and signaling/sensing applications.

Interaction of L-Phenylalanine with a Phospholipid Monolayer at the Water-Air Interface.

PubMed

Griffith, Elizabeth C; Perkins, Russell J; Telesford, Dana-Marie; Adams, Ellen M; Cwiklik, Lukasz; Allen, Heather C; Roeselová, Martina; Vaida, Veronica

2015-07-23

The interaction of L-phenylalanine with a 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monolayer at the air-water interface was explored using a combination of experimental techniques and molecular dynamics (MD) simulations. By means of Langmuir trough methods and Brewster angle microscopy, L-phenylalanine was shown to significantly alter the interfacial tension and the surface domain morphology of the DPPC film. In addition, confocal microscopy was used to explore the aggregation state of L-phenylalanine in the bulk aqueous phase. Finally, MD simulations were performed to gain molecular-level information on the interactions of L-phenylalanine and DPPC at the interface. Taken together, these results show that L-phenylalanine intercalates into a DPPC film at the air-water interface, thereby affecting the surface tension, phase morphology, and ordering of the DPPC film. The results are discussed in the context of biological systems and the mechanism of diseases such as phenylketonuria.

Electrochemical ion transfer across liquid/liquid interfaces confined within solid-state micropore arrays--simulations and experiments.

PubMed

Strutwolf, Jörg; Scanlon, Micheál D; Arrigan, Damien W M

2009-01-01

Miniaturised liquid/liquid interfaces provide benefits for bioanalytical detection with electrochemical methods. In this work, microporous silicon membranes which can be used for interface miniaturisation were characterized by simulations and experiments. The microporous membranes possessed hexagonal arrays of pores with radii between 10 and 25 microm, a pore depth of 100 microm and pore centre-to-centre separations between 99 and 986 microm. Cyclic voltammetry was used to monitor ion transfer across arrays of micro-interfaces between two immiscible electrolyte solutions (microITIES) formed at these membranes, with the organic phase present as an organogel. The results were compared to computational simulations taking into account mass transport by diffusion and encompassing diffusion to recessed interfaces and overlapped diffusion zones. The simulation and experimental data were both consistent with the situation where the location of the liquid/liquid (l/l) interface was on the aqueous side of the silicon membrane and the pores were filled with the organic phase. While the current for the forward potential scan (transfer of the ion from the aqueous phase to the organic phase) was strongly dependent on the location of the l/l interface, the current peak during the reverse scan (transfer of the ion from the organic phase to the aqueous phase) was influenced by the ratio of the transferring ion's diffusion coefficients in both phases. The diffusion coefficient of the transferring ion in the gelified organic phase was ca. nine times smaller than in the aqueous phase. Asymmetric cyclic voltammogram shapes were caused by the combined effect of non-symmetrical diffusion (spherical and linear) and by the inequality of the diffusion coefficient in both phases. Overlapping diffusion zones were responsible for the observation of current peaks instead of steady-state currents during the forward scan. The characterisation of the diffusion behaviour is an important requirement for application of these silicon membranes in electroanalytical chemistry.

Highly sensitive and simple liquid chromatography assay with ion-pairing extraction and visible detection for quantification of gold from nanoparticles.

PubMed

Pallotta, Arnaud; Philippe, Valentin; Boudier, Ariane; Leroy, Pierre; Clarot, Igor

2018-03-01

A simple isocratic HPLC method using visible detection was developed and validated for the quantification of gold in nanoparticles (AuNP). After a first step of oxidation of nanoparticles, an ion-pair between tetrachloroaurate anion and the cationic dye Rhodamine B was formed and extracted from the aqueous media with the help of an organic solvent. The corresponding Rhodamine B was finally quantified by reversed phase liquid chromatography using a Nucleosil C18 (150mm × 4.6mm, 3µm) column and with a mobile phase containing acetonitrile and 0.1% trifluoroacetic acid aqueous solution (25/75, V/V) at 1.0mLmin -1. and at a wavelength of 555nm. The method was validated using methodology described by the International Conference on Harmonization and was shown to be specific, precise (RSD < 11%), accurate and linear in the range of 0.1 - 30.0µM with a lower limit of quantification (LLOQ) of 0.1µM. This method was in a first time applied to AuNP quality control after their synthesis. In a second time, the absence of gold leakage (either as AuNP or gold salt form) from nanostructured multilayered polyelectrolyte films under shear stress was assessed. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of a surfactant-assisted dispersive liquid-liquid microextraction method along with central composite design for micro-volume based spectrophotometric determination of low level of Cr(VI) ions in aquatic samples.

PubMed

Sobhi, Hamid Reza; Azadikhah, Efat; Behbahani, Mohammad; Esrafili, Ali; Ghambarian, Mahnaz

2018-05-09

A fast, simple, low cost surfactant-assisted dispersive liquid-liquid microextraction method along with central composite design for the determination of low level of Cr(VI) ions in several aquatic samples has been developed. Initially, Cr(VI) ions present in the aqueous sample were readily reacted with 1,5‑diphenylcarbazide (DPC) in acidic medium through complexation. Sodium dodecyl sulfate (SDS), as an anionic surfactant, was then employed as an ion-pair agent to convert the cationic complex into the neutral one. Following on, the whole aqueous phase underwent a dispersive liquid-liquid microextraction (DLLME) leading to the transfer of the neutral complex into the fine droplet of organic extraction phase. A micro-volume spectrophotometer was used to determine Cr(VI) concentrations. Under the optimized conditions predicted by the statistical design, the limit of quantification (LOQ) obtained was reported to be 5.0 μg/L, and the calibration curve was linear over the concentration range of 5-100 μg/L. Finally, the method was successfully implemented for the determination of low levels of Cr(VI) ions in various real aquatic samples and the accuracies fell within the range of 83-102%, while the precision varied in the span of 1.7-5.2%. Copyright © 2018. Published by Elsevier B.V.

Preparation of a solid-in-oil nanosuspension containing L-ascorbic acid as a novel long-term stable topical formulation.

PubMed

Piao, Hongyu; Kamiya, Noriho; Cui, Fude; Goto, Masahiro

2011-11-25

L-Ascorbic acid (AA, vitamin C) easily decomposes into inactive compounds in aqueous solutions and this has limited its topical use. This work reports the preparation of a solid-in-oil nanosuspension (SONS) containing AA and validation of its basic storage stability. Although AA itself is water-soluble, it can readily be nanosuspended in squalane via complex formation involving a combination of sucrose erucate (i.e. lipophilic surfactant) and sucrose monolaureate (i.e. hydrophilic surfactant) to yield SONS with a very low moisture content (<500 ppm). To extract encapsulated AA, a lipase-based enzymatic degradation technique was used to degrade a formulation phase making it easier for AA to distribute into an extraction solution. Our results demonstrate that almost all the encapsulated AA (95.3%) was readily extracted from the SONS upon addition of medium-chain triglyceride, which offers the possibility of degrading the formulation phase using lipase. Finally, its storage stability study was investigated at 25°C over 90 days under protection from light. An aqueous solution containing AA was used as a control. Compared with the control, the SONS markedly increased the stability of AA due to its low moisture content and, thus, the potential usefulness SONSs as a novel long-term stable topical formulation of AA has been proved. Copyright © 2011 Elsevier B.V. All rights reserved.

Application of dual-cloud point extraction for the trace levels of copper in serum of different viral hepatitis patients by flame atomic absorption spectrometry: A multivariate study

NASA Astrophysics Data System (ADS)

Arain, Salma Aslam; Kazi, Tasneem G.; Afridi, Hassan Imran; Abbasi, Abdul Rasool; Panhwar, Abdul Haleem; Naeemullah; Shanker, Bhawani; Arain, Mohammad Balal

2014-12-01

An efficient, innovative preconcentration method, dual-cloud point extraction (d-CPE) has been developed for the extraction and preconcentration of copper (Cu2+) in serum samples of different viral hepatitis patients prior to couple with flame atomic absorption spectrometry (FAAS). The d-CPE procedure was based on forming complexes of elemental ions with complexing reagent 1-(2-pyridylazo)-2-naphthol (PAN), and subsequent entrapping the complexes in nonionic surfactant (Triton X-114). Then the surfactant rich phase containing the metal complexes was treated with aqueous nitric acid solution, and metal ions were back extracted into the aqueous phase, as second cloud point extraction stage, and finally determined by flame atomic absorption spectrometry using conventional nebulization. The multivariate strategy was applied to estimate the optimum values of experimental variables for the recovery of Cu2+ using d-CPE. In optimum experimental conditions, the limit of detection and the enrichment factor were 0.046 μg L-1 and 78, respectively. The validity and accuracy of proposed method were checked by analysis of Cu2+ in certified sample of serum (CRM) by d-CPE and conventional CPE procedure on same CRM. The proposed method was successfully applied to the determination of Cu2+ in serum samples of different viral hepatitis patients and healthy controls.

Non-aqueous solution preparation of doped and undoped lixmnyoz

DOEpatents

Boyle, Timothy J.; Voigt, James A.

1997-01-01

A method for generation of phase-pure doped and undoped Li.sub.x Mn.sub.y O.sub.z precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder.

Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

DOEpatents

Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

2001-01-01

An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

Use of Aqueous Foam to Mitigate Demolitions Noise

DTIC Science & Technology

1981-12-01

Training Nobe. From Rangei"liboratory too USE OF AQUEOUS FOAM TO MITIGATE DEMOLITIONS NOISE LEYVEL S• • , ELECTE by Richard Rapet INM Approved for public...Subtitle) S. TYPE OF REPORT A PERIOD CovERED Use of Aqueous Foam to Mitigate Demolitions Noise FINAL -6 PERf,’RMING ORO. REPORT NUMSER 7. AUTHOR(a) S...1noise reduction * ; foam i 20. A"iTn ACT 001 mi, mm OI* N n-*-my Old 01idmiup by block misw) This report describes an investigation into whether aqueous

Test plan for Geo-Cleanse{reg_sign} demonstration (in situ destruction of dense non-aqueous phase liquid (DNAPL))

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jerome, K.M.; Looney, B.B.; Accorsi, F.

1996-09-01

Soils and groundwater beneath an abandoned process sewer line in the A/M Area of the Savannah River Site (SRS) contain elevated levels of volatile organic compounds, specifically trichloroethylene (TCE) and tetrachloroethylene (PCE), two common chlorinated solvents. These compounds have low aqueous solubilities, thus when released to the subsurface in sufficient quantity, tend to exist as immiscible fluids or nonaqueous phase liquids (NAPLs). Because chlorinated solvents are also denser than water, they are referred to by the acronym DNAPLs, or dense non-aqueous phase liquids. Technologies targeted at the efficient characterization or removal of DNAPL are not currently proven. For example, mostmore » DNAPL studies rely on traditional soil and water sampling and the fortuitous observation of immiscible solvent. Once DNAPL is identified, soil excavation (which is only applicable to small contained spill sites) is the only proven cleanup method. New cleanup approaches based on destruction of DNAPL either in situ or ex situ have been proposed and tested at the pilot scale. The proposed demonstration, as described in this report will evaluate the applicability to DNAPL plumes of a technology proven for in situ destruction of light non-aqueous phase liquids (LNAPLs) such as oils.« less

Organic contamination of ground water at Gas Works Park, Seattle, Washington

USGS Publications Warehouse

Turney, G.L.; Goerlitz, D.F.

1990-01-01

Gas Works Park, in Seattle, Washington, is located on the site of a coal and oil gasification plant that ceased operation in 1956. During operation, many types of wastes, including coal, tar, and oil, accumulated on-site. The park soil is currently (1986) contaminated with compounds such as polynuclear aromatic hydrocarbons, volatile organic compounds, trace metals, and cyanide. Analyses of water samples from a network of observation wells in the park indicate that these compounds are also present in the ground water. Polynuclear aromatic hydrocarbons and volatile organic compounds were identified in ground water samples in concentrations as large as 200 mg/L. Concentrations of organic compounds were largest where ground water was in contact with a non-aqueous phase liquid in the soil. Where no non-aqueous phase liquid was present, concentrations were much smaller, even if the ground water was in contact with contaminated soils. This condition is attributed to weathering processes in which soluble, low-molecular-weight organic compounds are preferentially dissolved from the non-aqueous phase liquid into the ground water. Where no non-aqueous phase liquid is present, only stained soils containing relatively insoluble, high-molecular-weight compounds remain. Concentrations of organic contaminants in the soils may still remain large.

Ionization energies of aqueous nucleic acids: photoelectron spectroscopy of pyrimidine nucleosides and ab initio calculations.

PubMed

Slavícek, Petr; Winter, Bernd; Faubel, Manfred; Bradforth, Stephen E; Jungwirth, Pavel

2009-05-13

Vertical ionization energies of the nucleosides cytidine and deoxythymidine in water, the lowest ones amounting in both cases to 8.3 eV, are obtained from photoelectron spectroscopy measurements in aqueous microjets. Ab initio calculations employing a nonequilibrium polarizable continuum model quantitatively reproduce the experimental spectra and provide molecular interpretation of the individual peaks of the photoelectron spectrum, showing also that lowest ionization originates from the base. Comparison of calculated vertical ionization potentials of pyrimidine bases, nucleosides, and nucleotides in water and in the gas phase underlines the dramatic effect of bulk hydration on the electronic structure. In the gas phase, the presence of sugar and, in particular, of phosphate has a strong effect on the energetics of ionization of the base. Upon bulk hydration, the ionization potential of the base in contrast becomes rather insensitive to the presence of the sugar and phosphate, which indicates a remarkable screening ability of the aqueous solvent. Accurate aqueous-phase vertical ionization potentials provide a significant improvement to the corrected gas-phase values used in the literature and represent important information in assessing the threshold energies for photooxidation and oxidation free energies of solvent-exposed DNA components. Likewise, such energetic data should allow improved assessment of delocalization and charge-hopping mechanisms in DNA ionized by radiation.

Photo-oxidation of Nitrophenols in the Aqueous Phase: Reaction Kinetics, Mechanistic Insights, and Evolution of Light Absorption

NASA Astrophysics Data System (ADS)

Hems, R.; Abbatt, J.

2017-12-01

Nitrophenols are a class of water soluble, light absorbing compounds which can make up a significant fraction of biomass burning brown carbon. The atmospheric lifetime and aging of these compounds can have important implications for their impact on climate through the aerosol direct effect. Recent studies have shown that brown carbon aerosols can be bleached of their colour by direct photolysis and photo-oxidation reactions on the timescale of hours to days. However, during aqueous phase photo-oxidation of nitrophenol compounds light absorption is sustained or enhanced, even after the parent nitrophenol molecule has been depleted. In this work, we use online aerosol chemical ionization mass spectrometry (aerosol-CIMS) to investigate the aqueous phase photo-oxidation mechanism and determine the second order rate constants for the reaction of OH radicals with three commonly detected nitrophenol compounds: nitrocatechol, nitroguaiacol, and dinitrophenol. These nitrophenol compounds are found to have aqueous phase lifetimes with respect to oxidation by the OH radical ranging between 5 - 11 hours. Our results indicate that functionalization of the parent nitrophenol molecule by addition of hydroxyl groups leads to the observed absorption enhancement. Further photo-oxidation forms breakdown products that no longer absorb significantly in the visible light range.

A Simple Approach to Characterize Gas-Aqueous Liquid Two-phase Flow Configuration Based on Discrete Solid-Liquid Contact Electrification

PubMed Central

Choi, Dongwhi; Lee, Donghyeon; Sung Kim, Dong

2015-01-01

In this study, we first suggest a simple approach to characterize configuration of gas-aqueous liquid two–phase flow based on discrete solid-liquid contact electrification, which is a newly defined concept as a sequential process of solid-liquid contact and successive detachment of the contact liquid from the solid surface. This approach exhibits several advantages such as simple operation, precise measurement, and cost-effectiveness. By using electric potential that is spontaneously generated by discrete solid–liquid contact electrification, the configurations of the gas-aqueous liquid two-phase flow such as size of a gas slug and flow rate are precisely characterized. According to the experimental and numerical analyses on parameters that affect electric potential, gas slugs have been verified to behave similarly to point electric charges when the measuring point of the electric potential is far enough from the gas slug. In addition, the configuration of the gas-aqueous liquid two-phase microfluidic system with multiple gas slugs is also characterized by using the presented approach. For a proof-of-concept demonstration of using the proposed approach in a self-triggered sensor, a gas slug detector with a counter system is developed to show its practicality and applicability. PMID:26462437

A Simple Approach to Characterize Gas-Aqueous Liquid Two-phase Flow Configuration Based on Discrete Solid-Liquid Contact Electrification.

PubMed

Choi, Dongwhi; Lee, Donghyeon; Kim, Dong Sung

2015-10-14

In this study, we first suggest a simple approach to characterize configuration of gas-aqueous liquid two-phase flow based on discrete solid-liquid contact electrification, which is a newly defined concept as a sequential process of solid-liquid contact and successive detachment of the contact liquid from the solid surface. This approach exhibits several advantages such as simple operation, precise measurement, and cost-effectiveness. By using electric potential that is spontaneously generated by discrete solid-liquid contact electrification, the configurations of the gas-aqueous liquid two-phase flow such as size of a gas slug and flow rate are precisely characterized. According to the experimental and numerical analyses on parameters that affect electric potential, gas slugs have been verified to behave similarly to point electric charges when the measuring point of the electric potential is far enough from the gas slug. In addition, the configuration of the gas-aqueous liquid two-phase microfluidic system with multiple gas slugs is also characterized by using the presented approach. For a proof-of-concept demonstration of using the proposed approach in a self-triggered sensor, a gas slug detector with a counter system is developed to show its practicality and applicability.

Hydrothermal upgrading of algae paste: Inorganics and recycling potential in the aqueous phase.

PubMed

Patel, Bhavish; Guo, Miao; Chong, Chinglih; Sarudin, Syazwani Hj Mat; Hellgardt, Klaus

2016-10-15

Hydrothermal Liquefaction (HTL) for algal biomass conversion is a promising technology capable of producing high yields of biocrude as well as partitioning even higher quantity of nutrients in the aqueous phase. To assess the feasibility of utilizing the aqueous phase, HTL of Nannochloropsis sp. was carried out in the temperature range of 275 to 350°C and Residence Times (RT) ranging between 5 and 60min The effect of reaction conditions on the NO3(-),PO4(3-),SO4(2-),Cl(-),Na(+),andK(+) ions as well as Chemical Oxygen Demand (COD) and pH was investigated with view of recycling the aqueous phase for either cultivation or energy generation via Anaerobic Digestion (AD), quantified via Lifecycle Assessment (LCA). It addition to substantial nutrient partitioning at short RT, an increase in alkalinity to almost pH10 and decrease in COD at longer RT was observed. The LCA investigation found reaction conditions of 275°C/30min and 350°C/10min to be most suitable for nutrient and energy recovery but both processing routes offer environmental benefit at all reaction conditions, however recycling for cultivation has marginally better environmental credentials compared to AD. Copyright © 2016 Elsevier B.V. All rights reserved.

Ion exchange determines iodine-131 concentration in aqueous samples

NASA Technical Reports Server (NTRS)

Fairman, W. D.; Sedlet, J.

1967-01-01

Inorganic radioiodide in aqueous media is analyzed by separating the radioactive iodine-131 as the iodide ion on a silver chloride column. The activity in the final precipitate may be determined by beta or gamma counting.

Rapid isolation procedure for Δ9-tetrahydrocannabinolic acid A (THCA) from Cannabis sativa using two flash chromatography systems.

PubMed

Wohlfarth, Ariane; Mahler, Hellmut; Auwärter, Volker

2011-10-15

Two isolation procedures for Δ9-tetrahydrocannabinolic acid A (THCA), the biogenetic precursor in the biosynthesis of the psychoactive Δ9-tetrahydrocannabinol (THC) in the cannabis plant, are presented. Two flash chromatography systems that can be used independently from each other were developed to separate THCA from other compounds of a crude cannabis extract. In both systems UV absorption at 209 and 270 nm was monitored. Purity was finally determined by HPLC-DAD, NMR and GC-MS analysis with a focus on the impurity THC. System 1 consisted of a normal phase silica column (120 g) as well as cyclohexane and acetone--both spiked with the modifier pyridine--as mobile phases. Gradient elution was performed over 15 min. After the chromatographic run the fractions containing THCA fractions were pooled, extracted with hydrochloric acid to eliminate pyridine and evaporated to dryness. Loading 1800 mg cannabis extract yielded 623 mg THCA with a purity of 99.8% and a THC concentration of 0.09%. System 2 was based on a reversed-phase C18 column (150 g) combined with 0.55% formic acid and methanol as mobile phases. A very flat gradient was set over 20 minutes. After pooling the THCA-containing fractions methanol was removed in a rotary evaporator. THCA was re-extracted from the remaining aqueous phase with methyl tert-butyl ether. The organic phase was finally evaporated under high vacuum conditions. Loading 300 mg cannabis extract yielded 51 mg THCA with a purity of 98.8% and a THC concentration of 0.67%. Copyright © 2011 Elsevier B.V. All rights reserved.

Characterization of bonded stationary phase performance as a function of qualitative and quantitative chromatographic factors in chaotropic chromatography with risperidone and its impurities as model substances.

PubMed

Čolović, Jelena; Rmandić, Milena; Malenović, Anđelija

2018-05-17

Numerous stationary phases have been developed with the aim to provide desired performances during chromatographic analysis of the basic solutes in their protonated form. In this work, the procedure for the characterization of bonded stationary phase performance, when both qualitative and quantitative chromatographic factors were varied in chaotropic chromatography, was proposed. Risperidone and its three impurities were selected as model substances, while acetonitrile content in the mobile phase (20-30%), the pH of the aqueous phase (3.00-5.00), the content of chaotropic agents in the aqueous phase (10-100 mM), type of chaotropic agent (NaClO 4 , CF 3 COONa), and stationary phase type (Zorbax Eclipse XDB, Zorbax Extend) were studied as chromatographic factors. The proposed procedure implies the combination of D-optimal experimental design, indirect modeling, and polynomial-modified Gaussian model, while grid point search method was selected for the final choice of the experimental conditions which lead to the best possible stationary phase performance for basic solutes. Good agreement between experimentally obtained chromatogram and simulated chromatogram for chosen experimental conditions (25% acetonitrile, 75 mM of NaClO 4 , pH 4.00 on Zorbax Eclipse XDB column) confirmed the applicability of the proposed procedure. The additional point was selected for the verification of proposed procedure ability to distinguish changes in solutes' elution order. Simulated chromatogram for 21.5% acetonitrile, 85 mM of NaClO 4 , pH 5.00 on Zorbax Eclipse XDB column was in line with experimental data. Furthermore, the values of left and right peak half-widths obtained from indirect modeling were used in order to evaluate performances of differently modified stationary phases applying a half-width plots approach. The results from half-width plot approach as well as from the proposed procedure indicate higher efficiency and better separation performance of the stationary phase extra densely bonded and double end-capped with trimethylsilyl group than the stationary phase with the combination of end-capping and bidentate silane bonding for chromatographic analysis of basic solutes in RP-HPLC systems with chaotropic agents. Graphical abstract ᅟ.

