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Sample records for mass transfer liquid-liquid

  1. Methods to control phase inversions and enhance mass transfer in liquid-liquid dispersions

    DOEpatents

    Tsouris, Constantinos; Dong, Junhang

    2002-01-01

    The present invention is directed to the effects of applied electric fields on liquid-liquid dispersions. In general, the present invention is directed to the control of phase inversions in liquid-liquid dispersions. Because of polarization and deformation effects, coalescence of aqueous drops is facilitated by the application of electric fields. As a result, with an increase in the applied voltage, the ambivalence region is narrowed and shifted toward higher volume fractions of the dispersed phase. This permits the invention to be used to ensure that the aqueous phase remains continuous, even at a high volume fraction of the organic phase. Additionally, the volume fraction of the organic phase may be increased without causing phase inversion, and may be used to correct a phase inversion which has already occurred. Finally, the invention may be used to enhance mass transfer rates from one phase to another through the use of phase inversions.

  2. Liquid-liquid mass transfer of partitioning electron donors in chlorinated solvent source zones.

    PubMed

    Cápiro, Natalie L; Granbery, Emmie K; Lebrón, Carmen A; Major, David W; McMaster, Michaye L; Pound, Michael J; Löffler, Frank E; Pennell, Kurt D

    2011-02-15

    A combination of batch and column experiments evaluated the mass transfer of two candidate partitioning electron donors (PEDs), n-hexanol (nHex) and n-butyl acetate (nBA), for enhanced bioremediation of trichloroethene (TCE)-dense nonaqueous phase liquid (DNAPL). Completely mixed batch reactor experiments yielded equilibrium TCE-DNAPL and water partition coefficients (KNW) for nHex and nBA of 21.7 ± 0.27 and 330.43 ± 6.7, respectively, over a range of initial PED concentrations up to the aqueous solubility limit of ca. 5000 mg/L. First-order liquid-liquid mass transfer rates determined in batch reactors with nBA or nHex concentrations near the aqueous solubility were 0.22 min(-1) and 0.11 min(-1), respectively. Liquid-liquid mass transfer under dynamic flow conditions was assessed in one-dimensional (1-D) abiotic columns packed with Federal Fine Ottawa sand containing a uniform distribution of residual TCE-DNAPL. Following pulse injection of PED solutions at pore-water velocities (vp) ranging from 1.2 to 6.0 m/day, effluent concentration measurements demonstrated that both nHex and nBA partitioned strongly into residual TCE-DNAPL with maximum effluent levels not exceeding 35% and 7%, respectively, of the applied concentrations of 4000 to 5000 mg/L. PEDs persisted at effluent concentrations above 5 mg/L for up to 16 and 80 pore volumes for nHex and nBA, respectively. Mathematical simulations yielded KNW values ranging from 44.7 to 48.2 and 247 to 291 and liquid-liquid mass transfer rates of 0.01 to 0.03 min(-1) and 0.001 to 0.006 min(-1) for nHex and nBA, respectively. The observed TCE-DNAPL and water mass transfer behavior suggests that a single PED injection can persist in a treated source zone for prolonged time periods, thereby reducing the need for, or frequency of, repeated electron donor injections to support bacteria that derive reducing equivalents for TCE reductive dechlorination from PED fermentation.

  3. Model of Mass Transfer in Liquid-Liquid Extraction in a Turbulent Forward Flow

    NASA Astrophysics Data System (ADS)

    Laptev, A. G.; Farakhov, T. M.; Dudarovskaya, O. G.

    2015-01-01

    A mathematical description of the process of mass transfer in a continuous phase in the turbulent motion of two mutually insoluble liquids has been obtained on the basis of an assigned law of damping of turbulent pulsations in the boundary layer. The basic parameters of the model have been found in terms of the hydraulic resistance of a droplet in motion. Consideration has been given to the use of the mathematical mass-transfer model in apparatuses with mixing devices. Agreement has been shown between results of calculation of mass-transfer coefficients and experimental data.

  4. Exploring bubble oscillation and mass transfer enhancement in acoustic-assisted liquid-liquid extraction with a microfluidic device

    PubMed Central

    Xie, Yuliang; Chindam, Chandraprakash; Nama, Nitesh; Yang, Shikuan; Lu, Mengqian; Zhao, Yanhui; Mai, John D.; Costanzo, Francesco; Huang, Tony Jun

    2015-01-01

    We investigated bubble oscillation and its induced enhancement of mass transfer in a liquid-liquid extraction process with an acoustically-driven, bubble-based microfluidic device. The oscillation of individually trapped bubbles, of known sizes, in microchannels was studied at both a fixed frequency, and over a range of frequencies. Resonant frequencies were analytically identified and were found to be in agreement with the experimental observations. The acoustic streaming induced by the bubble oscillation was identified as the cause of this enhanced extraction. Experiments extracting Rhodanmine B from an aqueous phase (DI water) to an organic phase (1-octanol) were performed to determine the relationship between extraction efficiency and applied acoustic power. The enhanced efficiency in mass transport via these acoustic-energy-assisted processes was confirmed by comparisons against a pure diffusion-based process. PMID:26223474

  5. Exploring bubble oscillation and mass transfer enhancement in acoustic-assisted liquid-liquid extraction with a microfluidic device

    NASA Astrophysics Data System (ADS)

    Xie, Yuliang; Chindam, Chandraprakash; Nama, Nitesh; Yang, Shikuan; Lu, Mengqian; Zhao, Yanhui; Mai, John D.; Costanzo, Francesco; Huang, Tony Jun

    2015-07-01

    We investigated bubble oscillation and its induced enhancement of mass transfer in a liquid-liquid extraction process with an acoustically-driven, bubble-based microfluidic device. The oscillation of individually trapped bubbles, of known sizes, in microchannels was studied at both a fixed frequency, and over a range of frequencies. Resonant frequencies were analytically identified and were found to be in agreement with the experimental observations. The acoustic streaming induced by the bubble oscillation was identified as the cause of this enhanced extraction. Experiments extracting Rhodanmine B from an aqueous phase (DI water) to an organic phase (1-octanol) were performed to determine the relationship between extraction efficiency and applied acoustic power. The enhanced efficiency in mass transport via these acoustic-energy-assisted processes was confirmed by comparisons against a pure diffusion-based process.

  6. Exploring bubble oscillation and mass transfer enhancement in acoustic-assisted liquid-liquid extraction with a microfluidic device.

    PubMed

    Xie, Yuliang; Chindam, Chandraprakash; Nama, Nitesh; Yang, Shikuan; Lu, Mengqian; Zhao, Yanhui; Mai, John D; Costanzo, Francesco; Huang, Tony Jun

    2015-07-30

    We investigated bubble oscillation and its induced enhancement of mass transfer in a liquid-liquid extraction process with an acoustically-driven, bubble-based microfluidic device. The oscillation of individually trapped bubbles, of known sizes, in microchannels was studied at both a fixed frequency, and over a range of frequencies. Resonant frequencies were analytically identified and were found to be in agreement with the experimental observations. The acoustic streaming induced by the bubble oscillation was identified as the cause of this enhanced extraction. Experiments extracting Rhodanmine B from an aqueous phase (DI water) to an organic phase (1-octanol) were performed to determine the relationship between extraction efficiency and applied acoustic power. The enhanced efficiency in mass transport via these acoustic-energy-assisted processes was confirmed by comparisons against a pure diffusion-based process.