Behaviour of emerging contaminants in sewage sludge after anaerobic digestion.

PubMed

Boix, C; Ibáñez, M; Fabregat-Safont, D; Morales, E; Pastor, L; Sancho, J V; Sánchez-Ramírez, J E; Hernández, F

2016-11-01

Nowadays, there is an increasing concern over the presence of contaminants in the aquatic environment, where they can be introduced from wastewater after their incomplete removal in the treatment plants. In this work, degradation of selected emerging pollutants in the aqueous and solid phases of sewage sludge has been investigated after anaerobic digestion using two different digesters: mesophilic and thermophilic. Initially, sludge samples were screened by ultra-high-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC-QTOF MS) for identification of emerging contaminants in the samples. In a second step, a target quantitative method based on LC coupled to tandem MS was applied for selected pollutants identified in the previous screening. The behaviour of the compounds under anaerobic conditions was studied estimating the degradation efficiency and distribution of compounds between both sludge phases. Irbesartan and benzoylecgonine seemed to be notably degraded in both phases of the sludge. Venlafaxine showed a significant concentration decrease in the aqueous phase in parallel to an increase in the solid phase. The majority of the compounds showed an increase of their concentrations in both phases after the digestion. Concentrations in the solid phase were commonly higher than in the aqueous for most contaminants, indicating that they were preferentially adsorbed onto the solid particles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparative study of alkylthiols and alkylamines for the phase transfer of gold nanoparticles from an aqueous phase to n-hexane.

PubMed

Li, Lingxiangyu; Leopold, Kerstin; Schuster, Michael

2013-05-01

An efficient ligand-assisted phase transfer method has been developed to transfer gold nanoparticles (Au-NPs, d: 5-25 nm) from an aqueous solution to n-hexane. Four different ligands, namely 1-dodecanethiol (DDT), 1-octadecanethiol (ODT), dodecylamine (DDA), and octadecylamine (ODA) were investigated, and DDT was found to be the most efficient ligand. It appears that the molar ratio of DDT to Au-NPs is a critical factor affecting the transfer efficiency, and 270-310 is found to be the optimum range, under which the transfer efficiency is >96%. Moreover, the DDT-assisted phase transfer can preserve the shape and size of the Au-NPs, which was confirmed by UV-vis spectra and transmission electron microscopy (TEM). Additionally, the transferred Au-NPs still can be well dispersed in the n-hexane phase and remain stable for at least 2 weeks. On the other hand, the ODT-, DDA-, and ODA-assisted phase transfer is fraught with problems either related to transfer efficiency or NPs aggregation. Overall, the DDT-assisted phase transfer of Au-NPs provides a rapid and efficient method to recover Au-NPs from an aqueous solution to n-hexane. Copyright © 2013 Elsevier Inc. All rights reserved.

Ammonium fluoride as a mobile phase additive in aqueous normal phase chromatography.

PubMed

Pesek, Joseph J; Matyska, Maria T

2015-07-03

The use of ammonium fluoride as a mobile phase additive in aqueous normal phase chromatography with silica hydride-based stationary phases and mass spectrometry detection is evaluated. Retention times, peak shape, efficiency and peak intensity are compared to the more standard additives formic acid and ammonium formate. The test solutes were NAD, 3-hydroxyglutaric acid, α-ketoglutaric acid, p-aminohippuric acid, AMP, ATP, aconitic acid, threonine, N-acetyl carnitine, and 3-methyladipic acid. The column parameters are assessed in both the positive and negative ion detection modes. Ammonium fluoride is potentially an aggressive mobile phase additive that could have detrimental effects on column lifetime. Column reproducibility is measured and the effects of switching between different additives are also tested. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation and physicochemical characteristics of polylactide microspheres of emamectin benzoate by modified solvent evaporation/extraction method.

PubMed

Zhang, Shao Fei; Chen, Peng Hao; Zhang, Fei; Yang, Yan Fang; Liu, De Kun; Wu, Gang

2013-12-18

Emamectin benzoate is highly effective against insect pests and widely used in the world. However, its biological activity is limited because of high resistance of target insects and rapid degradation speed in fields. Preparation and physicochemical characterization of degradable microcapsules of emamectin benzoate were studied by modified solvent evaporation/extraction method using polylactide (PLA) as wall material. The influence of different compositions of the solvent in internal organic phase and external aqueous phase on diameter, span, pesticide loading, and entrapment rate of the microspheres was investigated. The results indicated that the process of solvent extraction and the formation of the microcapsules would be accelerated by adding water-miscible organic solvents such as ethyl ether, acetone, ethyl acetate, or n-butanol into internal organic phase and external aqueous phase. Accelerated formation of the microcapsules would result in entrapment rates of emamectin benzoate increased to as high as 97%. In addition, by adding ethanol into the external aqueous phase, diameters would reduce to 6.28 μm, whereas the loading efficiency of emamectin benzoate did not increase. The PLA microspheres prepared under optimum conditions were smoother and more spherical. The degradation rate in PLA microspheres of emamectin benzoate on the 10th day was 4.29 ± 0.74%, whereas the degradation rates of emamectin benzoate in methanol solution and solid technical material were 46.3 ± 2.11 and 22.7 ± 1.51%, respectively. The PLA skeleton had combined with emamectin benzoate in an amorphous or molecular state by using differential scanning calorimetry (DSC) determination. The results indicated that PLA microspheres of emamectin benzoate with high entrapment rate, loading efficiency, and physicochemical characteristics could be obtained by adding water-miscible organic solvents into the internal organic phase and external aqueous phase.

Chemical characterization of the main products formed through aqueous-phase photonitration of guaiacol

NASA Astrophysics Data System (ADS)

Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

2014-08-01

Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e., burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed atmospherically in the gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the main products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of hydrogen peroxide and nitrite. The formed guaiacol reaction products were concentrated by solid-phase extraction and then purified with semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state proton, carbon-13 and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of ultraviolet and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

Chemical characterization of the main secondary organic aerosol (SOA) products formed through aqueous-phase photonitration of guaiacol

NASA Astrophysics Data System (ADS)

Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

2014-04-01

Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e. burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed in the atmospheric gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the low-volatility SOA products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of H2O2 and nitrite. The formed guaiacol reaction products were concentrated by using solid-phase extraction (SPE) and then purified by means of semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state 1H, 13C and 2D nuclear magnetic resonance (NMR) spectroscopy and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of UV and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

Modeling photodegradation kinetics of three systemic neonicotinoids-dinotefuran, imidacloprid, and thiamethoxam-in aqueous and soil environment.

PubMed

Kurwadkar, Sudarshan; Evans, Amanda; DeWinne, Dustan; White, Peter; Mitchell, Forrest

2016-07-01

Environmental presence and retention of commonly used neonicotinoid insecticides such as dinotefuran (DNT), imidacloprid (IMD), and thiamethoxam (THM) are a cause for concern and prevention because of their potential toxicity to nontarget species. In the present study the kinetics of the photodegradation of these insecticides were investigated in water and soil compartments under natural light conditions. The results suggest that these insecticides are fairly unstable in both aqueous and soil environments when exposed to natural sunlight. All 3 insecticides exhibit strong first-order degradation rate kinetics in the aqueous phase, with rate constants kDNT , kIMD , and kTHM of 0.20 h(-1) , 0.30 h(-1) , and 0.18 h(-1) , respectively. However, in the soil phase, the modeled photodegradation kinetics appear to be biphasic, with optimal rate constants k1DNT and k2DNT of 0.0198 h(-1) and 0.0022 h(-1) and k1THM and k2THM of 0.0053 h(-1) and 0.0014 h(-1) , respectively. Differentially, in the soil phase, imidacloprid appears to follow the first-order rate kinetics with a kIMD of 0.0013 h(-1) . These results indicate that all 3 neonicotinoids are photodegradable, with higher degradation rates in aqueous environments relative to soil environments. In addition, soil-encapsulated imidacloprid appears to degrade slowly compared with dinotefuran and thiamethoxam and does not emulate the faster degradation rates observed in the aqueous phase. Environ Toxicol Chem 2016;35:1718-1726. © 2015 SETAC. © 2015 SETAC.

Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems

PubMed Central

Lewis, Scott; Lynch, Andrew; Bachas, Leonidas; Hampson, Steve; Ormsbee, Lindell; Bhattacharyya, Dibakar

2009-01-01

Abstract The primary objective of this research was to model and understand the chelate-modified Fenton reaction for the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. The addition of a nontoxic chelate (L), such as citrate or gluconic acid, allows for operation at near-neutral pH and controlled release of Fe(II)/Fe(III). For the standard Fenton reaction at low pH in two-phase systems, an optimum H2O2:Fe(II) molar ratio was found to be between 1:1 and 2:1. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinated TCE in both the aqueous and organic phases at pH 6–7 using low H2O2:Fe(II) molar ratios (4:1 to 8:1). Increasing the L:Fe ratio was found to decrease the rate of H2O2 degradation in both Fe(II) and Fe(III) systems at near-neutral pH. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using literature-reported hydroxyl radical reaction kinetics and mass transfer relationships. Additional aspects of this work include the reusability of the Fe–citrate complex under repeated H2O2 injections in real water systems as well as packed column studies for simulated groundwater injection. PMID:20418966

Theoretical and vibrational study of N-(3-chloro-4-fluoro-phenyl)-7-methoxy-6-(3-morpholin-4-ylpropoxy)-quinazolin-4-amine (gefitinib)

NASA Astrophysics Data System (ADS)

Mıhçıokur, Özlem; Özpozan, Talat

2015-12-01

N-(3-chloro-4fluoro-phenyl)-7-methoxy-6-(3-morpholin-4ylpropoxy)-quinazolin-4-amine (GEF), a quinalizoline derivative used as new anti-cancer agent, designed to target activity of epidermal growth factor receptor (EGFR) promoting the growth, division and spread of cancer cells, was examined from the vibrational and theoretical point of view. All calculations have been carried out both in gaseous and aqueous phases. In the calculations of both phases, the molecule has been optimized through conformer analysis beginning with the x-ray data. The conformer analyses have been carried out in each phases and the geometrical differences between the most stable structures in gaseous and in aqueous phases have been discussed. The solvent effect for GEF in aqueous solution was simulated by using self-consistent reaction field (SCRF) calculations employing the integral equation formalism variant (IEFPCM) model. NBO analysis has been performed to indicate the presence of intramolecular charge transfer. The complete assignments of the vibrational spectra (IR&Raman) were made with the aid of calculated spectra both in gaseous and aqueous phases. The observed spectral data of the title compound were compared with the calculated spectra obtained by DFT/B3LYP and DFT/B3PW91 methods using 6-31G(d,p) basis set. The theoretical results were found to be in good agreement with the measured experimental data especially for the interpretation of intra molecular interactions.

[Environment of tryptophan residues in proteins--a factor for stability to oxidative nitrosylation. I. Analysis of primary structure].

PubMed

Beda, N V; Nedospasov, A A

2001-01-01

Micellar catalysis under aerobic conditions effectively accelerates oxidative nitrosylation because of solubilization of NO and O2 by protein membranes and hydrophobic nuclei. Nitrosylating intermediates NOx (NO2, N2O3, N2O4) form mainly in the hydrophobic phase, and therefore their solubility in aqueous phase is low and hydrolysis is rapid, local concentration of NOx in the hydrophobic phase being essentially higher than in aqueous. Tryptophan is a hydrophobic residue and can nitrosylate with the formation of isomer N-nitrosotryptophans (NOW). Without denitrosylation mechanism, the accumulation of NOW in proteins of NO-synthesizing organisms would be constant, and long-living proteins would contain essential amounts of NOW, which is however not the case. Using Protein Data Bank (more than 78,000 sequences) we investigated the distribution of tryptophan residues environment (22 residues on each side of polypeptide chain) in proteins with known primary structure. Charged and polar residues (D, H, K, N, Q, R, S) are more incident in the immediate surrounding of tryptophan (-6, -5, -2, -1, 1, 2, 4) and hydrophobic residues (A, F, I, L, V, Y) are more rare than in remote positions. Hence, an essential part of tryptophan residues is situated in hydrophilic environment, which decreases the nitrosylation velocity because of lower NOx concentration in aqueous phase and allows the denitrosylation reactions course via nitrosonium ion transfer on nucleophils of functional groups of protein and low-molecular compounds in aqueous phase.

Metal Sulfide Cluster Complexes and their Biogeochemical Importance in the Environment

NASA Astrophysics Data System (ADS)

Luther, George W.; Rickard, David T.

2005-10-01

Aqueous clusters of FeS, ZnS and CuS constitute a major fraction of the dissolved metal load in anoxic oceanic, sedimentary, freshwater and deep ocean vent environments. Their ubiquity explains how metals are transported in anoxic environmental systems. Thermodynamic and kinetic considerations show that they have high stability in oxic aqueous environments, and are also a significant fraction of the total metal load in oxic river waters. Molecular modeling indicates that the clusters are very similar to the basic structural elements of the first condensed phase forming from aqueous solutions in the Fe-S, Zn-S and Cu-S systems. The structure of the first condensed phase is determined by the structure of the cluster in solution. This provides an alternative explanation of Ostwald's Rule, where the most soluble, metastable phases form before the stable phases. For example, in the case of FeS, we showed that the first condensed phase is nanoparticulate, metastable mackinawite with a particle size of 2 nm consisting of about 150 FeS subunits, representing the end of a continuum between aqueous FeS clusters and condensed material. These metal sulfide clusters and nanoparticles are significant in biogeochemistry. Metal sulfide clusters reduce sulfide and metal toxicity and help drive ecology. FeS cluster formation drives vent ecology and AgS cluster formation detoxifies Ag in Daphnia magna neonates. We also note a new reaction between FeS and DNA and discuss the potential role of FeS clusters in denaturing DNA.

Converting sugars to sugar alcohols by aqueous phase catalytic hydrogenation

DOEpatents

Elliott, Douglas C [Richland, WA; Werpy, Todd A [West Richland, WA; Wang, Yong [Richland, WA; Frye, Jr., John G.

2003-05-27

The present invention provides a method of converting sugars to their corresponding sugar alcohols by catalytic hydrogenation in the aqueous phase. It has been found that surprisingly superior results can be obtained by utilizing a relatively low temperature (less than 120.degree. C.), selected hydrogenation conditions, and a hydrothermally stable catalyst. These results include excellent sugar conversion to the desired sugar alcohol, in combination with long life under hydrothermal conditions.

Simultaneous separation/enrichment and detection of trace ciprofloxacin and lomefloxacin in food samples using thermosensitive smart polymers aqueous two-phase flotation system combined with HPLC.

PubMed

Lu, Yang; Chen, Bo; Yu, Miao; Han, Juan; Wang, Yun; Tan, Zhenjiang; Yan, Yongsheng

2016-11-01

Smart polymer aqueous two phase flotation system (SPATPF) is a new separation and enrichment technology that integrated the advantages of the three technologies, i.e., aqueous two phase system, smart polymer and flotation sublation. Ethylene oxide and propylene oxide copolymer (EOPO)-(NH4)2SO4 SPATPF is a pretreatment technique, and it is coupled with high-performance liquid chromatography to analyze the trace ciprofloxacin and lomefloxacin in real food samples. The optimized conditions of experiment were determined in the multi-factor experiment by using response surface methodology. The flotation efficiency of lomefloxacin and ciprofloxacin was 94.50% and 98.23% under the optimized conditions. The recycling experimentsshowed that the smart polymer EOPO could use repeatedly, which will reduce the cost in the future application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Aqueous phase partitioning of hexachlorocyclohexane (HCH) isomers by biosurfactant produced by Pseudomonas aeruginosa WH-2.

PubMed

Sharma, Suman; Singh, Partapbir; Raj, Mayil; Chadha, Bhupinder Singh; Saini, Harvinder Singh

2009-11-15

The different isomers of technical-grade hexachlorocyclohexane (t-HCH) including the insecticidal gamma-isomer, commonly known as lindane, have been reported to be toxic, carcinogenic and endocrine disrupters. The spatial arrangements of the chlorine atoms on different isomers and low aqueous phase solubility contribute to their persistence in environment, beta-HCH being the most resistance to transformation. The biosurfactant preparation of Pseudomonas aeruginosa isolate WH-2 was evaluated for its ability to improve the aqueous phase partitioning of different isomers of HCH-muck. Further, the ability of biosurfactant preparation to emulsify HCH and n-hexadecane was checked under different conditions, usually characteristic of sites contaminated with pollutants viz. wide range of pH, temperature, and salinity. The data obtained from this study will be helpful in designing suitable bioremediation strategies for huge stock piles of HCH-muck and sites polluted by reckless use/disposal of HCH-isomers.

Method and device for removing a non-aqueous phase liquid from a groundwater system

DOEpatents

Looney, Brian B.; Rossabi, Joseph; Riha, Brian D.

2002-01-01

A device for removing a non-aqueous phase liquid from a groundwater system includes a generally cylindrical push-rod defining an internal recess therein. The push-rod includes first and second end portions and an external liquid collection surface. A liquid collection member is detachably connected to the push-rod at one of the first and second end portions thereof. The method of the present invention for removing a non-aqueous phase liquid from a contaminated groundwater system includes providing a lance including an external hydrophobic liquid collection surface, an internal recess, and a collection chamber at the bottom end thereof. The lance is extended into the groundwater system such that the top end thereof remains above the ground surface. The liquid is then allowed to collect on the liquid collection surface, and flow downwardly by gravity into the collection chamber to be pumped upwardly through the internal recess in the lance.

Simultaneous determination of bromhexine hydrochloride and methyl and propyl p-hydroxybenzoate and determination of dextromethorphan hydrobromide in cough-cold syrup by high-performance liquid chromatography.

PubMed

Rauha, J P; Salomies, H; Aalto, M

1996-11-01

Liquid chromatographic methods were developed for the determination of bromhexine hydrochloride, methyl p-hydroxybenzoate and propyl p-hydroxybenzoate (method A) and dextromethorphan hydrobromide (method B) in cough-cold syrup formulations. Reversed-phase analytical columns (150 mm x 3.9 mm i.d.) were used with (A) C18 and (B) phenyl as stationary phases and mixtures of (A) acetonitrile and aqueous 15 mM triethylamine solution (43:57) and (B) methanol and aqueous 3% ammonium formate buffer solution (53:47) as mobile phases at a flow rate of 1.0 ml min-1. Both aqueous components were adjusted to pH 3.9. UV detection of analytes was at (A) 245 nm and (B) 278 nm. In both methods, the time required for an HPLC run giving good separations and recoveries was less than 8 min.

Extraction processes and solvents for recovery of cesium, strontium, rare earth elements, technetium and actinides from liquid radioactive waste

DOEpatents

Zaitsev, Boris N.; Esimantovskiy, Vyacheslav M.; Lazarev, Leonard N.; Dzekun, Evgeniy G.; Romanovskiy, Valeriy N.; Todd, Terry A.; Brewer, Ken N.; Herbst, Ronald S.; Law, Jack D.

2001-01-01

Cesium and strontium are extracted from aqueous acidic radioactive waste containing rare earth elements, technetium and actinides, by contacting the waste with a composition of a complex organoboron compound and polyethylene glycol in an organofluorine diluent mixture. In a preferred embodiment the complex organoboron compound is chlorinated cobalt dicarbollide, the polyethylene glycol has the formula RC.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OH, and the organofluorine diluent is a mixture of bis-tetrafluoropropyl ether of diethylene glycol with at least one of bis-tetrafluoropropyl ether of ethylene glycol and bis-tetrafluoropropyl formal. The rare earths, technetium and the actinides (especially uranium, plutonium and americium), are extracted from the aqueous phase using a phosphine oxide in a hydrocarbon diluent, and reextracted from the resulting organic phase into an aqueous phase by using a suitable strip reagent.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.

We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

Theoretical and Experimental Flow Cell Studies of a Hydrogen-Bromine Fuel Cell, Part 1. M.S. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Savinell, R. F.; Fritts, S. D.

1986-01-01

There is increasing interest in hydrogen-bromine fuel cells as both primary and regenerative energy storage systems. One promising design for a hydrogen-bromine fuel cell is a negative half cell having only a gas phase, which is separated by a cationic exchange membrane from a positive half cell having an aqueous electrolyte. The hydrogen gas and the aqueous bromide solution are stored external to the cell. In order to calculate the energy storage capacity and to predict and assess the performance of a single cell, the open circuit potential (OCV) must be estimated for different states of change, under various conditions. Theoretical expressions were derived to estimate the OCV of a hydrogen-bromine fuel cell. In these expressions temperature, hydrogen pressure, and bromine and hydrobromic acid concentrations were taken into consideration. Also included are the effects of the Nafion membrance separator and the various bromide complex species. Activity coefficients were taken into account in one of the expressions. The sensitivity of these parameters on the calculated OCV was studied.

Self-assembling semiconducting polymers--rods and gels from electronic materials.

PubMed

Clark, Andrew P-Z; Shi, Chenjun; Ng, Benny C; Wilking, James N; Ayzner, Alexander L; Stieg, Adam Z; Schwartz, Benjamin J; Mason, Thomas G; Rubin, Yves; Tolbert, Sarah H

2013-02-26

In an effort to favor the formation of straight polymer chains without crystalline grain boundaries, we have synthesized an amphiphilic conjugated polyelectrolyte, poly(fluorene-alt-thiophene) (PFT), which self-assembles in aqueous solutions to form cylindrical micelles. In contrast to many diblock copolymer assemblies, the semiconducting backbone runs parallel, not perpendicular, to the long axis of the cylindrical micelle. Solution-phase micelle formation is observed by X-ray and visible light scattering. The micelles can be cast as thin films, and the cylindrical morphology is preserved in the solid state. The effects of self-assembly are also observed through spectral shifts in optical absorption and photoluminescence. Solutions of higher-molecular-weight PFT micelles form gel networks at sufficiently high aqueous concentrations. Rheological characterization of the PFT gels reveals solid-like behavior and strain hardening below the yield point, properties similar to those found in entangled gels formed from surfactant-based micelles. Finally, electrical measurements on diode test structures indicate that, despite a complete lack of crystallinity in these self-assembled polymers, they effectively conduct electricity.

The effect of nanoparticles and humic acid on technology critical element concentrations in aqueous solutions with soil and sand.

PubMed

Stepka, Zane; Dror, Ishai; Berkowitz, Brian

2018-01-01

As a consequence of their growing use in electronic and industrial products, increasing amounts of technology critical elements (TCEs) are being released to the environment. Currently little is known about the fate of many of these elements. Initial research on their potential environmental impact identifies TCEs as emerging contaminants. TCE movement in the environment is often governed by water systems. Research on "natural" waters so far demonstrates that TCEs tend to be associated with suspended particulate matter (SPM), which influences TCE aqueous concentrations (here: concentration of TCEs in dissolved form and attached to SPM) and transport. However, the relative potential of different types of SPM to interact with TCEs is unknown. Here we examine the potential of various types of particulate matter, namely different nanoparticles (NPs; Al 2 O 3, SiO 2 , CeO 2 , ZnO, montmorillonite, Ag, Au and carbon dots) and humic acid (HA), to impact TCE aqueous concentrations in aqueous solutions with soil and sand, and thus influence TCE transport in soil-water environments. We show that a combination of NPs and HA, and not NPs or HA individually, increases the aqueous concentrations of TCEs in soil solutions, for all tested NPs regardless of their type. TCEs retained on SPM, however, settle with time. In solutions with sand, HA alone is as influential as NPs+HA in keeping TCEs in the aqueous phase. Among NPs, Ag-NPs and Au-NPs demonstrate the highest potential for TCE transport. These results suggest that in natural soil-water environments, once TCEs are retained by soil, their partitioning to the aqueous phase by through-flowing water is unlikely. However, if TCEs are introduced to soil-water environments as part of solutions rich in NPs and HA, it is likely that NP and HA combinations can increase TCE stability in the aqueous phase and prevent their retention on soil and sand, thus facilitating TCE transport. Copyright © 2017 Elsevier B.V. All rights reserved.

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

USGS Publications Warehouse

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

2013-01-01

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

Pulsed corona discharge: the role of ozone and hydroxyl radical in aqueous pollutants oxidation.

PubMed

Preis, S; Panorel, I C; Kornev, I; Hatakka, H; Kallas, J

2013-01-01

Ozone and hydroxyl radical are the most active oxidizing species in water treated with gas-phase pulsed corona discharge (PCD). The ratio of the species dependent on the gas phase composition and treated water contact surface was the objective for the experimental research undertaken for aqueous phenol (fast reaction) and oxalic acid (slow reaction) solutions. The experiments were carried out in the reactor, where aqueous solutions showered between electrodes were treated with 100-ns pulses of 20 kV voltage and 400 A current amplitude. The role of ozone increased with increasing oxygen concentration and the oxidation reaction rate. The PCD treatment showed energy efficiency surpassing that of conventional ozonation.

Mechanistic roles of soil humus and minerals in the sorption of nonionic organic compounds from aqueous and organic solutions

USGS Publications Warehouse

Chiou, C.T.; Shoup, T.D.; Porter, P.E.

1985-01-01

Mechanistic roles of soil humus and soil minerals and their contributions to soil sorption of nonionic organic compounds from aqueous and organic solutions are illustrated. Parathion and lindane are used as model solutes on two soils that differ greatly in their humic and mineral contents. In aqueous systems, observed sorptive characteristics suggest that solute partitioning into the soil-humic phase is the primary mechanism of soil uptake. By contrast, data obtained from organic solutions on dehydrated soil partitioning into humic phase and adsorption by soil minerals is influenced by the soil-moisture content and by the solvent medium from which the solute is sorbed. ?? 1985.

NMR Studies on the Aqueous Phase Photochemical Degradation of TNT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thorn, Kevin A.; Cox, Larry G.

2008-04-06

Aqueous phase photochemical degradation of 2,4,6-trinitrotoluene (TNT) is an important pathway in several environments, including washout lagoon soils, impact craters from partially detonated munitions that fill with rain or groundwater, and shallow marine environments containing unexploded munitions that have corroded. Knowledge of the degradation products is necessary for compliance issues on military firing ranges and formerly used defense sites. Previous laboratory studies have indicated that UV irradiation of aqueous TNT solutions results in a multicomponent product mixture, including polymerization compounds, that has been only partially resolved by mass spectrometric analyses. This study illustrates how a combination of solid and liquidmore » state 1H, 13C, and 15N NMR spectroscopy, including two dimensional analyses, provides complementary information on the total product mixture from aqueous photolysis of TNT, and the effect of reaction conditions. Among the degradation products detected were amine, amide, azoxy, azo, and carboxylic acid compounds.« less

Integrated process for the removal of emulsified oils from effluents in the steel industry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benito, J.M.; Rios, G.; Gutierrez, B.

1999-11-01

Emulsified oils contained in aqueous effluents from cold-rolling mills of the steel industry can be effectively removed via an integrated process consisting of a coagulation/flocculation stage followed by ultrafiltration of the resulting aqueous phase. The effects of CaCl{sub 2}, NaOH, and lime on the stability of different industrial effluents were studied in the coagulation experiments. The flocculants tested were inorganic prehydrolyzed aluminum salts and quaternary polyamines. Ultrafiltration of the aqueous phase from the coagulation/flocculation stage was carried out in a stirred cell using Amicon PM30 and XM300 organic membranes. Permeate fluxes were measured for industrial effluents to which the indicatedmore » coagulants and flocculants had been added. Oil concentrations in the permeate were 75% lower than the limits established by all European Union countries. Complete regeneration of the membrane was accomplished with an aqueous solution of a commercial detergent.« less

Application of a biphasic test for characterization of in vitro drug release of immediate release formulations of celecoxib and its relevance to in vivo absorption.

PubMed

Shi, Yi; Gao, Ping; Gong, Yuchuan; Ping, Haili

2010-10-04

A biphasic in vitro test method was used to examine release profiles of a poorly soluble model drug, celecoxib (CEB), from its immediate release formulations. Three formulations of CEB were investigated in this study, including a commercial Celebrex capsule, a solution formulation (containing cosolvent and surfactant) and a supersaturatable self-emulsifying drug delivery system (S-SEDDS). The biphasic test system consisted of an aqueous buffer and a water-immiscible organic solvent (e.g., octanol) with the use of both USP II and IV apparatuses. The aqueous phase provided a nonsink dissolution medium for CEB, while the octanol phase acted as a sink for CEB partitioning. For comparison, CEB concentration-time profiles of these formulations in the aqueous medium under either a sink condition or a nonsink condition were also explored. CEB release profiles of these formulations observed in the aqueous medium from either the sink condition test, the nonsink condition test, or the biphasic test have little relevance to the pharmacokinetic observations (e.g., AUC, C(max)) in human subjects. In contrast, a rank order correlation among the three CEB formulations is obtained between the in vitro AUC values of CEB from the octanol phase up to t = 2 h and the in vivo mean AUC (or C(max)) values. As the biphasic test permits a rapid removal of drug from the aqueous phase by partitioning into the organic phase, the amount of drug in the organic phase represents the amount of drug accumulated in systemic circulation in vivo. This hypothesis provides the scientific rationale for the rank order relationship among these CEB formulations between their CEB concentrations in the organic phase and the relative AUC or C(max). In addition, the biphasic test method permits differentiation and discrimination of key attributes among the three different CEB formulations. This work demonstrates that the biphasic in vitro test method appears to be useful as a tool in evaluating performance of formulations of poorly water-soluble drugs and to provide potential for establishing an in vitro-in vivo relationship.

Preparation, characterization and application of a reversed phase liquid chromatography/hydrophilic interaction chromatography mixed-mode C18-DTT stationary phase.

PubMed

Wang, Qing; Long, Yao; Yao, Lin; Xu, Li; Shi, Zhi-Guo; Xu, Lanying

2016-01-01

A mixed-mode chromatographic stationary phase, C18-DTT (dithiothreitol) silica (SiO2) was prepared through "thiol-ene" click chemistry. The obtained material was characterized by fourier transform infrared spectroscope, nitrogen adsorption analysis and contact angle analysis. Chromatographic performance of the C18-DTT was systemically evaluated by studying the effect of acetonitrile content, pH, buffer concentration of the mobile phase and column temperature. It was demonstrated that the novel stationary phase possessed reversed phase liquid chromatography (RPLC)/hydrophilic interaction liquid chromatography (HILIC) mixed-mode property. The stop-flow test revealed that C18-DTT exhibited excellent compatibility with 100% aqueous mobile phase. Additionally, the stability and column-to-column reproducibility of the C18-DTT material were satisfactory, with relative standard deviations of retention factor of the tested analytes (verapamil, fenbufen, guanine, tetrandrine and nicotinic acid) in the range of 1.82-3.72% and 0.85-1.93%, respectively. Finally, the application of C18-DTT column was demonstrated in the separation of non-steroidal anti-inflammatory drugs, aromatic carboxylic acids, alkaloids, nucleo-analytes and polycyclic aromatic hydrocarbons. It had great resolving power in the analysis of various compounds in HILIC and RPLC chromatographic conditions and was a promising RPLC/HILIC mixed-mode stationary phase. Copyright © 2015 Elsevier B.V. All rights reserved.

Process for recovering uranium from waste hydrocarbon oils containing the same. [Uranium contaminated lubricating oils from gaseous diffusion compressors

DOEpatents

Conrad, M.C.; Getz, P.A.; Hickman, J.E.; Payne, L.D.

1982-06-29

The invention is a process for the recovery of uranium from uranium-bearing hydrocarbon oils containing carboxylic acid as a degradation product. In one aspect, the invention comprises providing an emulsion of water and the oil, heating the same to a temperature effecting conversion of the emulsion to an organic phase and to an acidic aqueous phase containing uranium carboxylate, and recovering the uranium from the aqueous phase. The process is effective, simple and comparatively inexpensive. It avoids the use of toxic reagents and the formation of undesirable intermediates.

Synthesis of a mixed-model stationary phase derived from glutamine for HPLC separation of structurally different biologically active compounds: HILIC and reversed-phase applications.

PubMed

Aral, Tarık; Aral, Hayriye; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

2015-01-01

A novel mixed-mode stationary phase was synthesised starting from N-Boc-glutamine, aniline and spherical silica gel (4 µm, 60 Å). The prepared stationary phase was characterized by IR and elemental analysis. The new stationary phase bears an embedded amide group into phenyl ring, highly polar a terminal amide group and non-polar groups (phenyl and alkyl groups). At first, this new mixed-mode stationary phase was used for HILIC separation of four nucleotides and five nucleosides. The effects of different separation conditions, such as pH value, mobile phase and temperature, on the separation process were investigated. The optimum separation for nucleotides was achieved using HILIC isocratic elution with aqueous mobile phase and acetonitrile with 20°C column temperature. Under these conditions, the four nucleotides could be separated and detected at 265 nm within 14 min. Five nucleosides were separated under HILIC isocratic elution with aqueous mobile phase containing pH=3.25 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 265 nm within 14 min. Chromatographic parameters as retention factor, selectivity, theoretical plate number and peak asymmetry factor were calculated for the effect of temperature and water content in mobile phase on the separation process. The new column was also tested for nucleotides and nucleosides mixture and six analytes were separated in 10min. The chromatographic behaviours of these polar analytes on the new mixed-model stationary phase were compared with those of HILIC columns under similar conditions. Further, phytohormones and phenolic compounds were separated in order to see influence of the new stationary phase in reverse phase conditions. Eleven plant phytohormones were separated within 13 min using RP-HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 230 or 278 nm. The best separation conditions for seven phenolic compounds was also achieved using reversed-phase HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and seven phenolic compounds could be separated and detected at 230 nm within 16 min. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and photocatalytic activity of N-doped TiO2 produced in a solid phase reaction

NASA Astrophysics Data System (ADS)

Xin, Gang; Pan, Hongfei; Chen, Dan; Zhang, Zhihua; Wen, Bin

2013-02-01

N-doped TiO2 was synthesized by calcining a mixture of titanic acid and graphitic carbon nitride (g-C3N4) at temperatures above 500 °C. The final samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and UV-vis diffuse reflectance spectra. The photocatalytic activity of N-doped TiO2 was studied by assessing the degradation of methylene blue in an aqueous solution, under visible light and UV light irradiation. It was found that the N-doped TiO2 displayed higher photocatalytic activity than pure TiO2, under both visible and UV light.

Polyol-enhanced dispersive liquid-liquid microextraction coupled with gas chromatography and nitrogen phosphorous detection for the determination of organophosphorus pesticides from aqueous samples, fruit juices, and vegetables.

PubMed

Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Alizadeh Nabil, Ali Akbar

2015-12-01

Polyol-enhanced dispersive liquid-liquid microextraction has been proposed for the extraction and preconcentration of some organophosphorus pesticides from different samples. In the present study, a high volume of an aqueous phase containing a polyol (sorbitol) is prepared and then a disperser solvent along with an extraction solvent is rapidly injected into it. Sorbitol showed the best results and it was more effective on the extraction recoveries of the analytes than inorganic salts such as sodium chloride, potassium chloride, and sodium sulfate. Under the optimum extraction conditions, the method showed low limits of detection and quantification within the ranges of 12-56 and 44-162 pg/mL, respectively. Enrichment factors and extraction recoveries were in the ranges of 2799-3033 and 84-92%, respectively. The method precision was evaluated at a concentration of 10 ng/mL of each analyte, and relative standard deviations were found to be less than 5.9% for intraday (n = 6) and less than 7.8% for interday (n = 4). Finally, some aqueous samples were successfully analyzed using the proposed method and four analytes (diazinon, dimethoate, chlorpyrifos, and phosalone) were determined, some of them at ng/mL level. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Feasibility study of a cosmetic cream added with aqueous extract and oil from date (Phoenix dactylifera L.) fruit seed using experimental design.

PubMed

Lecheb, Fatma; Benamara, Salem

2015-01-01

This article reports on the feasibility study of a cosmetic cream added with aqueous extract and oil from date (Phoenix dactylifera L.) fruit seed using experimental design. First, the mixture design was applied to optimize the cosmetic formula. The responses (dependent variables) were the spreadability (YSp) and viscosity (YVis), the factors (independent variables) being the weight proportions of the fatty phase (X1), the aqueous date seed extract (X2), and the beeswax (X3). Second, the cosmetic stability study was conducted by applying a full factorial design. Here, three responses were considered [spreadability (Sp), viscosity (Vis), and peroxide index (PI)], the independent variables being the concentration of the date seed oil (DSO) (x1), storage temperature (x2), and storage time (x3). Results showed that in the case of mixture design, the second-order polynomial equations correctly described experimental data. Globally, results show that there is a relatively wide composition range to ensure a suitable cosmetic cream from the point of view of Sp and Vis. Regarding the cosmetic stability, the storage time was found to be the most influential factor on both Vis and PI, which are considered here as indicators of physical and chemical stability of the emulsion, respectively. Finally, the elaborated and commercial cosmetics were compared in terms of pH, Sp, and centrifugation test (Ct).

Air-assisted dispersive liquid-liquid microextraction based on a new hydrophobic deep eutectic solvent for the preconcentration of benzophenone-type UV filters from aqueous samples.

PubMed

Ge, Dandan; Zhang, Yi; Dai, Yixiu; Yang, Shumin

2018-04-01

Deep eutectic solvents are considered as new and green solvents that can be widely used in analytical chemistry such as microextraction. In the present work, a new dl-menthol-based hydrophobic deep eutectic solvent was synthesized and used as extraction solvents in an air-assisted dispersive liquid-liquid microextraction method for preconcentration and extraction of benzophenone-type UV filters from aqueous samples followed by high-performance liquid chromatography with diode array detection. In an experiment, the deep eutectic solvent formed by dl-menthol and decanoic acid was added to an aqueous solution containing the UV filters, and then the mixture was sucked up and injected five times by using a glass syringe, and a cloudy state was achieved. After extraction, the solution was centrifuged and the upper phase was subjected to high-performance liquid chromatography for analysis. Various parameters such as the type and volume of the deep eutectic solvent, number of pulling, and pushing cycles, solution pH and salt concentration were investigated and optimized. Under the optimum conditions, the developed method exhibited low limits of detection and limits of quantitation, good linearity, and precision. Finally, the proposed method was successfully applied to determine the benzophenone-type filters in environmental water samples with relative recoveries of 88.8-105.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Blast wave mitigation by dry aqueous foams

NASA Astrophysics Data System (ADS)

Del Prete, E.; Chinnayya, A.; Domergue, L.; Hadjadj, A.; Haas, J.-F.

2013-02-01

This paper presents results of experiments and numerical modeling on the mitigation of blast waves using dry aqueous foams. The multiphase formalism is used to model the dry aqueous foam as a dense non-equilibrium two-phase medium as well as its interaction with the high explosion detonation products. New experiments have been performed to study the mass scaling effects. The experimental as well as the numerical results, which are in good agreement, show that more than an order of magnitude reduction in the peak overpressure ratio can be achieved. The positive impulse reduction is less marked than the overpressures. The Hopkinson scaling is also found to hold particularly at larger scales for these two blast parameters. Furthermore, momentum and heat transfers, which have the main dominant role in the mitigation process, are shown to modify significantly the classical blast wave profile and thereafter to disperse the energy from the peak overpressure due to the induced relaxation zone. In addition, the velocity of the fireball, which acts as a piston on its environment, is smaller than in air. Moreover, the greater inertia of the liquid phase tends to project the aqueous foam far from the fireball. The created gap tempers the amplitude of the transmitted shock wave to the aqueous foam. As a consequence, this results in a lowering of blast wave parameters of the two-phase spherical decaying shock wave.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid

NASA Astrophysics Data System (ADS)

Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

2011-06-01

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid is an important intermediate in aqueous methylglyoxal oxidation and a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. Altieri et al. (2008) proposed that acetic acid was the precursor of oligoesters observed in methylglyoxal oxidation. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid at concentrations relevant to atmospheric waters (20 μM-10 mM) was oxidized by OH radical. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS), and IC-ESI-MS. The formation of glyoxylic, glycolic, and oxalic acids were observed. In contrast to methylglyoxal oxidation, succinic acid and oligomers were not detected. Using results from these and methylglyoxal + OH radical experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures.

PubMed

Kanno, H; Kajiwara, K; Miyata, K

2010-05-21

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for T(H) (homogeneous ice nucleation temperature) and T(m) (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the T(H) curve for a DMSO solution of R=20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at P(c2)= approximately 200 MPa and at T(c2)<-100 degrees C (P(c2): pressure of SCP, T(c2): temperature of SCP). The presence of two T(H) peaks for DMSO solutions (R=15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

NASA Astrophysics Data System (ADS)

Kanno, H.; Kajiwara, K.; Miyata, K.

2010-05-01

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2<-100 °C (Pc2: pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (<-90 °C). The pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

Triply Periodic Multiply Continuous Lyotropic Liquid Crystals Derived from Gemini Surfactants

NASA Astrophysics Data System (ADS)

Sorenson, Gregory P.

A subtle balance of non-covalent interactions directs the self-assembly of small molecule amphiphiles in aqueous media into supramolecular assemblies known as aqueous lyotropic liquid crystals (LLCs). Aqueous LLCs form many intricate, ordered nanoscale morphologies comprising distinct and structurally periodic hydrophobic and hydrophilic domains. Triply periodic multiply continuous (TPMC) LLC morphologies, which exhibit continuous hydrophobic and aqueous domains that percolate in three-dimensions, are of particular interest by virtue of their potentially wide ranging technological applications including advanced membranes for electrical energy storage and utilization, therapeutic delivery, and templates for new organic and inorganic mesoporous materials. However, robust molecular design criteria for amphiphiles that readily form TMPC morphologies are notably lacking in the literature. Recent reports have described the increased propensity for quaternary ammonium and phosphonium gemini surfactants, derived from dimerization of traditional single-tail surfactants at or near the hydrophilic headgroups through a hydrophobic linker, to stabilize TMPC mesophases. The generality of this surfactant design strategy remains untested in other amphiphiles classes bearing different headgroup chemistries. In this thesis, we describe the unusual aqueous LLC phase behavior of series of gemini dicarboxylate amphiphiles as a function of the alkyl tail length, hydrophobic linker length, and the charge-compensating counterion. These dicarboxylate surfactants unexpectedly exhibit a strong propensity to form TPMC LLCs over amphiphile concentration windows as wide as 20 wt% over a temperature range T = 25--100 °C. Through systematic modifications of the length of the hydrophobic linker and alkyl tails, we use small-angle X-ray scattering to demonstrate that these surfactants adopt new LLC mesophases including the first report of a single-gyroid phase (I4132 symmetry) and a new, tetracontinuous hexagonal network phase ( P63/mcm symmetry). Additionally, we probe the role of the linker position in the surfactant architecture. These data taken together indicate the sensitive dependence of the LLC phase behavior on counterion-headgroup correlations. Based on these molecular design criteria, we demonstrate the synthesis of a polymerizable gemini surfactant that may be self-assembled into a TPMC LLC phase and covalently fixed by a crosslinking photopolymerization. Comprised of aqueous nanochannels lined with metal carboxylates, the resulting LLC membranes exhibit high ionic conductivities.

Viscoelastic diamine surfactant for stable carbon dioxide/water foams over a wide range in salinity and temperature.