  7. Mass transfer of terpenes through a silicone rubber membrane in a liquid-liquid contacting system.

    PubMed

    Boontawan, Apichat; Stuckey, David C

    2005-01-01

    Terpenoids are important compounds for the fragrance industry, and recently, biocatalytic methods have been developed to produce them from cheap monoterpenes, such as alpha-pinene oxide. The biotransformation of alpha-pinene oxide using resting cells of Pseudomonas fluorescens NCIMB 11671 produces isonovalal (cis-2-methyl-5-isopropylhexa-2,5-dienal), which is a fragrance. However, this biotransformation has technical problems including the following: alpha-pinene oxide undergoes autoxidation in water and light; it is hydrophobic and relatively toxic to the biocatalyst; and it suffers from product inhibition. Therefore, removal of isonovalal as it is formed should reduce its toxicity and increase volumetric productivity and production yield. Aqueous-organic two-phase (AOTP) systems can be used in the biotransformation of hydrophobic substrates and can protect biocatalysts from toxic substrates and products. However, the formation of stable emulsions makes further downstream processing and continuous operation difficult. One solution to these problems is to use a solid-phase membrane between the aqueous and organic phases in a Membrane Bioreactor for Biotransformation (MBB). Since there are no data in the literature on the behavior of terpenes and terpenoids with solid-phase membranes, or their mass transfer behavior, the objective of this work was to measure these parameters for a wide range of compounds so as to be able to design an MBB, and to gain a greater understanding of their behavior in these types of systems. Organic/aqueous (P (org) (aq)) and membrane/aqueous (P (mem) (aq)) partition coefficients were measured first, and subsequently used to quantify the overall mass transfer coefficients (k(ov)). The overall mass transfer coefficient (k(ov)) of alpha-pinene oxide through the membrane was found to be 2.5 x 10(-5) m x s(-1) using thicknesses of both 250 and 1,000 microm. Extraction kinetics were successfully described using a resistance-in-series model and

  8. Periodic marangoni instability in surfactant (CTAB) liquid/liquid mass transfer.

    PubMed

    Lavabre, Dominique; Pradines, Vincent; Micheau, Jean-Claude; Pimienta, Véronique

    2005-04-21

    Periodic Marangoni convective instability has been observed in a biphasic system during the mass transfer of cetyltrimethylammonium bromide (CTAB) from an aqueous to a dichloromethane organic phase. Visualization of the convective fluxes was possible thanks to the CTAB crystals that are formed in the aqueous phase at a temperature below the Krafft point. Surface tension and electrical potential oscillations have been shown to be correlated with the fluid motion. Surface tension measurements, representative of the adsorption state, showed fast adsorption during the convective stage, followed by a slower desorption process in the quiet stage. To account for the electrical potential data, two components need to be taken into account. In the quiet stage, the signal was comparable to surface tension, and the main contribution would result from the electrical double layer formed at the interface by charged surfactants. In the convective stage, the electrical potential was furthermore related to the velocity of the fluid in the aqueous layer. Perturbations of the charge distribution in the Gouy-Chapman layer due to tangential flows could be at the origin of the phenomenon.

  9. Magnetic nanoparticles stimulation to enhance liquid-liquid two-phase mass transfer under static and rotating magnetic fields

    NASA Astrophysics Data System (ADS)

    Azimi, Neda; Rahimi, Masoud

    2017-01-01

    Rotating magnetic field (RMF) was applied on a micromixer to break the laminar flow and induce chaotic flow to enhance mass transfer between two-immiscible organic and aqueous phases. The results of RMF were compared to those of static magnetic field (SMF). For this purpose, experiments were carried out in a T-micromixer at equal volumetric flow rates of organic and aqueous phases. Fe3O4 nanoparticles were synthesized by co-precipitation technique and they were dissolved in organic phase. Results obtained from RMF and SMF were compared in terms of overall volumetric mass transfer coefficient (KLa) and extraction efficiency (E) at various Reynolds numbers. Generally, RMF showed higher effect in mass transfer characteristics enhancement compared with SMF. The influence of rotational speeds of magnets (ω) in RMF was investigated, and measurable enhancements of KLa and E were observed. In RMF, the effect of magnetic field induction (B) was investigated. The results reveal that at constant concentration of nanoparticles, by increasing of B, mass transfer characteristics will be enhanced. The effect of various nanoparticles concentrations (ϕ) within 0.002-0.01 (w/v) on KLa and E at maximum induction of RMF (B=76 mT) was evaluated. Maximum values of KLa (2.1±0.001) and E (0.884±0.001) were achieved for the layout of RMF (B=76 mT), ω=16 rad/s and MNPs concentration of 0.008-0.01 (w/v).