PubMed

Elhag, Amro S; Da, Chang; Chen, Yunshen; Mukherjee, Nayan; Noguera, Jose A; Alzobaidi, Shehab; Reddy, Prathima P; AlSumaiti, Ali M; Hirasaki, George J; Biswal, Sibani L; Nguyen, Quoc P; Johnston, Keith P

2018-07-15

The viscosity and stability of CO 2 /water foams at elevated temperature can be increased significantly with highly viscoelastic aqueous lamellae. The slow thinning of these viscoelastic lamellae leads to greater foam stability upon slowing down Ostwald ripening and coalescence. In the aqueous phase, the viscoelasticity may be increased by increasing the surfactant tail length to form more entangled micelles even at high temperatures and salinity. Systematic measurements of the steady state shear viscosity of aqueous solutions of the diamine surfactant (C 16-18 N(CH 3 )C 3 N(CH 3 ) 2 ) were conducted at varying surfactant concentrations and salinity to determine the parameters for formation of entangled wormlike micelles. The apparent viscosity and stability of CO 2 /water foams were compared for systems with viscoelastic entangled micellar aqueous phases relative to those with much less viscous spherical micelles. We demonstrated for the first time stable CO 2 /water foams at temperatures up to 120 °C and CO 2 volumetric fractions up to 0.98 with a single diamine surfactant, C 16-18 N(CH 3 )C 3 N(CH 3 ) 2 . The foam stability was increased by increasing the packing parameter of the surfactant with a long tail and methyl substitution on the amine to form entangled viscoelastic wormlike micelles in the aqueous phase. The foam was more viscous and stable compared to foams with spherical micelles in the aqueous lamellae as seen with C 12-14 N(EO) 2 and C 16-18 N(EO)C 3 N(EO) 2 . Copyright © 2018. Published by Elsevier Inc.

Reduction of 5in./54 Gun Blast Overpressure by Means of an Aqueous Foam- Filled Muzzle Device

DTIC Science & Technology

1981-08-01

aqueous foams have a certain drainage rate that causes the expansion ratio and bubble size to increase progressively. The Rockwood Aquafoam AFFF yields the...NSWC TR 81-128 REDUCTION OF 5"/54 GUN BLAST OVERPRESSURE BY MEANS OF AN AQUEOUS FOAM -FILLED MUZZLE DEVICE by G. STEVENS MILLER RICHARD E. MILLER, JR...128 4. TITLE (ad Subtitle) S. TYPE O r REPORT & PERIOD COVERED REDUCTION OF 5!V54 GUN BLAST OVERPRESSURE Final BY MEANS OF AN AQUEOUS FOAM -FILLED a

Aqueous foam as a less-than-lethal technology for prison applications

NASA Astrophysics Data System (ADS)

Goolsby, Tommy D.

1997-01-01

High expansion aqueous foam is an aggregation of bubbles that has the appearance of soap suds and is used to isolate individuals both visually and acoustically. It was developed in the 1920's in England to fight coal mine fires and has been widely used since for fire fighting and dust suppression. It was developed at Sandia National Laboratories (SNL) in the 1970's for nuclear safeguards and security applications. In late 1994, the National Institute of Justice (NIJ), the research arm of the Department of Justice, began a project with SNL to determine the applicability of high expansion aqueous foam for correctional applications. NIJ funded the project as part of its search for new and better less-than-lethal weapons for responding to violent and dangerous individuals, where other means of force could lead to serious injuries. The phase one objectives of the project were to select a low-to-no toxicity foam concentrate with physical characteristics suited for use in a single cell or large prison disturbances, and to determine if the selected foam concentrate could serve as a carrier for Oleoresin Capsicum (OC) irritant. The phase two objective were to conduct an extensive toxicology review of the selected foam concentrate and OC irritant, and to conduct respiration simulation experiments in the selected high expansion aqueous foam. The phase three objectives were to build a prototype individual cell aqueous foam system and to study the feasibility of aqueous foams for large prison facility disturbances. The phase four and five objectives were to use the prototype system to do large scale foam physical characteristics testing of the selected foam concentrate, and to have the prototype single cell system further evaluated by correctional representatives. Prison rather than street scenarios were evaluated as the first and most likely place for using the aqueous foam since prisons have recurrent incidents where officers and inmates might be seriously injured during violent confrontations. The very low density of the high expansion foam also makes it more suitable for indoor use. This paper summarizes the results of the project.

Materials Applications for Non-Lethal: Aqueous Foams

DOE Office of Scientific and Technical Information (OSTI.GOV)

GOOLSBY,TOMMY D.; SCOTT,STEVEN H.

High expansion aqueous foam is an aggregation of bubbles that has the appearance of soap suds and is used to isolate individuals both visually and acoustically. It was developed in the 1920's in England to fight coal mine fires and has been widely used since for fire fighting and dust suppression. It was developed at Sandia National Laboratories (SNL) in the 1970's for nuclear safeguards and security applications. In the mid-1990s, the National Institute of Justice (NIJ), the research arm of the Department of Justice, began a project with SNL to determine the applicability of high expansion aqueous foam formore » correctional applications. NIJ funded the project as part of its search for new and better less-than-lethal weapons for responding to violent and dangerous individuals, where other means of force could lead to serious injuries. The phase one objectives of the project were to select a low-to-no toxicity foam concentrate (foaming agent) with physical characteristics suited for use in a single cell or large prison disturbances, and to determine if the selected foam concentrate could serve as a carrier for Oleoresin Capsicum (OC) irritant. The phase two objectives were to conduct an extensive toxicology review of the selected foam concentrate and OC irritant, and to conduct respiration simulation experiments in the selected high expansion aqueous foam. The phase three objectives were to build a prototype individual cell aqueous foam system and to study the feasibility of aqueous foams for large prison facility disturbances. The phase four and five objectives were to use the prototype system to do large scale foam physical characteristics testing of the selected foam concentrate, and to have the prototype single cell system further evaluated by correctional representatives. Prison rather than street scenarios were evaluated as the first and most likely place for using the aqueous foam since prisons have recurrent incidents where officers and inmates might be seriously injured during violent confrontations. The very low density of the high expansion foam also makes it more suitable for indoor use. This paper summarizes the results of the project.« less

Drowning-out crystallisation of sodium sulphate using aqueous two-phase systems.

PubMed

Taboada, M E; Graber, T A; Asenjo, J A; Andrews, B A

2000-06-23

A novel method to obtain crystals of pure, anhydrous salt, using aqueous two-phase systems was studied. A concentrated salt solution is mixed with polyethylene glycol (PEG), upon which three phases are formed: salt crystals, a PEG-rich liquid and a salt-rich liquid. After removal of the solid salt, a two-phase system is obtained. Both liquid phases are recycled, allowing the design of a continuous process, which could be exploited industrially. The phase diagram of the system water-Na2SO4-PEG 3350 at 28 degrees C was used. Several process alternatives are proposed and their economic potential is discussed. The process steps needed to produce sodium sulphate crystals include mixing, crystallisation, settling and, optionally, evaporation of water. The yield of sodium sulphate increases dramatically if an evaporation step is used.

Partition in aqueous two-phase system: its application in downstream processing of tannase from Aspergillus niger.

PubMed

Rodríguez-Durán, Luis V; Spelzini, Darío; Boeris, Valeria; Aguilar, Cristóbal N; Picó, Guillermo A

2013-01-01

Tannase from Aspergillus niger was partitioned in aqueous two-phase systems composed by polyethyleneglycol of molar mass 400, 600 and 1000 and potassium phosphate. Tannase was found to be partitioned toward the salt-rich phase in all systems, with partition coefficients lower than 0.5. Partition coefficients values and low entropic and enthalpic changes associated with tannase partition suggest that the entropic effect may be the driving force of the concentration of the enzyme in the bottom phase due to the high molar mass of the enzyme. The process was significantly influenced by the top phase/bottom phase volume ratio. When the fungal culture broth was partitioned in these systems, a good performance was found, since the enzyme recovery in the bottom phase of the system composed by polyethyleneglycol 1000 was around 96% with a 7.0-fold increase in purity. Copyright © 2012 Elsevier B.V. All rights reserved.

Aqueous biphasic plutonium oxide extraction process with pH and particle control

DOEpatents

Chaiko, D.J.; Mensah-Biney, R.

1997-04-29

A method is described for simultaneously partitioning a metal oxide and silica from a material containing silica and the metal oxide, using a biphasic aqueous medium having immiscible salt and polymer phases. 2 figs.

Determination of the distribution constants of aromatic compounds and steroids in biphasic micellar phosphonium ionic liquid/aqueous buffer systems by capillary electrokinetic chromatography.

PubMed

Lokajová, Jana; Railila, Annika; King, Alistair W T; Wiedmer, Susanne K

2013-09-20

The distribution constants of some analytes, closely connected to the petrochemical industry, between an aqueous phase and a phosphonium ionic liquid phase, were determined by ionic liquid micellar electrokinetic chromatography (MEKC). The phosphonium ionic liquids studied were the water-soluble tributyl(tetradecyl)phosphonium with chloride or acetate as the counter ion. The retention factors were calculated and used for determination of the distribution constants. For calculating the retention factors the electrophoretic mobilities of the ionic liquids were required, thus, we adopted the iterative process, based on a homologous series of alkyl benzoates. Calculation of the distribution constants required information on the phase-ratio of the systems. For this the critical micelle concentrations (CMC) of the ionic liquids were needed. The CMCs were calculated using a method based on PeakMaster simulations, using the electrophoretic mobilities of system peaks. The resulting distribution constants for the neutral analytes between the ionic liquid and the aqueous (buffer) phase were compared with octanol-water partitioning coefficients. The results indicate that there are other factors affecting the distribution of analytes between phases, than just simple hydrophobic interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

Unexpected high yields of carbonyl and peroxide products of aqueous isoprene ozonolysis and implications

NASA Astrophysics Data System (ADS)

Wang, H. L.; Huang, D.; Zhang, X.; Zhao, Y.; Chen, Z. M.

2012-03-01

The aqueous phase reaction of volatile organic compounds (VOCs) has not been considered in most analyses of atmospheric chemical processes. However, some experimental evidence has shown that, compared to the corresponding gas phase reaction, the aqueous chemical processes of VOCs in the bulk solutions and surfaces of ambient wet particles (cloud, fog, and wet aerosols) may potentially contribute to the products and formation of secondary organic aerosol (SOA). In the present study, we performed a laboratory experiment of the aqueous ozonolysis of isoprene at different pHs (3-7) and temperatures (4-25 °C). We detected three important kinds of products, including carbonyl compounds, peroxide compounds, and organic acids. Our results showed that the molar yields of these products were nearly independent of the investigated pHs and temperatures. These products included (1) carbonyls: 56.7 ± 6.7% formaldehyde, 42.8 ± 2.5% methacrolein (MAC), and 57.7 ± 3.4% methyl vinyl ketone (MVK); (2) peroxides: 53.4 ± 4.1% hydrogen peroxide (H2O2) and 15.1 ± 3.1% hydroxylmethyl hydroperoxide (HMHP); and (3) organic acids: undetectable (< 1% estimated by the detection limit). Based on the amounts of products formed and the isoprene consumed, the total carbon yield was estimated to be 95 ± 4%. This implied that most of the products in the reaction system were detected. Of note, the combined yields of both MAC + MVK and H2O2 + HMHP in the aqueous isoprene ozonolysis were much higher than those observed in the corresponding gas phase reaction. We suggested that these unexpected high yields of carbonyls and peroxides were related to the greater capability of condensed water, compared to water vapor, to stabilize energy-rich Criegee radicals. This aqueous ozonolysis of isoprene (and possibly other biogenic VOCs) could potentially occur on the surfaces of ambient wet particles and plants. Moreover, the high-yield carbonyl and peroxide products might provide a considerable source of aqueous phase oxidants and SOA precursors. Thus, aqueous ozonolysis on the surface of plants, where carbonyls and peroxides form, might affect biogenic VOC emissions and the deposition of O3 and SO2 onto leaves to different extents in clean and polluted regions.

Primitive Liquid Water of the Solar System in an Aqueous Altered Carbonaceous Chondrite

NASA Technical Reports Server (NTRS)

Tsuchiyama, A.; Miyake, A.; Kitayama, A.; Matsuno, J.; Takeuchi, A.; Uesugi, K.; Suzuki, Y.; Nakano, T.; Zolensky, M. E.

2016-01-01

Non-destructive 3D observations of the aqueous altered CM chondrite Sutter's Mill using scanning imaging x-ray microscopy (SIXM) showed that some of calcite and enstatite grains contain two-phase inclusion, which is most probably composed of liquid water and bubbles. This water should be primitive water responsible for aqueous alteration in an asteroid in the early solar system.

Dispersive liquid-liquid microextraction based on the solidification of floating organic droplet for the determination of polychlorinated biphenyls in aqueous samples.

PubMed

Dai, Liping; Cheng, Jing; Matsadiq, Guzalnur; Liu, Lu; Li, Jun-Kai

2010-08-03

In the proposed method, an extraction solvent with a lower toxicity and density than the solvents typically used in dispersive liquid-liquid microextraction was used to extract seven polychlorinated biphenyls (PCBs) from aqueous samples. Due to the density and melting point of the extraction solvent, the extract which forms a layer on top of aqueous sample can be collected by solidifying it at low temperatures, which form a layer on top of the aqueous sample. Furthermore, the solidified phase can be easily removed from the aqueous phase. Based on preliminary studies, 1-undecanol was selected as the extraction solvent, and a series of parameters that affect the extraction efficiency were systematically investigated. Under the optimized conditions, enrichment factors for PCBs ranged between 494 and 606. Based on a signal-to-noise ratio of 3, the limit of detection for the method ranged between 3.3 and 5.4 ng L(-1). Good linearity, reproducibility and recovery were also obtained. 2010 Elsevier B.V. All rights reserved.

Purification of Active Myrosinase from Plants by Aqueous Two-Phase Counter-Current Chromatography

PubMed Central

Wade, Kristina L.; Ito, Yoichiro; Ramarathnam, Aarthi; Holtzclaw, W. David; Fahey, Jed W.

2014-01-01

Introduction Myrosinase (thioglucoside glucohydrolase; E.C. 3.2.1.147), is a plant enzyme of increasing interest and importance to the biomedical community. Myrosinase catalyses the formation of isothiocyanates such as sulforaphane (frombroccoli) and 4-(α-l-rhamnopyranosyloxy)benzyl isothiocyanate (from moringa), which are potent inducers of the cytoprotective phase-2 response in humans, by hydrolysis of their abundant glucosinolate (β-thioglucoside N-hydroxysulphate) precursors. Objective To develop an aqueous two-phase counter-current chromatography (CCC) system for the rapid, three-step purification of catalytically active myrosinase. Methods A high-concentration potassium phosphate and polyethylene glycol biphasic aqueous two-phase system (ATPS) is used with a newly developed CCC configuration that utilises spiral-wound, flat-twisted tubing (with an ovoid cross-section). Results Making the initial crude plant extract directly in the ATPS and injecting only the lower phase permitted highly selective partitioning of the myrosinase complex before a short chromatography on a spiral disk CCC. Optimum phase retention and separation of myrosinase from other plant proteins afforded a 60-fold purification. Conclusion Catalytically active myrosinase is purified from 3-day broccoli sprouts, 7-day daikon sprouts, mustard seeds and the leaves of field-grown moringa trees, in a CCC system that is predictably scalable. PMID:25130502

Purification of active myrosinase from plants by aqueous two-phase counter-current chromatography.

PubMed

Wade, Kristina L; Ito, Yoichiro; Ramarathnam, Aarthi; Holtzclaw, W David; Fahey, Jed W

2015-01-01

Myrosinase (thioglucoside glucohydrolase; E.C. 3.2.1.147), is a plant enzyme of increasing interest and importance to the biomedical community. Myrosinase catalyses the formation of isothiocyanates such as sulforaphane (from broccoli) and 4-(α-l-rhamnopyranosyloxy)benzyl isothiocyanate (from moringa), which are potent inducers of the cytoprotective phase-2 response in humans, by hydrolysis of their abundant glucosinolate (β-thioglucoside N-hydroxysulphate) precursors. To develop an aqueous two-phase counter-current chromatography (CCC) system for the rapid, three-step purification of catalytically active myrosinase. A high-concentration potassium phosphate and polyethylene glycol biphasic aqueous two-phase system (ATPS) is used with a newly developed CCC configuration that utilises spiral-wound, flat-twisted tubing (with an ovoid cross-section). Making the initial crude plant extract directly in the ATPS and injecting only the lower phase permitted highly selective partitioning of the myrosinase complex before a short chromatography on a spiral disk CCC. Optimum phase retention and separation of myrosinase from other plant proteins afforded a 60-fold purification. Catalytically active myrosinase is purified from 3-day broccoli sprouts, 7-day daikon sprouts, mustard seeds and the leaves of field-grown moringa trees, in a CCC system that is predictably scalable. Copyright © 2014 John Wiley & Sons, Ltd.

Extraction and separation of tungsten (VI) from aqueous media with Triton X-100-ammonium sulfate-water aqueous two-phase system without any extractant.

PubMed

Yongqiang Zhang; Tichang Sun; Tieqiang Lu; Chunhuan Yan

2016-11-25

An aqueous two-phase system composed of Triton X-100-(NH 4 ) 2 SO 4 -H 2 O was proposed for extraction and separation of tungsten(VI) from aqueous solution without using any extractant. The effects of aqueous pH, concentration of ammonium sulfate, Triton X-100 and tungsten, extracting temperature on the extraction of tungsten were investigated. The extraction of tungsten has remarkable relationship with aqueous pH and are to above 90% at pH=1.0-3.0 under studied pH range (pH=1.0-7.0) and increases gradually with increasing Triton X-100 concentration, but decreases slightly with increasing ammonium sulfate concentration. The extraction percentage of tungsten is hardly relevant to temperature but its distribution coefficient linearly increases with increasing temperature within 303.15-343.15K. The distribution coefficient of tungsten increases with the increase of initial tungsten concentration (0.1-3%) and temperature (303.15 K-333.15K). The solubilization capacity of tungsten in Triton X-100 micellar phase is independent of temperature. FT-IR analysis reveals that there is no evident interaction between polytungstate anion and ether oxygen unit in Triton X-100, and DLS analysis indicates that zeta potential of Triton X-100 micellar phase have a little change from positive to negative after extracting tungsten. Based on the above-mentioned results, it can be deduced that polytungstate anions are solubilized in hydrophilic outer shell of Triton X-100 micelles by electrostatic attraction depending on its relatively high hydrophobic nature. The stripping of tungsten is mainly influenced by temperature and can be easily achieved to 95% in single stage stripping. The tungsten (VI) is separated out from solution containing Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Al(III), Cr(III) and Mn(II) under the suitable conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Modification of the Magnetic Properties of α-Fe2O3 Powders by Ultrasonic Processing

NASA Astrophysics Data System (ADS)

Stolyar, S. V.; Bayukov, O. A.; Iskhakov, R. S.; Yaroslavtsev, R. N.; Ladygina, V. P.

2017-12-01

Hematite (α-Fe2O3) powders after ultrasonic treatment (UST) in the regime of cavitation in aqueous suspension and in that with an organic component (albumin protein) have been studied by Mössbauer spectroscopy and ferromagnetic resonance techniques. It is established that the UST in aqueous hematite suspensions with albumin results in the formation of a new magnetic phase with parameters coinciding with those of the α-Fe metallic phase.

Uranium(IV) Interaction with Aqueous/Solid Interfaces Studied by Nonlinear Optics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geiger, Franz

2015-03-27

This is the Final Technical Report for "Uranium(IV) Interaction with Aqueous/Solid Interfaces Studied by Nonlinear Optics", by Franz M. Geiger, PI, from Northwestern University, IL, USA, Grant Number SC0004101 and/or DE-PS02-ER09-07.

Development of a Compact and Efficient Ice Thermal Energy Storage Vessel

NASA Astrophysics Data System (ADS)

Sasaguchi, Kengo; Ishikawa, Masatoshi; Muta, Kenji; Yoshino, Kiyotaka; Hayashi, Hiroko; Baba, Yoshiyuki

In the present study, the authors propose the use of a low concentration aqueous solution as phase change material for static-type ice-storage-vessels, instead of pure water commonly used today. If an aqueous solution with low concentration is used, even when a large amount of solution (aqueous ethylene glycol in this study) is solidified and bridging of ice developed around cold tubes occurs, the pressure increase could be prevented by the existence of a continuous liquid phase in the solid-liquid two-phase layer (mushy layer) which opens to an air gap at the top of a vessel. Therefore, one can continue to solidify an aqueous solution after bridging, achieving a high ice packing factor (IPF). First, experiments using small-scale test cells have been conducted to confirm the present idea, and then we have performed experiments using a large vessel with an early practical size. It was seen that a large pressure increase is prevented for the initial concentration of the solution C0 of 1.0%, and IPF obtained using the solution is much greater than 0.65 using pure water for which the solidification must be stopped before the bridging.

Aqueous Alteration and Hydrogen Generation on Parent Bodies of Unequilibrated Ordinary Chondrites: Thermodynamic Modeling for the Semarkona Composition

NASA Technical Reports Server (NTRS)

Zolotov, M. Y.; Mironenko, M. V.; Shock, E. L.

2005-01-01

Ordinary chondrites are the most abundant class of meteorites that could represent rocky parts of solar system bodies. However, even the most primitive unequilibrated ordinary chondrites (UOC) reveal signs of mild alteration that affected the matrix and peripheral zones of chondrules. Major chemical changes include oxidation of kamacite, alteration of glass, removal of alkalis, Al, and Si from chondrules, and formation of phases enriched in halogens, alkalis, and hydrogen. Secondary mineralogical changes include formation of magnetite, ferrous olivine, fayalite, pentlandite, awaruite, smectites, phosphates, carbonates, and carbides. Aqueous alteration is consistent with the oxygen isotope data for magnetite. The presence of secondary magnetite, Ni-rich metal alloys, and ferrous silicates in UOC implies that H2O was the oxidizing agent. However, oxidation by H2O means that H2 is produced in each oxidative pathway. In turn, production of H2, and its redistribution and possible escape should have affected total pressure, as well as the oxidation state of gas, aqueous and mineral phases in the parent body. Here we use equilibrium thermodynamic modeling to explore water-rock reactions in UOC. The chemical composition of gas, aqueous, and mineral phases is considered.

Ionic liquid and aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of seven rare ginsenosides in Xue-Sai-Tong injection.

PubMed

Li, Lan-Jie; Jin, Yong-Ri; Wang, Xiao-Zhong; Liu, Ying; Wu, Qian; Shi, Xiao-Lei; Li, Xu-Wen

2015-09-01

A method of ionic liquid salt aqueous two-phase extraction coupled with high-performance liquid chromatography has been developed for the analysis of seven rare ginsenosides including Rg6 , F4 , 20(S)-Rg3 , 20(R)-Rg3 , Rk3 , Rk1 , and Rg5 in Xue-Sai-Tong injection. The injection was mixed with ionic liquid 1-butyl-3-methylimidazolium bromide aqueous solution, and a mixture was obtained. With the addition of sodium dodecyl sulfate and dipotassium phosphate into the mixture, the aqueous two-phase mixture was formed after ultrasonic treatment and centrifuged. Rare ginsenosides were extracted into the upper phase. To obtain a high extraction factors, various influences were considered systematically, such as the volume of ionic liquid, the category and amount of salts, the amount of sodium dodecyl sulfate, the pH value of system, and the time of ultrasonic treatment. Under the optimal condition, rare ginsenosides in Xue-Sai-Tong injection were enriched and detected, the recoveries of seven rare ginsenosides ranged from 90.05 to 112.55%, while relative standard deviations were lower than 2.50%. The developed method was reliable, rapid and sensitive for the determination of seven rare ginsenosides in the injections. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laboratory Experiments and Modeling of Pooled NAPL Dissolution in Porous Media

NASA Astrophysics Data System (ADS)

Copty, N. K.; Sarikurt, D. A.; Gokdemir, C.

2017-12-01

The dissolution of non-aqueous phase liquids (NAPLs) entrapped in porous media is commonly modeled at the continuum scale as the product of a chemical potential and an interphase mass transfer coefficient, the latter expressed in terms of Sherwood correlations that are related to flow and porous media properties. Because of the lack of precise estimates of the interface area separating the NAPL and aqueous phase, numerous studies have lumped the interfacial area into the interphase mass transfer coefficient. In this paper controlled dissolution experiments from a pooled NAPL were conducted. The immobile NAPL mass is placed at the bottom of a flow cell filled with porous media with water flowing on top. Effluent aqueous phase concentrations were measured for a wide range of aqueous phase velocities and for two types of porous media. To interpret the experimental results, a two-dimensional pore network model of the NAPL dissolution was developed. The well-defined geometry of the NAPL-water interface and the observed effluent concentrations were used to compute best-fit mass transfer coefficients and non-lumped Sherwood correlations. Comparing the concentrations predicted with the pore network model to simple previously used one-dimensional analytic solutions indicates that the analytic model which ignores the transverse dispersion can lead to over-estimation of the mass transfer coefficient. The predicted Sherwood correlations are also compared to previously published data and implications on NAPL remediation strategies are discussed.

Extraction of steroidal glucosiduronic acids from aqueous solutions by anionic liquid ion-exchangers

PubMed Central

Mattox, Vernon R.; Litwiller, Robert D.; Goodrich, June E.

1972-01-01

A pilot study on the extraction of three steroidal glucosiduronic acids from water into organic solutions of liquid ion-exchangers is reported. A single extraction of a 0.5mm aqueous solution of either 11-deoxycorticosterone 21-glucosiduronic acid or cortisone 21-glucosiduronic acid with 0.1m-tetraheptylammonium chloride in chloroform took more than 99% of the conjugate into the organic phase; under the same conditions, the very polar conjugate, β-cortol 3-glucosiduronic acid, was extracted to the extent of 43%. The presence of a small amount of chloride, acetate, or sulphate ion in the aqueous phase inhibited extraction, but making the aqueous phase 4.0m with ammonium sulphate promoted extraction strongly. An increase in the concentration of ion-exchanger in the organic phase also promoted extraction. The amount of cortisone 21-glucosiduronic acid extracted by tetraheptylammonium chloride over the pH range of 3.9 to 10.7 was essentially constant. Chloroform solutions of a tertiary, a secondary, or a primary amine hydrochloride also will extract cortisone 21-glucosiduronic acid from water. The various liquid ion exchangers will extract steroidal glucosiduronic acid methyl esters from water into chloroform, although less completely than the corresponding free acids. The extraction of the glucosiduronic acids from water by tetraheptylammonium chloride occurs by an ion-exchange process; extraction of the esters does not involve ion exchange. PMID:5075264

Short-column anion-exchange chromatography for soil and peat humic substances profiling by step-wise gradient of high pH aqueous sodium ethylenediaminetetraacetate.

PubMed

Hutta, Milan; Ráczová, Janka; Góra, Róbert; Pessl, Juraj

2015-08-21

Novel anion-exchange liquid chromatographic method with step gradient of aqueous EDTA(4-) based mobile phase elution has been developed to profile available Slovak soil humic substances and alkaline extracts of various soils. The method utilize short glass column (30mm×3mm) filled in with hydrolytically stable particles (60μm diameter) Separon HEMA-BIO 1000 having (diethylamino)ethyl functional groups. Step gradient was programmed by mixing mobile phase composed of aqueous solution of sodium EDTA (pH 12.0; 5mmolL(-1)) and mobile phase constituted of aqueous solution of sodium EDTA (pH 12.0, 500mmolL(-1)). The FLD of HSs was set to excitation wavelength 480nm and emission wavelength 530nm (λem). Separation mechanism was studied by use of selected aromatic acids related to humic acids with the aid of UV spectrophotometric detection at 280nm. The proposed method benefits from high ionic strength (I=5molL(-1)) of the end mobile phase buffer and provides high recovery of humic acids (98%). Accurate and reproducible profiling of studied humic substances, alkaline extracts of various types of soils enables straightforward characterization and differentiation of HSs in arable and forest soils. Selected model aromatic acids were used for separation mechanism elucidation. Copyright © 2015 Elsevier B.V. All rights reserved.

Extension of the CAPRAM mechanism with the improved mechanism generator GECKO-A

NASA Astrophysics Data System (ADS)

Herrmann, H.; Bräuer, P.; Mouchel-Vallon, C.; Tilgner, A.; Wolke, R.; Aumont, B.

2013-12-01

The ubiquitous abundance of organic compounds in natural and anthropogenically influenced eco-systems has put these compounds into the focus of environmental research. To investigate the chemistry of organic compounds in the tropospheric multiphase system, modelling can provide a useful tool. While in the gas phase several comprehensive near-explicit mechanisms exist, in the aqueous phase those mechanisms are very limited. The present study aims to advance the currently most comprehensive aqueous phase mechanism CAPRAM 3.0n (Tilgner and Herrmann, 2010; Bräuer et al., 2013) by means of automated mechanism self-construction. Therefore, the mechanism generator GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere; see Aumont et al., 2005) has been advanced to the aqueous phase. A protocol has been designed for automated mechanism construction based on reviewed experimental data and evaluated prediction methods. The generator is able to describe the oxidation of aliphatic organic compounds by OH and NO3. For the mechanism construction, mainly structure-activity relationships are used. They are completed by Evans-Polanyi-type correlations, which have been further improved for the purpose of automated mechanism self-construction. GECKO-A has been used to create new CAPRAM versions, where branching ratios are introduced and new chemical subsystems with species with up to 4 carbon atoms are added. The currently most comprehensive version, CAPRAM 3.5alpha, includes about 2000 aqueous phase species and more than 3300 reactions in the aqueous phase. Process studies with the box model SPACCIM (SPectral Aerosol Cloud Chemistry Interaction Model; Wolke et al., 2005) have been performed using a meteorological scenario with non-permanent clouds. Besides the investigation of the concentration-time profiles, detailed time-resolved flux analyses have been performed. Several aqueous phase subsystems have been investigated, such as the formation of oxidised mono- and diacids in the aqueous phase as well as interactions to inorganic cycles and the influence on the gas phase chemistry and composition. Results have been compared to results of previous versions and show a significant improvement in CAPRAM 3.5alpha when comparing the modelled data to literature data from field experiments. For example, in CAPRAM 3.5alpha there is a malonic acid production of about 80 ng/m3 compared to a few ng m-3 in CAPRAM 3.0n. The results in CAPRAM 3.5alpha confirm recent measurements by Bao et al. (2012), who measured up to 137 ng m-3. Moreover, several attempts have been undertaken to validate the mechanisms created by GECKO-A with own experiments, such as the HCCT-2010 campaign and LEAK chamber experiments. References Aumont, B et al., Atmos. Chem. Phys., 5, 2497-2517, 2005. Bräuer, P. et al., J. Atmos. Chem., 70(1), 1 - 34, 2013. Bao, L. et al., Atmos. Env., 47, 546 - 553, 2012. Tilgner, A. and Herrmann, H., Atmos. Environ., 44, 5415 - 5422, 2010. Wolke, R. et al., Atmos. Environ., 39, 4375 - 4388, 2005.

Evaluation of toxicity of trichloroethylene for plants

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, S.B.; Davis, L.C.; Dana, J.

1996-12-31

Trichloroethylene (TCE) exposure of several species of plants was studied. Although earlier studies indicated that the root systems of plants could tolerate an aqueous phase concentration of 1 mM for a day, toxicity to whole plants was observed at somewhat lower levels in the gas phase in this study. The tested species included pumpkin (Cucurbita maxima), tomato (Lycopersicon esculentum), sweet potato (Dioscoria batata), tobacco (Nicotiana tabacum), soybean (Glycine max L. Merr), and alfalfa (Medicago sativa). Damage was observable as wilting or failure of the gravitropic response of shoots at levels above about 0.2 mM in the gas phase, which correspondsmore » to 0.5 mM in the aqueous phase. Plants were usually killed quickly at gas phase concentrations above 0.4 mM.« less

Mobility of arsenic in a Bangladesh aquifer: Inferences from geochemical profiles, leaching data, and mineralogical characterization

NASA Astrophysics Data System (ADS)

Swartz, Christopher H.; Blute, Nicole Keon; Badruzzman, Borhan; Ali, Ashraf; Brabander, Daniel; Jay, Jenny; Besancon, James; Islam, Shafiqul; Hemond, Harold F.; Harvey, Charles F.

2004-11-01

Aquifer geochemistry was characterized at a field site in the Munshiganj district of Bangladesh where the groundwater is severely contaminated by As. Vertical profiles of aqueous and solid phase parameters were measured in a sandy deep aquifer (depth >150 m) below a thick confining clay (119 to 150 m), a sandy upper aquifer (3.5 to 119 m) above this confining layer, and a surficial clay layer (<3.5 m). In the deep aquifer and near the top of the upper aquifer, aqueous As levels are low (<10 μg/L), but aqueous As approaches a maximum of 640 μg/L at a depth of 30 to 40 m and falls to 58 μg/L near the base (107 m) of the upper aquifer. In contrast, solid phase As concentrations are uniformly low, rarely exceeding 2 μg/g in the two sandy aquifers and never exceeding 10 μg/g in the clay layers. Solid phase As is also similarly distributed among a variety of reservoirs in the deep and upper aquifer, including adsorbed As, As coprecipitated in solids leachable by mild acids and reductants, and As incorporated in silicates and other more recalcitrant phases. One notable difference among depths is that sorbed As loads, considered with respect to solid phase Fe extractable with 1 N HCl, 0.2 M oxalic acid, and a 0.5 M Ti(III)-citrate-EDTA solution, appear to be at capacity at depths where aqueous As is highest; this suggests that sorption limitations may, in part, explain the aqueous As depth profile at this site. Competition for sorption sites by silicate, phosphate, and carbonate oxyanions appear to sustain elevated aqueous As levels in the upper aquifer. Furthermore, geochemical profiles are consistent with the hypothesis that past or ongoing reductive dissolution of Fe(III) oxyhydroxides acts synergistically with competitive sorption to maintain elevated dissolved As levels in the upper aquifer. Microprobe data indicate substantial spatial comapping between As and Fe in both the upper and deep aquifer sediments, and microscopic observations reveal ubiquitous Fe coatings on most solid phases, including quartz, feldspars, and aluminosilicates. Extraction results and XRD analysis of density/magnetic separates suggest that these coatings may comprise predominantly Fe(II) and mixed valence Fe solids, although the presence of Fe(III) oxyhydroxides can not be ruled out. These data suggest As release may continue to be linked to dissolution processes targeting Fe, or Fe-rich, phases in these aquifers.

Insights into water-mediated ion clustering in aqueous CaSO4 solutions: pre-nucleation cluster characteristics studied by ab initio calculations and molecular dynamics simulations.

PubMed

Li, Hui-Ji; Yan, Dan; Cai, Hou-Qin; Yi, Hai-Bo; Min, Xiao-Bo; Xia, Fei-Fei

2017-05-10

The molecular structure of growth units building crystals is a fundamental issue in the crystallization processes from aqueous solutions. In this work, a systematic investigation of pre-nucleation clusters and their hydration characteristics in aqueous CaSO 4 solutions was performed using ab initio calculations and molecular dynamics (MD) simulations. The results of ab initio calculations and MD simulations indicate that the dominant species in aqueous CaSO 4 solutions are monodentate ion-associated structures. Compared with charged ion clusters, neutral clusters are more likely to be present in an aqueous CaSO 4 solution. Neutral (CaSO 4 ) m clusters are probably the growth units involved in the pre-nucleation or crystallization processes. Meanwhile, hydration behavior around ion associated species in aqueous CaSO 4 solutions plays an important role in related phase/polymorphism selections. Upon ion clustering, the residence of some water molecules around Ca 2+ in ion-associated species is weakened while that of some bridging waters is enhanced due to dual interaction by Ca 2+ and SO 4 2- . Some phase/polymorphism selections can be achieved in aqueous CaSO 4 solutions by controlling the hydration around pre-nucleation clusters. Moreover, the association trend between calcium and sulfate is found to be relatively strong, which hints at the low solubility of calcium sulfate in water.

Hot-water and solid-phase extraction of fluorescent whitening agents in paper materials and infant clothes followed by unequivocal determination with ion-pair chromatography-tandem mass spectrometry.

PubMed

Chen, Hsin-Chang; Ding, Wang-Hsien

2006-03-10

A comprehensive method for the determination of four stilbene-type disulfonate and one distyrylbiphenyl-type fluorescent whitening agents (FWAs) in paper materials (napkin and paper tissue) and infant clothes was developed. FWAs were extracted from paper material and cloth samples using a hot-water extraction, and the aqueous extracts were then preconcentrated with the newly developed Oasis WAX (mixed-mode of weak anion exchange and reversed-phase sorbent) solid-phase extraction cartridge. The analytes were unequivocal determined by ion pair chromatography coupled with negative electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS-MS), applying a di-n-hexyl-ammonium acetate (DHAA) as the ion-pairing reagent in mobile phase. Limits of quantitation (LOQ) were established between 0.2 and 0.9 ng/g in 2 g of samples. Recovery of five FWAs in spiked commercial samples was between 42 and 95% and RSD (n = 3) ranging from 2 to 11%. The method was finally applied to commercial samples, showing that two stilbene-type disulfonates were predominant FWAs detected in napkin and infant cloth samples.

Bio-Oil Hydrotreatment for Enhancing Solubility in Biodiesel and the Oxydation Stability of Resulting Blends.

PubMed

Botella, Lucía; Stankovikj, Filip; Sánchez, José L; Gonzalo, Alberto; Arauzo, Jesús; Garcia-Pérez, Manuel

2018-01-01

The major challenge for the pyrolytic conversion of lignocellulosic materials into crude bio-oil is the poor quality of the final product. Several strategies (addition of solvents, production of emulsions, and extraction with biodiesel) have been studied to improve its fuel properties. The extraction with biodiesel is an interesting solution because it allows direct utilization of some bio-oil fractions as fuels. However, fraction extracted with biodiesel is typically between 10 and 18 wt. %. In this paper we studied mild hydrotreatment of pyrolysis oil to enhance its solubility in biodiesel. The study was conducted with BTG and Amaron oils hydrotreated at temperatures between 200 and 325°C in the presence of Ru/C catalyst. Hydrotreated oils generated three phases: top oil (light hydrocarbons), middle aqueous phase and bottom heavy oil phase. Each of the phases was characterized and the content of acetic acid, phenols, aromatic compounds, and linear alkane hydrocarbons quantified. The upgraded bio-oils were more soluble in biodiesel than the crude bio-oils, obtaining blends with up to 48 and 38 wt. % for the BTG and Amaron bio-oil, respectively. Some of the fuel properties of the resulting blends are also reported here.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundaramurthi, Prakash; Patapoff, Thomas W.; Suryanarayanan, Raj

To study the crystallization of trehalose in frozen solutions and to understand the phase transitions during the entire freeze-drying cycle. Aqueous trehalose solution was cooled to -40 C in a custom-designed sample holder. The frozen solution was warmed to -18 C and annealed, and then dried in the sample chamber of the diffractometer. XRD patterns were continuously collected during cooling, annealing and drying. After cooling, hexagonal ice was the only crystalline phase observed. However, upon annealing, crystallization of trehalose dihydrate was evident. Seeding the frozen solution accelerated the solute crystallization. Thus, phase separation of the lyoprotectant was observed in frozenmore » solutions. During drying, dehydration of trehalose dihydrate yielded a substantially amorphous anhydrous trehalose. Crystallization of trehalose, as trehalose dihydrate, was observed in frozen solutions. The dehydration of the crystalline trehalose dihydrate to substantially amorphous anhydrate occurred during drying. Therefore, analyzing the final lyophile will not reveal crystallization of the lyoprotectant during freeze-drying. The lyoprotectant crystallization can only become evident by continuous monitoring of the system during the entire freeze-drying cycle. In light of the phase separation of trehalose in frozen solutions, its ability to serve as a lyoprotectant warrants further investigation.« less

Bio-oil Hydrotreatment for Enhancing Solubility in Biodiesel and the Oxydation Stability of Resulting Blends

NASA Astrophysics Data System (ADS)

Botella, Lucía; Stankovikj, Filip; Sánchez, José L.; Gonzalo, Alberto; Arauzo, Jesús; Garcia-Pérez, Manuel

2018-04-01

The major challenge for the pyrolytic conversion of lignocellulosic materials into crude bio-oil is the poor quality of the final product. Several strategies (addition of solvents, production of emulsions, and extraction with biodiesel) have been studied to improve its fuel properties. The extraction with biodiesel is an interesting solution because it allows direct utilization of some bio-oil fractions as fuels. However, fraction extracted with biodiesel is typically between 10 and 18 wt. %. In this paper we studied mild hydrotreatment of pyrolysis oil to enhance its solubility in biodiesel. The study was conducted with BTG and Amaron oils hydrotreated at temperatures between 200 and 325 °C in the presence of Ru/C catalyst. Hydrotreated oils generated three phases: top oil (light hydrocarbons), middle aqueous phase and bottom heavy oil phase. Each of the phases was characterized and the content of acetic acid, phenols, aromatic compounds and linear alkane hydrocarbons quantified. The upgraded bio-oils were more soluble in biodiesel than the crude bio-oils, obtaining blends with up to 48 and 38 wt. % for the BTG and Amaron bio-oil, respectively. Some of the fuel properties of the resulting blends are also reported here.

Bio-Oil Hydrotreatment for Enhancing Solubility in Biodiesel and the Oxydation Stability of Resulting Blends

PubMed Central

Botella, Lucía; Stankovikj, Filip; Sánchez, José L.; Gonzalo, Alberto; Arauzo, Jesús; Garcia-Pérez, Manuel

2018-01-01

The major challenge for the pyrolytic conversion of lignocellulosic materials into crude bio-oil is the poor quality of the final product. Several strategies (addition of solvents, production of emulsions, and extraction with biodiesel) have been studied to improve its fuel properties. The extraction with biodiesel is an interesting solution because it allows direct utilization of some bio-oil fractions as fuels. However, fraction extracted with biodiesel is typically between 10 and 18 wt. %. In this paper we studied mild hydrotreatment of pyrolysis oil to enhance its solubility in biodiesel. The study was conducted with BTG and Amaron oils hydrotreated at temperatures between 200 and 325°C in the presence of Ru/C catalyst. Hydrotreated oils generated three phases: top oil (light hydrocarbons), middle aqueous phase and bottom heavy oil phase. Each of the phases was characterized and the content of acetic acid, phenols, aromatic compounds, and linear alkane hydrocarbons quantified. The upgraded bio-oils were more soluble in biodiesel than the crude bio-oils, obtaining blends with up to 48 and 38 wt. % for the BTG and Amaron bio-oil, respectively. Some of the fuel properties of the resulting blends are also reported here. PMID:29675406

THE CHEMISTRY OF TRIBUTYL PHOSPHATE: A REVIEW

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burger, L.L.

1955-10-27

The preparation, purification, and chemical properties of THP have been reviewed with emphasis on the hydrolytic reactions. TBP is chemically a very stable compound as evidenced by its thermal stability and resistance to oxidation. The most important reactions are hydrolytic which cleave the butyl or butoxy group and normally produce butyl alcohol together with dibutyl and monobutyl phosphate (DBP and MBP, respectively), and eventually H/sub 3/PO/sub 4/. Hydrolysis occurs in either the organic phase or the aqueous phase and is first order with respect to the ester. Although the rate in the aqueous phase is much faster than in themore » organic phase, the solubility is so low in aqueous solutions that the organic phase reactions become more important. Acid hydrolysis depends on both the nature of the acid and the concentration. The order with respect to acid concentration is close to one but often less than one. Hydrolysis is catalyzed by both acids and bases. In the latter case, the reaction occurs only in the aqueous phase and normally stops with the formation of dibutyl phosphate. The hydrolysis rate increases greatly as the temperature is raised and an activation energy of the order of 20 kcal is often found. The rates observed in the presence of 5 M acid at 60 and 70 deg C may be high enough to cause some concern in solvent extraction technology, since the product, dibutyl phosphate, has undesirable properties. Impurities produced during manufacture or by thermal degradation during purification such as the pyrophosphates, if present, would yield the same objectionable products as TBP hydrolysis, but at a faster rate. Included in the survey is a selected tabulation of physical properties of TBP. (auth)« less

Measuring the Densities of Aqueous Glasses at Cryogenic Temperatures.

PubMed

Shen, Chen; Julius, Ethan F; Tyree, Timothy J; Dan, Ritwik; Moreau, David W; Thorne, Robert

2017-06-28

We demonstrate a method for determining the vitreous phase cryogenic temperature densities of aqueous mixtures, and other samples that require rapid cooling, to prepare the desired cryogenic temperature phase. Microliter to picoliter size drops are cooled by projection into a liquid nitrogen-argon (N2-Ar) mixture. The cryogenic temperature phase of the drop is evaluated using a visual assay that correlates with X-ray diffraction measurements. The density of the liquid N2-Ar mixture is adjusted by adding N2 or Ar until the drop becomes neutrally buoyant. The density of this mixture and thus of the drop is determined using a test mass and Archimedes principle. With appropriate care in drop preparation, management of gas above the liquid cryogen mixture to minimize icing, and regular mixing of the cryogenic mixture to prevent density stratification and phase separation, densities accurate to <0.5% of drops as small as 50 pL can readily be determined. Measurements on aqueous cryoprotectant mixtures provide insight into cryoprotectant action, and provide quantitative data to facilitate thermal contraction matching in biological cryopreservation.