  10. Determination of alkylmethylphosphonic acids, the main metabolites of organophosphorus nerve agents, in biofluids by gas chromatography-mass spectrometry and liquid-liquid-solid-phase-transfer-catalyzed pentafluorobenzylation.

    PubMed

    Miki, A; Katagi, M; Tsuchihashi, H; Yamashita, M

    1999-01-01

    A simple gas chromatography-mass spectrometry (GC-MS) procedure has been developed for the main metabolites of organophosphorus nerve agents, alkylmethylphosphonic acids (AMPAs; alkyl = Et, i-Pr, and pinacolyl) in biofluids via extractive pentafluorobenzylation. The derivatization was carried out under liquid-liquid-solid-phase-transfer conditions using a polymer-bound tri-n-butylmethylphosphonium bromide as a catalyst. AMPAs in aqueous samples were semiquantitatively extracted into a small-volume organic layer as their pentafluorobenzyl derivatives at pH 4.5 (85 degrees C). Sample pretreatments for urine, serum, and saliva were each examined to minimize matrix interference. The detection limits of APMAs by electron-impact ionization GC-MS were around 50 ng/mL and 2.5-10 ng/mL in the full-scan and selected-ion monitoring modes, respectively. In order to detect trace-level AMPAs, negative-ion chemical ionization (NICI) was also employed to enhance sensitivity. The detection limits of AMPAs in biofluids were typically 60 pg/mL by GC-NICI-MS.

  11. A rubber transfer gasket to improve the throughput of liquid-liquid extraction in 96-well plates: application to vitamin D testing.

    PubMed

    Hoofnagle, Andrew N; Laha, Thomas J; Donaldson, Thomas F

    2010-06-01

    The unmitigated rise in demand for the assessment of vitamin D status has taxed the ability of clinical mass spectrometry laboratories to preserve turn-around times. We aimed to improve the throughput of liquid-liquid extraction of plasma/serum for the assay of 25-hydroxy vitamin D. We designed and fabricated a flexible rubber gasket that seals two 96-well plates together to quantitatively transfer the contents of one plate to another. Using the transfer gasket and a dry-ice acetone bath to freeze the aqueous infranatant, we developed a novel liquid-liquid extraction workflow in a 96-well plate format. We applied the technology to the mass spectrometric quantification of 25-hydroxy vitamin D. Cross-contamination between wells was < or = 0.13%. The interassay imprecision over 132 days of clinical implementation was less than 10%. The method compared favorably to a standard liquid-liquid extraction in glass tubes (Deming slope=1.018, S(x|y)=0.022). The accuracy of the assay was 102-105% as assessed with the recently released control materials from NIST. The development of a plate-sealing gasket permits the liquid-liquid extraction of clinical specimens in a moderate-throughput workflow and the reliable assay of vitamin D status. In the future, the gasket may also prove useful in other sample preparation techniques for HPLC or mass spectrometry. Copyright 2010 Elsevier B.V. All rights reserved.

  12. Phase transfer membrane supported liquid-liquid-liquid microextraction combined with large volume sample injection capillary electrophoresis-ultraviolet detection for the speciation of inorganic and organic mercury.

    PubMed

    Li, Pingjing; Zhang, Xing; Hu, Bin

    2011-12-30

    In this paper, a novel sample pretreatment technique termed phase transfer based liquid-liquid-liquid microextraction (PT-LLLME) was proposed for the simultaneous extraction of inorganic and organic mercury species. In PT-LLLME, an intermediate solvent (acetonitrile) was added into the donor phase to improve the contacting between target mercury species and complexing reagent. Meanwhile, a membrane supported (MS)-LLLME unit was designed to realize the PT-LLLME procedure. By using nylon membrane as supporting carrier, larger than 50 μL of acceptor solution could be hung up. Following PT/MS-LLLME, the acceptor solutions were directly analyzed by large volume sample stacking capillary electrophoresis/ultraviolet detection (LVSS-CE/UV). Accordingly, a new method of PT/MS-LLLME combined with LVSS-CE/UV was developed for the simultaneous speciation of inorganic and organic mercury species. Parameters affecting the extraction efficiency of PT/MS-LLLME were investigated in details. Under the optimized conditions, enrichment factors (EFs) ranging from 160- to 478-fold were obtained for the extraction of target mercury species by PT/MS-LLLME. By combining PT/MS-LLLME with LVSS-CE/UV, EFs were magnified up to 12,138-fold and the limits of detection (at a signal-to-noise ratio of 3) were at sub ppb level. The established approach of PT/MS-LLLME-LVSS-CE/UV was successfully applied to simultaneous determination of inorganic and organic mercury species in biological samples and environmental water samples.