In-situ phase transition from microemulsion to liquid crystal with the potential of prolonged parenteral drug delivery.

PubMed

Ren, Xiazhong; Svirskis, Darren; Alany, Raid G; Zargar-Shoshtari, Sara; Wu, Zimei

2012-07-15

This study is the first to investigate and demonstrate the potential of microemulsions (MEs) for sustained release parenteral drug delivery, due to phase transition behavior in aqueous environments. Phase diagrams were constructed with Miglyol 812N oil and a blend of (co)surfactants Solutol HS 15 and Span 80 with ethanol. Liquid crystal (LC) and coarse emulsion (CE) regions were found adjacent to the ME region in the water-rich corner of the phase diagram. Two formulations were selected, a LC-forming ME and a CE-forming ME and each were investigated with respect to their rheology, particle size, drug release profiles and particularly, the phase transition behavior. The spreadability in an aqueous environment was determined and release profiles from MEs were generated with gamma-scintigraphy. The CE-forming ME dispersed readily in an aqueous environment, whereas the LC-forming ME remained in a contracted region possibly due to the transition of ME to LC at the water/ME interface. Gamma-scintigraphy showed that the LC-forming ME had minimal spreadability and a slow release of (99m)Tc in the first-order manner, suggesting phase conversion at the interface. In conclusion, owing to the potential of phase transition, LC-forming MEs could be used as extravascular injectable drug delivery vehicles for prolonged drug release. Copyright © 2012 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortiz, E.; Kraatz, M.; Luthy, R.G.

The dissolution of naphthalene, phenanthrene, and pyrene from viscous organic phases into water was studied in continuous-flow systems for time periods ranging from several months to more than 1 year. By selecting nonaqueous phases ranging from low viscosity to semisolid, i.e., from a light lubricating oil to paraffin, the governance of mass transfer was shown to vary from water phase control to nonaqueous phase control. An advancing depleted-zone model is proposed to explain the dissolution of PAHs from a viscous organic phase wherein the formation of a depleted zone within the organic phase increases the organic phase resistance to themore » dissolution of PAHs. The experimental data suggest the formation of a depleted zone within the organic phase for systems comprising a high-viscosity oil, petrolatum (petroleum jelly), and paraffin. Organic phase resistance to naphthalene dissolution became dominant over aqueous phase resistance after flushing for several days. Such effects were not evident for low viscosity lubricating oil. The transition from aqueous-phase dissolution control to nonaqueous-phase dissolution control appears predictable, and this provides a more rational framework to assess long-term release of HOCs from viscous nonaqueous phase liquids and semisolids.« less

Calix[4]arene-bis(t-octylbenzo-18-crown-6) as an extraordinarily effective macrocyclic receptor for the univalent thallium cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makrlik, Emanuel; Toman, Petr; Vanura, Petr

2013-01-01

From extraction experiments and -activity measurements, the exchange extraction constant corresponding to the equilibrium Tl+ (aq) + 1 Cs+ (org) 1 Tl+ (org) + Cs+ (aq) taking place in the two-phase water phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as log Kex (Tl+, 1 Cs+) = 1.7 0.1. Further, the extraordinarily high stability constant of the 1 Tl+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log org(1 Tl+) = 13.1 0.2. Finally, by using quantum mechanical DFT calculations, themore » most probable structure of the cationic complex species 1 Tl+ was derived. In the resulting 1 Tl+ complex, the central cation Tl+ is bound by eight bond interactions to six oxygen atoms from the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent receptor 1 via cation interaction.« less

Interaction of the cesium cation with calix[4]arene-bis(t-octylbenzo-18-crown-6): Extraction and DFT study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makrlik, Emanuel; Toman, Petr; Vanura, Petr

2013-01-01

From extraction experiments and c-activity measurements, the extraction constant corresponding to the equilibrium Cs+ (aq) + I (aq) + 1 (org),1Cs+ (org) + I (org) taking place in the two-phase water-phenyltrifluoromethyl sulfone (abbrev. FS 13) system (1 = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, org = FS 13 phase) was evaluated as logKex (1Cs+, I) = 2.1 0.1. Further, the stability constant of the 1Cs+ complex in FS 13 saturated with water was calculated for a temperature of 25 C: log borg (1Cs+) = 9.9 0.1. Finally, by using quantum mechanical DFT calculations, the most probable structure of the cationic complexmore » species 1Cs+ was derived. In the resulting 1Cs+ complex, the central cation Cs+ is bound by eight bond interactions to six oxygen atoms of the respective 18-crown-6 moiety and to two carbons of the corresponding two benzene rings of the parent ligand 1 via cation p interaction.« less

Interaction of the univalent silver cation with [Gly6]-antamanide: Experimental and theoretical study

NASA Astrophysics Data System (ADS)

Makrlík, Emanuel; Böhm, Stanislav; Kvíčala, Jaroslav; Vaňura, Petr; Ruzza, Paolo

2018-03-01

On the basis of extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Ag+(aq) + 1.Na+(nb) ⇄ 1.Ag+ (nb) + Na+(aq) occurring in the two-phase water - nitrobenzene system (1 = [Gly6]-antamanide; aq = aqueous phase, nb = nitrobenzene phase) was determined as log Kex (Ag+,1·Na+) = 1.5 ± 0.1. Further, the stability constant of the 1·Ag+ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log βnb (1·Ag+) = 4.5 ± 0.2. Finally, by using quantum chemical DFT calculations, the most probable structure of the cationic complex species 1·Ag+ was derived. In the resulting complex, the "central" cation Ag+ is coordinated by four noncovalent interactions to the corresponding four carbonyl oxygen atoms of the parent ligand 1. Besides, the whole 1·Ag+ complex structure is stabilized by two intramolecular hydrogen bonds. The interaction energy of the considered 1·Ag+ complex was found to be -465.5 kJ/mol, confirming also the formation of this cationic species.

Method and apparatus for destroying organic contaminants in aqueous liquids

DOEpatents

Donaldson, T.L.; Wilson, J.H.

1993-09-21

A method and apparatus for destroying organic contaminants, such as trichloroethylene, in aqueous liquids, such as groundwater, utilizing steam stripping integrated with biodegradation. The contaminated aqueous liquid is fed into a steam stripper causing the volatilization of essentially all of the organic contaminants and a portion of the aqueous liquid. The majority of the aqueous liquid is discharged from the steam stripper. The volatilized vapors are then condensed to the liquid phase and introduced into a bioreactor. The bioreactor contains methanotrophic microorganisms which convert the organic contaminants into mainly carbon dioxide. The effluent from the bioreactor is then recycled back to the steam stripper for further processing. 2 figures.

Method and apparatus for destroying organic contaminants in aqueous liquids

DOEpatents

Donaldson, Terrence L.; Wilson, James H.

1993-01-01

A method and apparatus for destroying organic contaminants, such as trichloroethylene, in aqueous liquids, such as groundwater, utilizing steam stripping integrated with biodegradation. The contaminated aqueous liquid is fed into a steam stripper causing the volatilization of essentially all of the organic contaminants and a portion of the aqueous liquid. The majority of the aqueous liquid is discharged from the steam stripper. The volatilized vapors are then condensed to the liquid phase and introduced into a bioreactor. The bioreactor contains methanotrophic microorganisms which convert the organic contaminants into mainly carbon dioxide. The effluent from the bioreactor is then recycled back to the steam stripper for further processing.

Enantioselective synthesis of (S)-naproxen using immobilized lipase on chitosan beads.

PubMed

Gilani, Saeedeh L; Najafpour, Ghasem D; Heydarzadeh, Hamid D; Moghadamnia, Aliakbar

2017-06-01

S-naproxen by enantioselective hydrolysis of racemic naproxen methyl ester was produced using immobilized lipase. The lipase enzyme was immobilized on chitosan beads, activated chitosan beads by glutaraldehyde, and Amberlite XAD7. In order to find an appropriate support for the hydrolysis reaction of racemic naproxen methyl ester, the conversion and enantioselectivity for all carriers were compared. In addition, effects of the volumetric ratio of two phases in different organic solvents, addition of cosolvent and surfactant, optimum pH and temperature, reusability, and inhibitory effect of methanol were investigated. The optimum volumetric ratio of two phases was defined as 3:2 of aqueous phase to organic phase. Various water miscible and water immiscible solvents were examined. Finally, isooctane was chosen as an organic solvent, while 2-ethoxyethanol was added as a cosolvent in the organic phase of the reaction mixture. The optimum reaction conditions were determined to be 35 °C, pH 7, and 24 h. Addition of Tween-80 in the organic phase increased the accessibility of immobilized enzyme to the reactant. The optimum organic phase compositions using a volumetric ratio of 2-ethoxyethanol, isooctane and Tween-80 were 3:7 and 0.1% (v/v/v), respectively. The best conversion and enantioselectivity of immobilized enzyme using chitosan beads activated by glutaraldehyde were 0.45 and 185, respectively. © 2017 Wiley Periodicals, Inc.

Effects of aggregation on the excitation dynamics of LH2 from Thermochromatium tepidum in aqueous phase and in chromatophores.

PubMed

Yang, Fan; Yu, Long-Jiang; Wang, Peng; Ai, Xi-Cheng; Wang, Zheng-Yu; Zhang, Jian-Ping

2011-06-23

We carried out femtosecond magic-angle and polarized pump-probe spectroscopies for the light-harvesting complex 2 (LH2) from Thermochromatium (Tch.) tepidum in aqueous phase and in chromatophores. To examine the effects of LH2 aggregation on the dynamics of excitation energy transfer, dominant monodispersed and aggregated LH2s were prepared by controlling the surfactant concentrations. The aqueous preparations solubilized with different concentrations of n-dodecyl-β-D-maltoside (DDM) show similar visible-to-near-infrared absorption spectra, but distinctively different aggregation states, as revealed by using dynamic light scattering. The B800 → B850 intra-LH2 energy transfer time was determined to be 1.3 ps for isolated LH2, which, upon aggregation in aqueous phase or clustering in chromatophores, shortened to 1.1 or 0.9 ps, respectively. The light-harvesting complex 1 (LH1) of this thermophilic purple sulfur bacterium contains bacteriochlorophyll a absorbing at 915 nm (B915), and the LH2(B850) → LH1(B915) intercomplex transfer time in chromatophores was found to be 6.6 ps. For chromatophores, a depolarization time of 21 ps was derived from the anisotropy kinetics of B850*, which is attributed to the migration of B850* excitation before being trapped by LH1. In addition, the B850* annihilation is accelerated upon LH2 aggregation in aqueous phase, but it is much less severe upon LH2 clustering in the intracytoplasmic membrane. These results are helpful in understanding the light-harvesting function of a bacterial photosynthetic membrane incorporating different types of antenna complexes.

Theoretical Evidence for the Stronger Ability of Thymine to Disperse SWCNT than Cytosine and Adenine: self-stacking of DNA bases vs their cross-stacking with SWCNT

PubMed Central

Wang, Yixuan

2008-01-01

Self-stacking of four DNA bases, adenine (A), cytosine (C), guanine (G) and thymine (T), and their cross-stacking with (5,5) as well as (10,0) single walled carbon nanotubes (SWCNTs) were extensively investigated with a novel hybrid DFT method, MPWB1K/cc-pVDZ. The binding energies were further corrected with MP2/6-311++G(d,p) method in both gas phase and aqueous solution, where the solvent effects were included with conductor-like polarized continuum model (CPCM) model and UAHF radii. The strongest self-stacking of G and A takes displaced anti-parallel configuration, but un-displaced or “eclipsed” anti-parallel configuration is the most stable for C and T. In gas phase the self-stacking of nucleobases decreases in the sequence G>A>C>T, while because of quite different solvent effects their self-stacking in aqueous solution exhibits a distinct sequence A>G>T>C. For a given base, cross-stacking is stronger than self-stacking in both gas phase and aqueous solution. Binding energy for cross-stacking in gas phase varies as G>A>T>C for both (10,0) and (5,5) SWCNTs, and the binding of four nucleobases to (10,0) is slightly stronger than to (5,5) SWCNT by a range of 0.1–0.5 kcal/mol. The cross-stacking in aqueous solution varies differently from that gas phase: A>G>T>C for (10,0) SWCNT and G>A>T>C for (5,5) SWCNT. It is suggested that the ability of nucleobases to disperse SWCNT depends on relative strength (ΔΔEbinsol) of self-stacking and cross-stacking with SWCNT in aqueous solution. Of the four investigated nucleobases thymine (T) exhibits the highest (ΔΔEbinsol) which can well explain the experimental finding that T more efficiently functionalizes SWCNT than C and A. PMID:18946514

Study of the Solvent Extraction of V(V) from Nitrate Medium by Tri- n-Octylamine Dissolved in Kerosene

NASA Astrophysics Data System (ADS)

Biswas, Ranjit Kumar; Karmakar, Aneek Krishna; Mottakin, Mohammad

2017-10-01

The liquid-liquid extraction of V(V) from a nitrate medium by tri- n-Octylamine [( n-C8H17)3N; abbreviated as TOA] dissolved in distilled colorless kerosene has been investigated as a function of various experimental parameters. The equilibration time is less than 10 min. It is observed that the extraction ratio increases with increasing [V(V)] in the aqueous phase, which is possibly a result of the formation of V10O26(OH) 2 4- (via reaction: 10 VO2 + + 8 H2O → V10O26(OH) 2 4- + 14 H+) with increasing concentration in the aqueous phase. The nature of the species extracted into the organic phase depends on the existing aqueous species prevailing at a certain pH. At lower pH values, the extraction of VO2 + occurs via cation (H+) exchange of (C8H17)3NHNO3. On the other hand, at higher pH values, anionic V(V) species such as V10O26(OH) 2 4- , V10O27(OH)5-, V10O28 6- etc. are extracted by solvated ion-pair formation mechanism. The TOA concentration dependence varies from 2 at a lower pH region ( 2.3) to 1 at a higher pH region ( 5.7). The extraction is also found to be favored by a rise of nitrate concentration in the aqueous phase. Temperature has a pronounced effect with Δ H < -58 kJ/mol. Kerosene is demonstrated as the best diluent for this system. Increased organic to aqueous phase volume ratio (O/A) enhances extraction ratio. The extracted species can be stripped by 0.75 mol/L NH4OH solution to the extent of 72% in a single stage. But stage-wise stripping is not so effective. It is observed a very high loading, of the order of 2.3 mol V(V) per mol TOA.

Determination of ammonium in aqueous samples using new headspace dynamic in-syringe liquid-phase microextraction with in situ derivitazation coupled with liquid chromatography-fluorescence detection.

PubMed

Muniraj, Sarangapani; Yan, Cheing-Tong; Shih, Hou-Kung; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

2012-11-19

A new simultaneous derivatization and extraction method for the preconcentration of ammonia using new one-step headspace dynamic in-syringe liquid-phase microextraction with in situ derivatization was developed for the trace determination of ammonium in aqueous samples by liquid chromatography with fluorescence detection (LC-FLD). The acceptor phase (as derivatization reagent) containing o-phthaldehyde and sodium sulfite was held within a syringe barrel and immersed in the headspace of sample container. The gaseous ammonia from the alkalized aqueous sample formed a stable isoindole derivative with the acceptor phase inside the syringe barrel through the reciprocated movements of plunger. After derivatization-cum-extraction, the acceptor phase was directly injected into LC-FLD for analysis. Parameters affecting the ammonia evolution and the extraction/derivatization efficiency such as sample matrix, pH, temperature, sampling time, and the composition of derivatization reagent, reaction temperature, and frequency of reciprocated plunger, were studied thoroughly. Results indicated that the maximum extraction efficiency was obtained by using 100μL derivatization reagent in a 1-mL gastight syringe under 8 reciprocated movements of plunger per min to extract ammonia evolved from a 20mL alkalized aqueous solution at 70°C (preheated 4min) with 380rpm stirring for 8min. The detection was linear in the concentration range of 0.625-10μM with the correlation coefficient of 0.9967 and detection limit of 0.33μM (5.6ng mL(-1)) based on SN(-1)=3. The method was applied successfully to determine ammonium in real water samples without any prior cleanup of the samples, and has been proved to be a simple, sensitive, efficient and cost-effective procedure for trace ammonium determination in aqueous samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Organic aerogel microspheres

DOEpatents

Mayer, S.T.; Kong, F.M.; Pekala, R.W.; Kaschmitter, J.L.

1999-06-01

Organic aerogel microspheres are disclosed which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonstick gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Organic aerogel microspheres

DOEpatents

Mayer, Steven T.; Kong, Fung-Ming; Pekala, Richard W.; Kaschmitter, James L.

1999-01-01

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Organic aerogel microspheres and fabrication method therefor

DOEpatents

Mayer, S.T.; Kong, F.M.; Pekala, R.W.; Kaschmitter, J.L.

1996-04-16

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Organic aerogel microspheres and fabrication method therefor

DOEpatents

Mayer, Steven T.; Kong, Fung-Ming; Pekala, Richard W.; Kaschmitter, James L.

1996-01-01

Organic aerogel microspheres which can be used in capacitors, batteries, thermal insulation, adsorption/filtration media, and chromatographic packings, having diameters ranging from about 1 micron to about 3 mm. The microspheres can be pyrolyzed to form carbon aerogel microspheres. This method involves stirring the aqueous organic phase in mineral oil at elevated temperature until the dispersed organic phase polymerizes and forms nonsticky gel spheres. The size of the microspheres depends on the collision rate of the liquid droplets and the reaction rate of the monomers from which the aqueous solution is formed. The collision rate is governed by the volume ratio of the aqueous solution to the mineral oil and the shear rate, while the reaction rate is governed by the chemical formulation and the curing temperature.

Investigations of kinetics and mechanism of chloropinnoite in boric acid aqueous solution at 303 K by Raman spectroscopy.

PubMed

Xiaoping, Li; Shiyang, Gao; Shuping, Xia

2004-10-01

Raman spectroscopy of dissolution and transformation of chloropinnoite in 4.5% (wt.%) boric acid aqueous solution at 303 K has been recorded. The Raman spectra of kinetics process have been obtained. The phase transformation product is 2MgO.3B2O3.15H2O (kurnakovite). The main polyborate anions and their interaction in aqueous solution have been proposed according to the Raman spectrum. Some assignments were tentatively given and the relations between the existing forms of polyborate anions and the crystallizing solid phases have been gained. A mechanism of dissolution and crystallization reactions and the formation condition of kurnakovite in Qinghai-Tibet plateau were proposed and discussed.

Metal separations using aqueous biphasic partitioning systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaiko, D.J.; Zaslavsky, B.; Rollins, A.N.

1996-05-01

Aqueous biphasic extraction (ABE) processes offer the potential for low-cost, highly selective separations. This countercurrent extraction technique involves selective partitioning of either dissolved solutes or ultrafine particulates between two immiscible aqueous phases. The extraction systems that the authors have studied are generated by combining an aqueous salt solution with an aqueous polymer solution. They have examined a wide range of applications for ABE, including the treatment of solid and liquid nuclear wastes, decontamination of soils, and processing of mineral ores. They have also conducted fundamental studies of solution microstructure using small angle neutron scattering (SANS). In this report they reviewmore » the physicochemical fundamentals of aqueous biphase formation and discuss the development and scaleup of ABE processes for environmental remediation.« less

Dynamic Mass Transfer of Hemoglobin at the Aqueous/Ionic-Liquid Interface Monitored with Liquid Core Optical Waveguide.

PubMed

Chen, Xuwei; Yang, Xu; Zeng, Wanying; Wang, Jianhua

2015-08-04

Protein transfer from aqueous medium into ionic liquid is an important approach for the isolation of proteins of interest from complex biological samples. We hereby report a solid-cladding/liquid-core/liquid-cladding sandwich optical waveguide system for the purpose of monitoring the dynamic mass-transfer behaviors of hemoglobin (Hb) at the aqueous/ionic liquid interface. The optical waveguide system is fabricated by using a hydrophobic IL (1,3-dibutylimidazolium hexafluorophosphate, BBimPF6) as the core, and protein solution as one of the cladding layer. UV-vis spectra are recorded with a CCD spectrophotometer via optical fibers. The recorded spectra suggest that the mass transfer of Hb molecules between the aqueous and ionic liquid media involve accumulation of Hb on the aqueous/IL interface followed by dynamic extraction/transfer of Hb into the ionic liquid phase. A part of Hb molecules remain at the interface even after the accomplishment of the extraction/transfer process. Further investigations indicate that the mass transfer of Hb from aqueous medium into the ionic liquid phase is mainly driven by the coordination interaction between heme group of Hb and the cationic moiety of ionic liquid, for example, imidazolium cation in this particular case. In addition, hydrophobic interactions also contribute to the transfer of Hb.

The redox chemistry of neptunium in γ-irradiated aqueous nitric acid in the presence of an organic phase

DOE PAGES

Mincher, Bruce J.; Precek, Martin; Paulenova, Alena

2015-10-17

The radiolytic changes in oxidation state for solutions of initially Np(V) and/or Np(VI) were investigated by gamma-irradiation in conjunction with UV/Vis spectroscopy of the aqueous phase. Samples were irradiated in varying concentrations of nitric acid, and with or without the presence of 30% TBP in dodecane. At short irradiation times Np(V) was oxidized to Np(VI), even in the presence of the organic phase. Upon the radiolytic production of sufficient amounts of nitrous acid, reduction of Np(VI) to Np(V) occurred in both phases. This was accompanied by stripping of the previously extracted Np(VI). Nitric acid concentrations of 6 M mitigated thismore » reduction.« less

The redox chemistry of neptunium in γ-irradiated aqueous nitric acid in the presence of an organic phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mincher, Bruce J.; Precek, Martin; Paulenova, Alena

The radiolytic changes in oxidation state for solutions of initially Np(V) and/or Np(VI) were investigated by gamma-irradiation in conjunction with UV/Vis spectroscopy of the aqueous phase. Samples were irradiated in varying concentrations of nitric acid, and with or without the presence of 30% TBP in dodecane. At short irradiation times Np(V) was oxidized to Np(VI), even in the presence of the organic phase. Upon the radiolytic production of sufficient amounts of nitrous acid, reduction of Np(VI) to Np(V) occurred in both phases. This was accompanied by stripping of the previously extracted Np(VI). Nitric acid concentrations of 6 M mitigated thismore » reduction.« less

Evaluation of the Determination of Free Urea in Water-Soluble Liquid Fertilizers Containing Urea and Ureaforms by Urease and HPLC Methods.