  13. Direct analysis in real time mass spectrometry combined with single-drop liquid-liquid-liquid microextraction for the rapid analysis of multiple phytohormones in fruit juice.

    PubMed

    Bai, Yu; Zhang, Jialing; Bai, Yu; Liu, Huwei

    2012-06-01

    A rapid, simple, and efficient method for the fast determination of multiple phytohormones was developed in this work, based on single-drop liquid-liquid-liquid microextraction (SD-LLLME) combined with direct analysis in real-time mass spectrometry (DART-MS). Six phytohormones--indole-3-acetic acid (IAA), indole-3-butyric acid (IBA), jasmonic acid (JA), salicylic acid (SA), abscisic acid (ABA), and gibberellin A(3) (GA(3))--were analyzed simultaneously using this method, and the conditions employed for DART-MS and SD-LLLME were optimized systematically. Satisfactory results were obtained in terms of linearity (R (2) values for all phytohormones were 0.991-0.996), sensitivity (limits of detection were 0.65-72 ng/mL), and repeatability (RSD values were 6.9-14%). In addition, the proposed method was applied to determine the endogenous phytohormones in three kinds of fruit juice. Different concentrations of phytohormones were detected with satisfactory recoveries, and the whole analytical procedure took no more than 30 min. Therefore, this combination of SD-LLLME and DART-MS was shown to be a suitable and effective approach for the fast analysis of targets present at trace level concentrations in complex matrices.

  14. Ion-transfer voltammetric behavior of propranolol at nanoscale liquid-liquid interface arrays.

    PubMed

    Liu, Yang; Strutwolf, Jörg; Arrigan, Damien W M

    2015-04-21

    In this work, the ion-transfer voltammetric detection of the protonated β-blocker propranolol was explored at arrays of nanoscale interfaces between two immiscible electrolyte solutions (ITIES). Silicon nitride nanoporous membranes with 400 pores in a hexagonal arrangement, with either 50 or 17 nm radius pores, were used to form regular arrays of nanoITIES. It was found that the aqueous-to-organic ion-transfer current continuously increased steadily rather than reaching a limiting current plateau after the ion-transfer wave; the slope of this limiting current region was concentration dependent and associated with the high ion flux at the nanointerfaces. Electrochemical data were examined in terms of an independent nanointerface approach and an equivalent microdisc approach, supported by finite element simulation. In comparison to the larger interface configuration (50 nm radius), the array of 17 nm radius nanoITIES exhibited a 6.5-times higher current density for propranolol detection due to the enhanced ion flux arising from the convergent diffusion to smaller electrochemical interfaces. Both nanoITIES arrays achieved the equivalent limits of detection, 0.8 μM, using cyclic voltammetry. Additionally, the effect of scan rate on the charging and faradaic currents at these nanoITIES arrays, as well as their stability over time, was investigated. The results demonstrate that arrays of nanoscale liquid-liquid interfaces can be applied to study electrochemical drug transfer, and provide the basis for the development of miniaturized and integrated detection platforms for drug analysis.

  15. Ion-transfer voltammetric determination of folic acid at meso-liquid-liquid interface arrays.

    PubMed

    Jiang, Xuheng; Gao, Kui; Hu, Daopan; Wang, Huanhuan; Bian, Shujuan; Chen, Yong

    2015-04-21

    Voltammetric studies on the simple ion transfer (IT) behaviors of an important water-soluble B-vitamin, folic acid (FA), at the liquid-liquid (L-L) interface were firstly performed and then applied as a novel detection method for FA under physiological conditions. Meso-water-1,6-dichlorohexane (W-DCH) and meso-water-organogel interface arrays were built by using a hybrid mesoporous silica membrane (HMSM) with a unique structure of pores-in-pores and employed as the new platforms for the IT voltammetric study. In view of the unique structure of the HMSM, the impact of the ionic surfactant cetyltrimethylammonium bromide (CTAB), self-assembled within the silica nanochannels of the HMSM, was investigated. In particular, its effect on the IT voltammetric behavior and detection of FA at meso-L-L interface arrays was systematically examined by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and differential pulse stripping voltammetry (DPSV). It was found that all the voltammetric responses of CV, DPV, and DPSV and the corresponding detection limit of FA at such meso-L-L interface arrays are closely related to the CTAB in the HMSM. Significantly, the calculated detection limit of FA could be improved to 80 nM after the combination of the DPSV technique with the additional preconcentration of FA in the silica-CTAB nanochannels, achieved through an anion-exchange process between FA(-) and the bromide of CTAB in HMSM. This provides a new and attractive strategy for the detection of those biological anions.

  16. Automated on-line liquid-liquid extraction system for temporal mass spectrometric analysis of dynamic samples.

    PubMed

    Hsieh, Kai-Ta; Liu, Pei-Han; Urban, Pawel L

    2015-09-24

    Most real samples cannot directly be infused to mass spectrometers because they could contaminate delicate parts of ion source and guides, or cause ion suppression. Conventional sample preparation procedures limit temporal resolution of analysis. We have developed an automated liquid-liquid extraction system that enables unsupervised repetitive treatment of dynamic samples and instantaneous analysis by mass spectrometry (MS). It incorporates inexpensive open-source microcontroller boards (Arduino and Netduino) to guide the extraction and analysis process. Duration of every extraction cycle is 17 min. The system enables monitoring of dynamic processes over many hours. The extracts are automatically transferred to the ion source incorporating a Venturi pump. Operation of the device has been characterized (repeatability, RSD = 15%, n = 20; concentration range for ibuprofen, 0.053-2.000 mM; LOD for ibuprofen, ∼0.005 mM; including extraction and detection). To exemplify its usefulness in real-world applications, we implemented this device in chemical profiling of pharmaceutical formulation dissolution process. Temporal dissolution profiles of commercial ibuprofen and acetaminophen tablets were recorded during 10 h. The extraction-MS datasets were fitted with exponential functions to characterize the rates of release of the main and auxiliary ingredients (e.g. ibuprofen, k = 0.43 ± 0.01 h(-1)). The electronic control unit of this system interacts with the operator via touch screen, internet, voice, and short text messages sent to the mobile phone, which is helpful when launching long-term (e.g. overnight) measurements. Due to these interactive features, the platform brings the concept of the Internet-of-Things (IoT) to the chemistry laboratory environment. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Stir-membrane solid-liquid-liquid microextraction for the determination of parabens in human breast milk samples by ultra high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Rodríguez-Gómez, Rocío; Roldán-Pijuán, Mercedes; Lucena, Rafael; Cárdenas, Soledad; Zafra-Gómez, Alberto; Ballesteros, Oscar; Navalón, Alberto; Valcárcel, Miguel

    2014-08-08

    In this article, stir-membrane solid-liquid-liquid microextraction (SM-SLLME) is tailored for the analysis of solid matrices and it has been evaluated for the determination of parabens in l breast milk samples. A three-phase microextraction mode was used for the extraction of the target compounds taking advantage of their acid-base properties. The unit allows the simultaneous extraction of the target compounds from the solid sample to an organic media and the subsequent transference of the analytes to an aqueous acceptor phase. The method includes the identification and quantification of the analytes by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). All the variables involved in the extraction procedure have been accurately studied and optimized. The analytes were detected and quantified using a triple quadrupole mass spectrometer (QqQ). The selection of two specific fragmentation transitions for each compound allowed simultaneous quantification and identification. The method has been analytically characterized on the basis of its linearity, sensitivity and precision. Limits of detection ranged from 0.1 to 0.2ngmL(-1) with precision better than 8%, (expressed as relative standard deviation). Relative recoveries were in the range from 91 to 106% which demonstrated the applicability of the stir-membrane solid-liquid-liquid microextraction for the proposed analytical problem. Moreover, the method has been satisfactorily applied for the determination of parabens in lyophilized breast milk samples from 10 randomly selected individuals.