PubMed

Hojjatie, Michael M; Abrams, Dean

2015-01-01

Currently there are three AOAC Official Methods for the determination of urea in fertilizers. AOAC Official Method 959.03, Urea in Fertilizers, Urease Method, First Action 1959, Final Action 1960, is based on the use of fresh commercial 1% urease solution, or preparation of such solution from urease powder in water, or from jack bean meal in water. AOAC Official Method 983.01, Urea and Methyleneureas (Water-Soluble) in Fertilizers, First Action 1983, Final Action 1984, is based on LC with a refractive index detector using water as the mobile phase and a C18 column. AOAC Official Method 2003.14, Determination of Urea in Water- Soluble Urea-Formaldehyde Fertilizer Products and in Aqueous Urea Solutions, First Action 2003, Final Action 2008, is based on LC with a UV detector using acetonitrile-water (85+15, v/v) mobile phase and a propylamine column. The urea method, AOAC Official Method 959.03, is very much dependent on the nature of the urease enzyme. The method was developed in 1960 and used for simple urea fertilizer solutions. With the advent of complex fertilizer compositions, especially with the class of liquid triazone fertilizers and water-soluble urea forms, the analyses of free urea in these fertilizers by the urease method is often inaccurate and inconsistent. AOAC Official Method 983.01 is not always reliable due to the interference of some of the components of these fertilizers, and due to the fact that the use of water as the mobile phase does not always separate the free urea from other components. AOAC Official Method 2003.14 was subjected to ring test studies that showed it could be used for the determination of "free urea" in these classes of fertilizers with good accuracy and precision.

Headspace and direct immersion solid phase microextraction procedures for selenite determination in urine, saliva and milk by gas chromatography mass spectrometry.

PubMed

Kapsimali, D C; Zachariadis, G A

2009-10-01

Two solid phase microextraction modes were investigated and compared for their performance on the determination of selenites in various biological liquids like human urine and saliva and various types of milk. Using sodium tetraethylborate (NaBEt(4)) as ethylating reagent, selenites are converted in situ to volatile diethylselenides (DESe) in aqueous medium. The derivative is collected in situ by solid phase microextraction (SPME) using a silica fiber coated with poly(dimethylsiloxane) (PDMS) either from the headspace (HS-SPME) or directly from the liquid phase (LP-SPME) and finally determined by capillary GC/MS. Under optimum conditions of SPME, the GC separation was also optimized. Between the two examined microextraction techniques, direct immersion of the PDMS fiber in the liquid phase was proved less satisfactory. In contrast, the headspace procedure appears to be more efficient. The quantification of selenites was achieved in SIM mode with good analytical performance. A non-fat milk powder certified reference material was analyzed to evaluate the accuracy of the method. The overall precision of the method was ranged between 6.2% and 9.7%. Detection limits achieved were 0.05microgL(-1) for human urine, 0.08microgL(-1) for saliva and 0.03-0.06microgL(-1) in various milk matrices.

Negative/positive chemotaxis of a droplet: Dynamic response to a stimulant gas

NASA Astrophysics Data System (ADS)

Sakuta, Hiroki; Magome, Nobuyuki; Mori, Yoshihito; Yoshikawa, Kenichi

2016-05-01

We report here the repulsive/attractive motion of an oil droplet floating on an aqueous phase caused by the application of a stimulant gas. A cm-sized droplet of oleic acid is repelled by ammonia vapor. In contrast, a droplet of aniline on an aqueous phase moves toward hydrochloric acid as a stimulant. The mechanisms of these characteristic behaviors of oil droplets are discussed in terms of the spatial gradient of the interfacial tension caused by the stimulant gas.

Non-aqueous solution preparation of doped and undoped Li{sub x}Mn{sub y}O{sub z}

DOEpatents

Boyle, T.J.; Voigt, J.A.

1997-05-20

A method is described for generation of phase-pure doped and undoped Li{sub x}Mn{sub y}O{sub z} precursors. The method of this invention uses organic solutions instead of aqueous solutions or nonsolution ball milling of dry powders to produce phase-pure precursors. These precursors can be used as cathodes for lithium-polymer electrolyte batteries. Dopants may be homogeneously incorporated to alter the characteristics of the powder. 1 fig.

Selective Extraction of Uranium from Liquid or Supercritical Carbon Dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farawila, Anne F.; O'Hara, Matthew J.; Wai, Chien M.

2012-07-31

Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc -CO2) system was designed tomore » mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc -CO2 and are capable of extracting uranium directly from UO2, UO3 and U3O8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO3 loaded Sc-CO2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercritical fluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc -CO2 pressure and temperature, TBP/HNO3 complex used, reductant or complexant used for selectivity, and ionic liquids used as supportive media. To complete the extraction and recovery cycle, we then demonstrate uranium back extraction from the TBP loaded sc-CO2 phase into an aqueous phase and the characterization of the uranium complex formed at the end of this process. Another aspect of this project was to limit proliferation risks by either co-extracting uranium and plutonium, or by leaving plutonium behind by selectively extracting uranium. We report that the former is easily achieved, since plutonium is in the tetravalent or hexavalent oxidation state in the oxidizing environment created by the TBP-nitric acid complex, and is therefore co-extracted. The latter is more challenging, as a reductant or complexant to plutonium has to be used to selectively extract uranium. After undertaking experiments on different reducing or complexing systems (e.g., AcetoHydroxamic Acid (AHA), Fe(II), ascorbic acid), oxalic acid was chosen as it can complex tetravalent actinides (Pu, Np, Th) in the aqueous phase while allowing the extraction of hexavalent uranium in the sc-CO2 phase. Finally, we show results using an alternative media to commonly used aqueous phases: ionic liquids. We show the dissolution of uranium in ionic liquids and its extraction using sc-CO2 with and without the presence of AHA. The possible separation of trivalent actinides from uranium is also demonstrated in ionic liquids using neodymium as a surrogate and diglycolamides as the extractant.« less

NAPL: SIMULATOR DOCUMENTATION

EPA Science Inventory

A mathematical and numerical model is developed to simulate the transport and fate of NAPLs (Non-Aqueous Phase Liquids) in near-surface granular soils. The resulting three-dimensional, three phase simulator is called NAPL. The simulator accommodates three mobile phases: water, NA...

Molar mass fractionation in aqueous two-phase polymer solutions of dextran and poly(ethylene glycol).

PubMed

Zhao, Ziliang; Li, Qi; Ji, Xiangling; Dimova, Rumiana; Lipowsky, Reinhard; Liu, Yonggang

2016-06-24

Dextran and poly(ethylene glycol) (PEG) in phase separated aqueous two-phase systems (ATPSs) of these two polymers, with a broad molar mass distribution for dextran and a narrow molar mass distribution for PEG, were separated and quantified by gel permeation chromatography (GPC). Tie lines constructed by GPC method are in excellent agreement with those established by the previously reported approach based on density measurements of the phases. The fractionation of dextran during phase separation of ATPS leads to the redistribution of dextran of different chain lengths between the two phases. The degree of fractionation for dextran decays exponentially as a function of chain length. The average separation parameters, for both dextran and PEG, show a crossover from mean field behavior to Ising model behavior, as the critical point is approached. Copyright © 2016 Elsevier B.V. All rights reserved.

Demixing of aqueous polymer two-phase systems in low gravity

NASA Technical Reports Server (NTRS)

Bamberger, S.; Harris, J. M.; Baird, J. K.; Boyce, J.; Vanalstine, J. M.; Snyder, R. S.; Brooks, D. E.

1986-01-01

When polymers such as dextran and poly(ethylene glycol) are mixed in aqueous solution biphasic systems often form. On Earth the emulsion formed by mixing the phases rapidly demixes because of phase density differences. Biological materials can be purified by selective partitioning between the phases. In the case of cells and other particulates the efficiency of these separations appears to be somewhat compromised by the demixing process. To modify this process and to evaluate the potential of two-phase partitioning in space, experiments on the effects of gravity on phase emulsion demixing were undertaken. The behavior of phase systems with essentially identical phase densities was studied at one-g and during low-g parabolic aircraft maneuvers. The results indicate the demixing can occur rather rapidly in space, although more slowly than on Earth. The demixing process was examined from a theoretical standpoint by applying the theory of Ostwald ripening. This theory predicts demizing rates many orders of magnitude lower than observed. Other possible demixing mechanisms are considered.

Metal-Catalyzed Aqueous Oxidation Processes in Merged Microdroplets

NASA Astrophysics Data System (ADS)

Davis, R. D.; Wilson, K. R.

2017-12-01

Iron-catalyzed production of reactive oxygen species (ROS) from hydrogen peroxide (Fenton's reaction) is a fundamental process throughout nature, from groundwater to cloud droplets. In recent years, Fenton's chemistry has gained further interest in atmospheric science as a potentially important process in the oxidation of aqueous secondary organic aerosol (e.g., Chu et al., Sci. Rep., 2017), with some observations indicating that Fenton's reaction proceeds at a higher rate at aerosol interfaces compared to in the bulk (Enami et al., PNAS, 2014). However, a fundamental-level mechanistic understanding of this process remains elusive and the relative importance of interfacial versus bulk chemistry for aqueous organic processing via Fenton's has yet to be fully established. Here, we present a microreactor experimental approach to studying aqueous-phase Fenton's chemistry in microdroplets by rapidly mixing droplets of different composition. Utilizing two on-demand droplet generators, a stream of microdroplets containing aqueous iron chloride were merged with a separate stream of microdroplets containing aqueous hydrogen peroxide and a range of aromatic organic compounds, initiating ROS production and subsequent aqueous-phase oxidation reactions. Upon merging, mixing of the microdroplets occurred in submillisecond timescales, thus allowing the reaction progress to be monitored with high spatial and temporal resolution. For relatively large microreactor (droplet) sizes (50 µm diameter post-merging), the Fenton-initiated aqueous oxidation of aromatic organic compounds in merged microdroplets was consistent with bulk predictions with hydroxyl radicals as the ROS. The microdroplet-size dependence of this observation, along with the role of other ROS species produced from Fenton and Fenton-like processes, will be discussed in the context of relative importance to aqueous organic processing of atmospheric particles.

Design of Heterogeneous Hoveyda-Grubbs Second-Generation Catalyst-Lipase Conjugates.

PubMed

Neville, Anthony; Iniesta, Javier; Palomo, Jose M

2016-12-06

Heterogeneous catalysts have been synthesi zed by the conjugation of Hoveyda-Grubbs second-generation catalyst with a lipase. The catalytic properties of the organometallic compound in solution were firstly optimized, evaluating the activity of Ru in the ring-closing metathesis of diethyldiallymalonate at 25 °C at different solvents and in the presence of different additives. The best result was found using tetrahydrofuran as a solvent. Some additives such as phenylboronic acid or polyetheneglycol slightly improved the activity of the Ru catalyst whereas others, such as pyridine or dipeptides affected it negatively. The organometallic compound immobilized on functionalized-surface materials activated with boronic acid or epoxy groups (around 50-60 µg per mg support) and showed 50% conversion at 24 h in the ring-closing metathesis. Cross-linked enzyme aggregates (CLEA's) of the Hoveyda-Grubbs second-generation catalyst with Candida antarctica lipase (CAL-B) were prepared, although low Ru catalyst was found to be translated in low conversion. Therefore, a sol-gel preparation of the Hoveyda-Grubbs second-generation and CAL-B was performed. This catalyst exhibited good activity in the metathesis of diethyldiallymalonate in toluene and in aqueous media. Finally, a new sustainable approach was used by the conjugation lipase-Grubbs in solid phase in aqueous media. Two strategies were used: one using lipase previously covalently immobilized on an epoxy-Sepharose support (hydrophilic matrix) and then conjugated with grubbs; and in the second, the free lipase was incubated with organometallic in aqueous solution and then immobilized on epoxy-Sepharose. The different catalysts showed excellent conversion values in the ring-closing metathesis of diethyldiallymalonate in aqueous media at 25 °C.

Application of dual-cloud point extraction for the trace levels of copper in serum of different viral hepatitis patients by flame atomic absorption spectrometry: a multivariate study.

PubMed

Arain, Salma Aslam; Kazi, Tasneem G; Afridi, Hassan Imran; Abbasi, Abdul Rasool; Panhwar, Abdul Haleem; Naeemullah; Shanker, Bhawani; Arain, Mohammad Balal

2014-12-10

An efficient, innovative preconcentration method, dual-cloud point extraction (d-CPE) has been developed for the extraction and preconcentration of copper (Cu(2+)) in serum samples of different viral hepatitis patients prior to couple with flame atomic absorption spectrometry (FAAS). The d-CPE procedure was based on forming complexes of elemental ions with complexing reagent 1-(2-pyridylazo)-2-naphthol (PAN), and subsequent entrapping the complexes in nonionic surfactant (Triton X-114). Then the surfactant rich phase containing the metal complexes was treated with aqueous nitric acid solution, and metal ions were back extracted into the aqueous phase, as second cloud point extraction stage, and finally determined by flame atomic absorption spectrometry using conventional nebulization. The multivariate strategy was applied to estimate the optimum values of experimental variables for the recovery of Cu(2+) using d-CPE. In optimum experimental conditions, the limit of detection and the enrichment factor were 0.046μgL(-1) and 78, respectively. The validity and accuracy of proposed method were checked by analysis of Cu(2+) in certified sample of serum (CRM) by d-CPE and conventional CPE procedure on same CRM. The proposed method was successfully applied to the determination of Cu(2+) in serum samples of different viral hepatitis patients and healthy controls. Copyright © 2014 Elsevier B.V. All rights reserved.

Lipophilic oligonucleotides spontaneously insert into lipid membranes, bind complementary DNA strands, and sequester into lipid-disordered domains.

PubMed

Bunge, Andreas; Kurz, Anke; Windeck, Anne-Kathrin; Korte, Thomas; Flasche, Wolfgang; Liebscher, Jürgen; Herrmann, Andreas; Huster, Daniel

2007-04-10

For the development of surface functionalized bilayers, we have synthesized lipophilic oligonucleotides to combine the molecular recognition mechanism of nucleic acids and the self-assembly characteristics of lipids in planar membranes. A lipophilic oligonucleotide consisting of 21 thymidine units and two lipophilic nucleotides with an alpha-tocopherol moiety as a lipophilic anchor was synthesized using solid-phase methods with a phosphoramadite strategy. The interaction of the water soluble lipophilic oligonucleotide with vesicular lipid membranes and its capability to bind complementary DNA strands was studied using complementary methods such as NMR, EPR, DSC, fluorescence spectroscopy, and fluorescence microscopy. This oligonucleotide inserted stably into preformed membranes from the aqueous phase. Thereby, no significant perturbation of the lipid bilayer and its stability was observed. However, the non-lipidated end of the oligonucleotide is exposed to the aqueous environment, is relatively mobile, and is free to interact with complementary DNA strands. Binding of the complementary single-stranded DNA molecules is fast and accomplished by the formation of Watson-Crick base pairs, which was confirmed by 1H NMR chemical shift analysis and fluorescence resonance energy transfer. The molecular structure of the membrane bound DNA double helix is very similar to the free double-stranded DNA. Further, the membrane bound DNA double strands also undergo regular melting. Finally, in raft-like membrane mixtures, the lipophilic oligonucleotide was shown to preferentially sequester into liquid-disordered membrane domains.

Synthesis of CO2/N2-triggered reversible stability-controllable poly(2-(diethylamino)ethyl methacrylate)-grafted-AuNPs by surface-initiated atom transfer radical polymerization.

PubMed

Kitayama, Yukiya; Takeuchi, Toshifumi

2014-10-28

CO2/N2-triggered stability-controllable gold nanoparticles (AuNPs) grafted with poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) layers (PDEAEMA-g-AuNPs) were synthesized by the surface-initiated atom transfer radical polymerization of DEAEMA with AuNPs bearing the bis[2-(2-bromoisobutyryloxy)undecyl] layer (grafting from method). Extension of the PDEAEMA chain length increased the stability of the PDEAEMA-g-AuNPs in CO2-bubbled water because of the electrosteric repulsion of the protonated PDEAEMA layer. The chain-length-dependent stability of PDEAEMA-g-AuNPs was confirmed by DLS and UV-vis spectra by using the localized surface plasmon resonance property of the AuNPs, where the extinction wavelength was shifted toward shorter wavelength with increasing PDEAEMA chain length. The reversible stability change with the gas stimuli of CO2/N2 was also successfully demonstrated. Finally, the transfer across the immiscible interface between water and organic solvent was successfully demonstrated by N2-triggered insolubilization of PDEAEMA layer on AuNPs in the aqueous phase, leading to the successful collection of AuNPs using organic solvent from the aqueous phase. Our "grafting from" method of reversible stability-controllable AuNPs can be applied to develop advanced materials such as reusable optical AuNP-based nanosensors because the molecular recognition layer can be constructed by two-step polymerization.

Review of unsaturated-zone transport and attenuation of volatile organic compound (VOC) plumes leached from shallow source zones

NASA Astrophysics Data System (ADS)

Rivett, Michael O.; Wealthall, Gary P.; Dearden, Rachel A.; McAlary, Todd A.

2011-04-01

Reliable prediction of the unsaturated zone transport and attenuation of dissolved-phase VOC (volatile organic compound) plumes leached from shallow source zones is a complex, multi-process, environmental problem. It is an important problem as sources, which include solid-waste landfills, aqueous-phase liquid discharge lagoons and NAPL releases partially penetrating the unsaturated zone, may persist for decades. Natural attenuation processes operating in the unsaturated zone that, uniquely for VOCs includes volatilisation, may, however, serve to protect underlying groundwater and potentially reduce the need for expensive remedial actions. Review of the literature indicates that only a few studies have focused upon the overall leached VOC source and plume scenario as a whole. These are mostly modelling studies that often involve high strength, non-aqueous phase liquid (NAPL) sources for which density-induced and diffusive vapour transport is significant. Occasional dissolved-phase aromatic hydrocarbon controlled infiltration field studies also exist. Despite this lack of focus on the overall problem, a wide range of process-based unsaturated zone — VOC research has been conducted that may be collated to build good conceptual model understanding of the scenario, particularly for the much studied aromatic hydrocarbons and chlorinated aliphatic hydrocarbons (CAHs). In general, the former group is likely to be attenuated in the unsaturated zone due to their ready aerobic biodegradation, albeit with rate variability across the literature, whereas the fate of the latter is far less likely to be dominated by a single mechanism and dependent upon the relative importance of the various attenuation processes within individual site — VOC scenarios. Analytical and numerical modelling tools permit effective process representation of the whole scenario, albeit with potential for inclusion of additional processes — e.g., multi-mechanistic sorption phase partitioning, and provide good opportunity for further sensitivity analysis and development to practitioner use. There remains a significant need to obtain intermediate laboratory-scale and particularly field-scale (actual site and controlled release) datasets that address the scenario as a whole and permit validation of the available models. Integrated assessment of the range of simultaneous processes that combine to influence leached plume generation, transport and attenuation in the unsaturated zone is required. Component process research needs are required across the problem scenario and include: the simultaneous volatilisation and dissolution of source zones; development of appropriate field-scale dispersion estimates for the unsaturated zone; assessment of transient VOC exchanges between aqueous, vapour and sorbed phases and their influence upon plume attenuation; development of improved field methods to recognise and quantify biodegradation of CAHs; establishment of the influence of co-contaminants; and, finally, translation of research findings into more robust practitioner practice.

Laboratory studies of the low-temperature deliquescence of calcium chloride salts: Relevance to aqueous solutions on Mars and in the Antarctic Dry Valleys

NASA Astrophysics Data System (ADS)

Gough, R. V.; Chevrier, V.; Tolbert, M. A.

2013-12-01

There is significant interest in the possible existence of liquid water on current Mars. This water would likely exist as a brine in order to be stable on Mars today. It has been proposed that soil salts could form aqueous solutions through either the melting of ice by low-eutectic salts, or by the deliquescence of hygroscopic salts present in the Martian soil. The focus thus far has largely been on perchlorate species, which can melt ice at temperatures as low as 206 K and can deliquesce at relative humidity values as low as 38% RH. A Mars-relevant salt that has been neglected thus far is calcium chloride (CaCl2). Calcium has been reported to be an abundant cation at the Phoenix landing site and Mars Science Laboratory instruments have recently identified calcium as well. Simulations suggest subsurface CaCl2 is an ideal candidate to produce brines with seasonality consistent with observed recurring slope lineae (RSL) (Chevrier et al., 2012). Finally, the only terrestrial site where RSL-like features have been observed (near Don Juan Pond in the Antarctic Dry Valleys) contains abundant CaCl2. These seasonal slope streaks are thought to form when CaCl2 in the soil deliquesces due to contact with atmospheric water vapor (Dickson et al., 2013). It is important to understand how this CaCl2 interacts with water vapor at low temperatures relevant to Mars and the Martian analog sites. Here we use a Raman microscope and environmental cell to monitor the low-temperature (223 - 273 K) deliquescence (solid to aqueous phase transition) and efflorescence (aqueous to solid phase transition) of three hydration states of CaCl2 (dihydrate, tetrahydrate, hexahydrate). We have found that the deliquescence relative humidity (DRH) increases with increasing hydration state, which is an expected result. Average DRH values over the temperature range studied are 20.0 × 2.6% RH for the dihydrate, 31.8 × 6.3% RH for the tetrahydrate and 60.7 × 1.6% RH for the hexahydrate. Once the aqueous solution has formed, efflorescence (recrystallization) of the salt is kinetically hindered and supersaturated solutions can exist at humidities far below the DRH. Regardless of temperature or initial hydration state of the solid salt, we do not observe efflorescence of the aqueous solutions to occur until single digit RH values are reached. We show here that calcium chloride is at least as deliquescent as many perchlorate salts, and that solutions of calcium chloride are even more difficult to recrystallize once a brine solution has formed. These experimental results will assist with interpretation of observations of deliquescence in the Antarctic Dry Valleys and will help us understand potential liquid water formation on Mars. In addition to formation of brines through melting, deliquescence of salts such as CaCl2 is a reasonable mechanism for formation of aqueous solutions on current Mars.