  18. Dispersive liquid-liquid microextraction with little solvent consumption combined with gas chromatography-mass spectrometry for the pretreatment of organochlorine pesticides in aqueous samples.

    PubMed

    Tsai, Wan-Chun; Huang, Shang-Da

    2009-07-03

    Dispersive liquid-liquid microextraction with little solvent consumption (DLLME-LSC), a novel dispersive liquid-liquid microextraction (DLLME) technique with few solvent requirements (13 microL of a binary mixture of disperser solvent and extraction solvent in the ratio of 6:4) and short extraction time (90 s), has been developed for extraction of organochlorine pesticides (OCPs) from water samples prior to gas chromatography/mass spectrometry analysis. In DLLME-LSC, much less volume of organic solvent is used as compared to DLLME. The new technique is less harmful to environment and yields a higher enrichment factor (1885-2648-fold in this study). Fine organic droplets were formed in the sample solution by manually shaking the test tube containing the mixture of sample solution and extraction solvent. The large surface area of the organic solvent droplets increases the rate of mass transfer from the water sample to the extractant and produces efficient extraction in a short period of time. DLLME-LSC shows good repeatability (RSD: 4.1-9.7% for reservoir water; 5.6-8.9% for river water) and high sensitivity (limits of detection: 0.8-2.5 ng/L for reservoir water; 0.4-1.3 ng/L for river water). The method can be used on various water samples (river water, tap water, sea water and reservoir water). It can be used for routine work for the investigation of OCPs.

  19. Ion-transfer- and photo-electrochemistry at liquid|liquid|solid electrode triple phase boundary junctions: perspectives.

    PubMed

    Marken, Frank; Watkins, John D; Collins, Andrew M

    2011-06-07

    Ion transfer at liquid|liquid junctions is one of the most fundamental processes in nature. It occurs coupled to simultaneous electron transfer at the line junction (or triple phase boundary) formed by the two liquids in contact to an electrode surface. The triple phase boundary can be assembled from a redox active microdroplet deposit of a water-immiscible liquid on a suitable electrode surface immersed into aqueous electrolyte. Ion transfer voltammetry measurements at this type of electrode allow both thermodynamic and kinetic parameters for coupled ion and electron transfer processes to be obtained. This overview summarises some recent advances in understanding and application of triple phase boundary redox processes at organic liquid|aqueous electrolyte|working electrode junctions. The design of novel types of electrodes is considered based on (i) extended triple phase boundaries, (ii) porous membrane processes, (iii) hydrodynamic effects, and (iv) generator-collector triple phase boundary systems. Novel facilitated ion transfer processes and photo-electrochemical processes at triple phase boundary electrodes are proposed. Potential future applications of triple phase boundary redox systems in electrosynthesis, sensing, and light energy harvesting are indicated.

  20. Chronoamperometry at micropipet electrodes for determination of diffusion coefficients and transferred charges at liquid/liquid interfaces.

    PubMed

    Yuan, Yi; Wang, Lei; Amemiya, Shigeru

    2004-09-15

    Chronoamperometry was carried out at liquid/liquid interfaces supported at the tip of micropipet electrodes for direct determination of the diffusion coefficient of a species in the outer solution. The diffusion coefficient was used for subsequent determination of the transferred charges per species from the diffusion-limited steady-state current. A large tip resistance of the micropipets causes prolonged charging current so that the faradic current can be measured accurately only at a long-time regime (typically t > 5 ms). At the same time, the long-time current response at the interfaces surrounded by a thin glass wall of the pipets is enhanced by diffusion of the species from behind the pipet tip. Therefore, numerical simulations of the long-time chronoamperometric response were carried out using the finite element method for accurate determination of diffusion coefficients. Validity of the simulation results was confirmed by studying simple transfer of tetraethylammonium ion. The technique was applied for transfer/adsorption reactions of the natural polypeptide protamine and also for Ca2+ and Mg2+ transfers facilitated by ionophore ETH 129. With the diffusion coefficient of protamine determined to be (1.2 +/- 0.1) x 10(-6) cm(2)/s, the ionic charge transferred by each protamine molecule was obtained as +20 +/- 1, which is close to the excess positive charge of protamine. Also, the diffusion coefficient of ETH 129 was determined to demonstrate that each ionophore molecule transfers +0.67 and +1 charge per Ca2+ and Mg2+ transfer, respectively, which corresponds to formation of 1:3 and 1:2 complexes with the respective ions.