Development of sodium acetate trihydrate-ethylene glycol composite phase change materials with enhanced thermophysical properties for thermal comfort and therapeutic applications.

PubMed

Kumar, Rohitash; Vyas, Sumita; Kumar, Ravindra; Dixit, Ambesh

2017-07-12

The heat packs using phase change materials (PCMs) are designed for possible applications such as body comfort and medical applications under adverse situations. The development and performance of such heat packs rely on thermophysical properties of PCMs such as latent heat, suitable heat releasing temperature, degree of supercooling, effective heat releasing time, crystallite size, stability against spontaneous nucleation in metastable supercooled liquid state and thermal stability during heating and cooling cycles. Such PCMs are rare and the available PCMs do not exhibit such properties simultaneously to meet the desired requirements. The present work reports a facile approach for the design and development of ethylene glycol (EG) and aqueous sodium acetate trihydrate (SAT) based composite phase change materials, showing these properties simultaneously. The addition of 2-3 wt% EG in aqueous SAT enhances the softness of SAT crystallites, its degree of supercooling and most importantly the effective heat releasing time by ~10% with respect to aqueous SAT material. In addition, the maximum heat releasing temperature of aqueous SAT has been tailored from 56.5 °C to 55 °C, 54.9 °C, 53.5 °C, 51.8 °C and 43.2 °C using 2%, 3%, 5%, 7% and 10 wt% EG respectively, making the aqueous SAT-EG composite PCMs suitable for desired thermal applications.

Adsorption of water from aqueous acetonitrile on silica-based stationary phases in aqueous normal-phase liquid chromatography.

PubMed

Soukup, Jan; Jandera, Pavel

2014-12-29

Excess adsorption of water from aqueous acetonitrile mobile phases was investigated on 16 stationary phases using the frontal analysis method and coulometric Karl-Fischer titration. The stationary phases include silica gel and silica-bonded phases with different polarities, octadecyl and cholesterol, phenyl, nitrile, pentafluorophenylpropyl, diol and zwitterionic sulfobetaine and phosphorylcholine ligands bonded on silica, hybrid organic-silica and hydrosilated matrices. Both fully porous and core-shell column types were included. Preferential uptake of water by the columns can be described by Langmuir isotherms. Even though a diffuse rather than a compact adsorbed discrete layer of water on the adsorbent surface can be formed because of the unlimited miscibility of water with acetonitrile, for convenience, the preferentially adsorbed water was expressed in terms of a hypothetical monomolecular water layer equivalent in the inner pores. The uptake of water strongly depends on the polarity and type of the column. Less than one monomolecular water layer equivalent was adsorbed on moderate polar silica hydride-based stationary phases, Ascentis Express F5 and Ascentis Express CN column at the saturation capacity, while on more polar stationary phases, several water layer equivalents were up-taken from the mobile phase. The strongest affinity to water was observed on the ZIC cHILIC stationary phases, where more than nine water layer equivalents were adsorbed onto its surface at its saturation capacity. Columns with bonded hydroxyl and diol ligands show stronger water adsorption in comparison to bare silica. Columns based on hydrosilated silica generally show significantly decreased water uptake in comparison to stationary phases bonded on ordinary silica. Significant correlations were found between the water uptake and the separation selectivity for compounds with strong polarity differences. Copyright © 2014 Elsevier B.V. All rights reserved.

Organised surfactant assemblies in analytical atomic spectrometry

NASA Astrophysics Data System (ADS)

Sanz-Medel, Alfredo; Fernandez de la Campa, Maria del Rosario; Gonzalez, Elisa Blanco; Fernandez-Sanchez, Maria Luisa

1999-02-01

The use of surfactant-based organised assemblies in analytical atomic spectroscopy is extensively and critically reviewed along three main lines: first, the ability of organised media to enhance detection of atomic spectroscopic methods by favourable manipulation of physical and chemical properties of the sample solution second, the extension of separation mechanisms by resorting to organised media and third a discussion of synergistic combinations of liquid chromatography separations and atomic detectors via the use of vesicular mobile phases. Changes in physical properties of sample solutions aspirated in atomic spectrometry by addition of surfactants can be advantageously used in at least four different ways: (i) to improve nebulisation efficiency; (ii) to enhance wettability of solid surfaces used for atomisation; (iii) to improve compatibility between aqueous and organic phases; and (iv) to achieve good dispersion of small particles in "slurry" techniques. Controversial results and statements published so far are critically discussed. The ability of surfactant-based organised assemblies, such as micelles and vesicles, to organise reactants at the molecular level has also been applied to enhance the characteristics of chemical generation of volalite species of metals and semi-metals (e.g., hydride or ethylide generation of As, Pb, Cd, Se, Sn, and cold vapour Hg generation) used in atomic methods. Enhancements in efficiency/transport of volatile species, increases in the reaction kinetics, stabilisation of some unstable species and changes in the selectivity of the reactions by surfactants are dealt with. Non-chromatographic cloud-point separations to design pre-concentration procedures with subsequent metal determination by atomic methods are addressed along with chromatographic separations of expanded scope by addition of surfactants to the conventional aqueous mobile phases of reversed-phase high-performance liquid chromatography. Finally, the synergistic effect of using vesicles to improve both the separation capabilities of reversed-phase HPLC and the detectability of atomic detectors by on-line vesicular hydride generation is described. In particular, the possible separation mechanisms responsible for micellar and vesicular mobile phases in reversed-phase chromatographies are analysed and compared. The possible effect of modification of stationary phases by monomers of the surfactants should also be taken into account. The application of such on-line couplings to develop new hybrid approaches to tackle modern problems of trace element speciation for As, Hg, Se, and Cd completes this revision of the present interface between analytical atomic spectroscopy and surfactant-based organised assemblies.

Factors influencing the stability and type of hydroxyapatite stabilized Pickering emulsion.

PubMed

Zhang, Ming; Wang, Ai-Juan; Li, Jun-Ming; Song, Na; Song, Yang; He, Rui

2017-01-01

Hydroxyapatite (HAp) nanoparticle stabilized Pickering emulsion was fabricated with poly(l-lactic acid) dissolved in dichloromethane (CH 2 Cl 2 ) solution as oil phase and HAp aqueous dispersion as aqueous phase. Pickering emulsion was cured via in situ solvent evaporation method. Effect of PLLA concentrations, pH value, HAp concentrations, oil-water ratio, emulsification rates and times were studied on emulsion stability and emulsion type, etc. The results indicated emulsion stability increased with the increase of HAp concentration, emulsification rate and time; it is very stable when pH value of aqueous phase was adjusted to 10. Stable W/O and O/W emulsions were fabricated successfully using as-received HAp particles as stabilizer by adjusting the fabricating parameters. The interaction between HAp and PLLA played an important role to stabilize Pickering emulsions. SEM results indicated that both microsphere and porous materials were fabricated using emulsion stabilized by unmodified HAp nanoparticles, implying that both W/O and O/W emulsion type were obtained. Copyright © 2016 Elsevier B.V. All rights reserved.

Ketonization of levulinic acid and γ-valerolactone to hydrocarbon fuel precursors

DOE PAGES

Lilga, Michael A.; Padmaperuma, Asanga B.; Auberry, Deanna L.; ...

2017-06-21

We studied a new process for direct conversion of either levulinic acid (LA) or γ-valerolactone (GVL) to hydrocarbon fuel precursors. The process involves passing an aqueous solution of LA or GVL containing a reducing agent, such as ethylene glycol or formic acid, over a ketonization catalyst at 380–400 °C and atmospheric pressure to form a biphasic liquid product. The organic phase is significantly oligomerized and deoxygenated and comprises a complex mixture of open-chain alkanes and olefins, aromatics, and low concentrations of ketones, alcohols, ethers, and carboxylates or lactones. Carbon content in the aqueous phase decreases with decreasing feed rate; themore » aqueous phase can be reprocessed through the same catalyst to form additional organic oils to improve carbon yield. Catalysts are readily regenerated to restore initial activity. Furthermore, the process might be valuable in converting cellulosics to biorenewable gasoline, jet, and diesel fuels as a means to decrease petroleum use and decrease greenhouse gas emissions.« less

Enhanced Hydrothermal Stability and Catalytic Activity of La x Zr y O z Mixed Oxides for the Ketonization of Acetic Acid in the Aqueous Condensed Phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez-Ruiz, Juan A.; Cooper, Alan R.; Li, Guosheng

Common ketonization catalysts such as ZrO2, CeO2, CexZryOz, and TiO2-based catalysts have been reported to lose surface area, undergo phase-transformation, and lose catalytic activity when utilized in the condensed aqueous phase. In this work, we synthesized and tested a series of LaxZryOz mixed metal oxides with different La:Zr atomic ratios with the goal of enhancing the catalytic activity and stability for the ketonization of acetic acid in condensed aqueous media at 568 K. We synthesized a hydrothermally stable LaxZryOz mixed-metal oxide catalyst with enhanced ketonization activities 360 and 40 times more active than La2O3 and ZrO2, respectively. Catalyst characterization techniquesmore » suggest that the formation of a hydrothermally stable catalyst which is isomorphic with tetragonal-ZrO2 under hydrothermal reaction conditions.« less

Achieving High Levels of NMR-Hyperpolarization in Aqueous Media With Minimal Catalyst Contamination Using SABRE.

PubMed

Iali, Wissam; Olaru, Alexandra M; Green, Gary G R; Duckett, Simon B

2017-08-04

Signal amplification by reversible exchange (SABRE) is shown to allow access to strongly enhanced 1 H NMR signals in a range of substrates in aqueous media. To achieve this outcome, phase-transfer catalysis is exploited, which leads to less than 1.5×10 -6  mol dm -3 of the iridium catalyst in the aqueous phase. These observations reflect a compelling route to produce a saline-based hyperpolarized bolus in just a few seconds for subsequent in vivo MRI monitoring. The new process has been called catalyst separated hyperpolarization through signal amplification by reversible exchange or CASH-SABRE. We illustrate this method for the substrates pyrazine, 5-methylpyrimidine, 4,6-d 2 -methyl nicotinate, 4,6-d 2 -nicotinamide and pyridazine achieving 1 H signal gains of approximately 790-, 340-, 3000-, 260- and 380-fold per proton at 9.4 T at the time point at which phase separation is complete. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Metal-ion retention properties of water-soluble amphiphilic block copolymer in double emulsion systems (w/o/w) stabilized by non-ionic surfactants.

PubMed

Palencia, Manuel; Rivas, Bernabé L

2011-11-15

Metal-ion retention properties of water-soluble amphiphilic polymers in presence of double emulsion were studied by diafiltration. Double emulsion systems, water-in-oil-in-water, with a pH gradient between external and internal aqueous phases were prepared. A poly(styrene-co-maleic anhydride) (PSAM) solution at pH 6.0 was added to the external aqueous phase of double emulsion and by application of pressure a divalent metal-ion stream was continuously added. Metal-ions used were Cu(2+) and Cd(2+) at the same pH of polymer solution. According to our results, metal-ion retention is mainly the result of polymer-metal interaction. Interaction between PSMA and reverse emulsion globules is strongly controlled by amount of metal-ions added in the external aqueous phase. In addition, as metal-ion concentration was increased, a negative effect on polymer retention capacity and promotion of flocculation phenomena were produced. Copyright © 2011 Elsevier Inc. All rights reserved.

Biochar enables anaerobic digestion of aqueous phase from intermediate pyrolysis of biomass.

PubMed

Torri, Cristian; Fabbri, Daniele

2014-11-01

Intermediate pyrolysis produces a two-phase liquid whose aqueous phase is characterized by low heating value and high water content (aqueous pyrolysis liquid, APL). Anaerobic digestion can be the straightest way to produce a fuel (methane) from this material. Batch tests showed poor performance in anaerobic digestion of APL, which underlined the inhibition of biological process. Nutrient supplementation was ineffective, whereas biochar addition increased yield of methane (60±15% of theoretical) with respect to pure APL (34±6% of theoretical) and improved the reaction rate. On the basis of batch results, a semi-continuous biomethanation test was set up, by adding an increasingly amount of APL in a 30ml reactor preloaded with biochar (0.8gml(-1)). With a daily input of 5gd(-1)l(-1) of APL (corresponding to overall amount of 0.1kgl(-1) added before the end of the study) the yield of methane was 65±5% of the theoretical. Copyright © 2014 Elsevier Ltd. All rights reserved.

Modified resins for solid-phase extraction

DOEpatents

Fritz, James S.; Sun, Jeffrey J.

1993-07-27

A process of treating aqueous solutions to remove organic solute contaminants by contacting an aqueous solution containing polar organic solute contaminants with a functionalized polystyrene-divinyl benzene adsorbent resin, with the functionalization of said resin being accomplished by organic hydrophilic groups such as hydroxymethyl, acetyl and cyanomethyl.

Modified resins for solid-phase extraction

DOEpatents

Fritz, James S.; Sun, Jeffrey J.

1991-12-10

A process of treating aqueous solutions to remove organic solute contaminants by contacting an aqueous solution containing polar organic solute contaminants with a functionalized polystyrene-divinyl benzene adsorbent resin, with the functionalization of said resin being accomplished by organic hydrophilic groups such as hydroxymethyl, acetyl and cyanomethyl.

EXTRACTION METHOD FOR SEPARATING URANIUM, PLUTONIUM, AND FISSION PRODUCTS FROM COMPOSITIONS CONTAINING SAME

DOEpatents

Seaborg, G.T.

1957-10-29

Methods for separating plutonium from the fission products present in masses of neutron irradiated uranium are reported. The neutron irradiated uranium is first dissolved in an aqueous solution of nitric acid. The plutonium in this solution is present as plutonous nitrate. The aqueous solution is then agitated with an organic solvent, which is not miscible with water, such as diethyl ether. The ether extracts 90% of the uraryl nitrate leaving, substantially all of the plutonium in the aqueous phase. The aqueous solution of plutonous nitrate is then oxidized to the hexavalent state, and agitated with diethyl ether again. In the ether phase there is then obtained 90% of plutonium as a solution of plutonyl nitrate. The ether solution of plutonyl nitrate is then agitated with water containing a reducing agent such as sulfur dioxide, and the plutonium dissolves in the water and is reduced to the plutonous state. The uranyl nitrate remains in the ether. The plutonous nitrate in the water may be recovered by precipitation.

Self-assembly of large-scale crack-free gold nanoparticle films using a ‘drain-to-deposit’ strategy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Guang; Hallinan, Daniel T.

2016-04-26

Gold nanoparticles are widely studied due to the ease of controlled synthesis, facile surface modification, and interesting physical properties. However, a technique for depositing large-area, crack-free monolayers on solid substrates is lacking. Herein is presented a method for accomplishing this. Spherical gold nanoparticles were synthesized as an aqueous dispersion. Assembly into monolayers and ligand exchange occurred simultaneously at an organic/aqueous interface. Then the monolayer film was deposited onto arbitrary solid substrates by slowly pumping out the lower, aqueous phase. This allowed the monolayer film (and liquid–liquid interface) to descend without significant disturbance, eventually reaching substrates contained in the aqueous phase.more » The resulting macroscopic quality of the films was found to be superior to films transferred by Langmuir techniques. The surface plasmon resonance and Raman enhancement of the films were evaluated and found to be uniform across the surface of each film.« less

SEPARATION OF PLUTONIUM FROM AQUEOUS SOLUTIONS BY ION-EXCHANGE

DOEpatents

Schubert, J.

1958-06-01

A process is described for the separation of plutonium from an aqueous solution of a plutonium salt, which comprises adding to the solution an acid of the group consisting of sulfuric acid, phosphoric acid, and oxalic acid, and mixtures thereof to provide an acid concentration between 0.0001 and 1 M, contacting the resultant solution with a synthetic organic anion exchange resin, and separating the aqueous phase and the resin which contains the plutonium.

Crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics for immobilization of simulated sulfate bearing high-level liquid waste

NASA Astrophysics Data System (ADS)

Wu, Lang; Xiao, Jizong; Wang, Xin; Teng, Yuancheng; Li, Yuxiang; Liao, Qilong

2018-01-01

The crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics with different content (0-30 wt %) of simulated sulfate bearing high-level liquid waste (HLLW) were evaluated. The sulfate phase segregation in vitrification process was also investigated. The results show that the glass-ceramics with 0-20 wt% of HLLW possess mainly zirconolite phase along with a small amount baddeleyite phase. The amount of perovskite crystals increases while the amount of zirconolite crystals decreases when the HLLW content increases from 20 to 30 wt%. For the samples with 20-30 wt% HLLW, yellow phase was observed during the vitrification process and it disappeared after melting at 1150 °C for 2 h. The viscosity of the sample with 16 wt% HLLW (HLLW-16) is about 27 dPa·s at 1150 °C. The addition of a certain amount (≤20 wt %) of HLLW has no significant change on the aqueous stability of glass-ceramic waste forms. After 28 days, the 90 °C PCT-type normalized leaching rates of Na, B, Si, and La of the sample HLLW-16 are 7.23 × 10-3, 1.57 × 10-3, 8.06 × 10-4, and 1.23 × 10-4 g·m-2·d-1, respectively.

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry's Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds.

PubMed

Hilal, S H; Saravanaraj, A N; Carreira, L A

2014-02-01

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry's Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aqueous pKa values, relative pKa values in the gas phase, and aqueous HLC for neutral compounds have been used to develop monopole interaction models that quantify the energy differences upon moving an ionic solute molecule from the gas phase to the liquid phase. Inter-molecular interaction energies were factored into mechanistic contributions of monopoles with polarizability, dipole, H-bonding, and resonance. The monopole ionic models were validated by a wide range of measured gas phase pKa data for 450 acidic compounds. The RMS deviation error and R(2) for the OH, SH, CO2 H, CH3 and NR2 acidic reaction centers (C) were 16.9 kcal/mol and 0.87, respectively. The calculated HLCs of ions were compared to the HLCs of 142 ions calculated by quantum mechanics. Effects of inter-molecular interaction of the monopoles with polarizability, dipole, H-bonding, and resonance on acidity of the solutes in the gas phase are discussed. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of Analytical Quality by Design concept for bilastine and its degradation impurities determination by hydrophilic interaction liquid chromatographic method.

PubMed

Terzić, Jelena; Popović, Igor; Stajić, Ana; Tumpa, Anja; Jančić-Stojanović, Biljana

2016-06-05

This paper deals with the development of hydrophilic interaction liquid chromatographic (HILIC) method for the analysis of bilastine and its degradation impurities following Analytical Quality by Design approach. It is the first time that the method for bilastine and its impurities is proposed. The main objective was to identify the conditions where an adequate separation in minimal analysis duration could be achieved within a robust region. Critical process parameters which have the most influence on method performance were defined as acetonitrile content in the mobile phase, pH of the aqueous phase and ammonium acetate concentration in the aqueous phase. Box-Behnken design was applied for establishing a relationship between critical process parameters and critical quality attributes. The defined mathematical models and Monte Carlo simulations were used to identify the design space. Fractional factorial design was applied for experimental robustness testing and the method is validated to verify the adequacy of selected optimal conditions: the analytical column Luna(®) HILIC (100mm×4.6mm, 5μm particle size); mobile phase consisted of acetonitrile-aqueous phase (50mM ammonium acetate, pH adjusted to 5.3 with glacial acetic acid) (90.5:9.5, v/v); column temperature 30°C, mobile phase flow rate 1mLmin(-1), wavelength of detection 275nm. Copyright © 2016 Elsevier B.V. All rights reserved.

A hybrid approach to device integration on a genetic analysis platform

NASA Astrophysics Data System (ADS)

Brennan, Des; Jary, Dorothee; Kurg, Ants; Berik, Evgeny; Justice, John; Aherne, Margaret; Macek, Milan; Galvin, Paul

2012-10-01

Point-of-care (POC) systems require significant component integration to implement biochemical protocols associated with molecular diagnostic assays. Hybrid platforms where discrete components are combined in a single platform are a suitable approach to integration, where combining multiple device fabrication steps on a single substrate is not possible due to incompatible or costly fabrication steps. We integrate three devices each with a specific system functionality: (i) a silicon electro-wetting-on-dielectric (EWOD) device to move and mix sample and reagent droplets in an oil phase, (ii) a polymer microfluidic chip containing channels and reservoirs and (iii) an aqueous phase glass microarray for fluorescence microarray hybridization detection. The EWOD device offers the possibility of fully integrating on-chip sample preparation using nanolitre sample and reagent volumes. A key challenge is sample transfer from the oil phase EWOD device to the aqueous phase microarray for hybridization detection. The EWOD device, waveguide performance and functionality are maintained during the integration process. An on-chip biochemical protocol for arrayed primer extension (APEX) was implemented for single nucleotide polymorphism (SNiP) analysis. The prepared sample is aspirated from the EWOD oil phase to the aqueous phase microarray for hybridization. A bench-top instrumentation system was also developed around the integrated platform to drive the EWOD electrodes, implement APEX sample heating and image the microarray after hybridization.

Dehydration induced phase transitions in a microfluidic droplet array for the separation of biomolecules

NASA Astrophysics Data System (ADS)

Nelson, Chris; Anna, Shelley

2013-11-01

Droplet-based strategies for fluid manipulation have seen significant application in microfluidics due to their ability to compartmentalize solutions and facilitate highly parallelized reactions. Functioning as micro-scale reaction vessels, droplets have been used to study protein crystallization, enzyme kinetics, and to encapsulate whole cells. Recently, the mass transport out of droplets has been used to concentrate solutions and induce phase transitions. Here, we show that droplets trapped in a microfluidic array will spontaneously dehydrate over the course of several hours. By loading these devices with an initially dilute aqueous polymer solution, we use this slow dehydration to observe phase transitions and the evolution of droplet morphology in hundreds of droplets simultaneously. As an example, we trap and dehydrate droplets of a model aqueous two-phase system consisting of polyethylene glycol and dextran. Initially the drops are homogenous, then after some time the polymer concentration reaches a critical point and two phases form. As water continues to leave the system, the drops transition from a microemulsion of DEX in PEG to a core-shell configuration. Eventually, changes in interfacial tension, driven by dehydration, cause the DEX core to completely de-wet from the PEG shell. Since aqueous two phase systems are able to selectively separate a variety of biomolecules, this core shedding behavior has the potential to provide selective, on-chip separation and concentration.