  1. Detection of Posaconazole by Surface-Assisted Laser Desorption/Ionization Mass Spectrometry with Dispersive Liquid-Liquid Microextraction

    NASA Astrophysics Data System (ADS)

    Lin, Sheng-Yu; Chen, Pin-Shiuan; Chang, Sarah Y.

    2015-03-01

    A simple, rapid, and sensitive method for the detection of posaconazole using dispersive liquid-liquid microextraction (DLLME) coupled to surface-assisted laser desorption/ionization mass spectrometric detection (SALDI/MS) was developed. After the DLLME, posaconazole was detected using SALDI/MS with colloidal gold and α-cyano-4-hydroxycinnamic acid (CHCA) as the co-matrix. Under optimal extraction and detection conditions, the calibration curve, which ranged from 1.0 to 100.0 nM for posaconazole, was observed to be linear. The limit of detection (LOD) at a signal-to-noise ratio of 3 was 0.3 nM for posaconazole. This novel method was successfully applied to the determination of posaconazole in human urine samples.

  2. Determination of N-nitrosamines by automated dispersive liquid-liquid microextraction integrated with gas chromatography and mass spectrometry.

    PubMed

    Amayreh, Mousa; Chanbasha, Basheer; Alhooshani, Khalid; Mu'azu, Nuhu Dalhat; Lee, Hian Kee

    2015-05-01

    An automated dispersive liquid-liquid microextraction integrated with gas chromatography and mass spectrometric procedure was developed for the determination of three N-nitrosamines (N-nitroso-di-n-propylamine, N-nitrosopiperidine, and N-nitroso di-n-butylamine) in water samples. Response surface methodology was employed to optimize relevant extraction parameters including extraction time, dispersive solvent volume, water sample pH, sodium chloride concentration, and agitation (stirring) speed. The optimal dispersive liquid-liquid microextraction conditions were 28 min of extraction time, 33 μL of methanol as dispersive solvent, 722 rotations per minute of agitation speed, 23% w/v sodium chloride concentration, and pH of 10.5. Under these conditions, good linearity for the analytes in the range from 0.1 to 100 μg/L with coefficients of determination (r(2) ) from 0.988 to 0.998 were obtained. The limits of detection based on a signal-to-noise ratio of 3 were between 5.7 and 124 ng/L with corresponding relative standard deviations from 3.4 to 5.9% (n = 4). The relative recoveries of N-nitroso-di-n-propylamine, N-nitrosopiperidine, and N-nitroso di-n-butylamine from spiked groundwater and tap water samples at concentrations of 2 μg/L of each analyte (mean ± standard deviation, n = 3) were (93.9 ± 8.7), (90.6 ± 10.7), and (103.7 ± 8.0)%, respectively. The method was applied to determine the N-nitrosamines in water samples of different complexities, such as tap water, and groundwater, before and after treatment, in a local water treatment plant.

  3. Analysis of Whiskey by Dispersive Liquid-Liquid Microextraction Coupled with Gas Chromatography/Mass Spectrometry: An Upper Division Analytical Chemistry Experiment Guided by Green Chemistry

    ERIC Educational Resources Information Center

    Owens, Janel E.; Zimmerman, Laura B.; Gardner, Michael A.; Lowe, Luis E.

    2016-01-01

    Analysis of whiskey samples prepared by a green microextraction technique, dispersive liquid-liquid microextraction (DLLME), before analysis by a qualitative gas chromatography-mass spectrometry (GC/MS) method, is described as a laboratory experiment for an upper division instrumental methods of analysis laboratory course. Here, aroma compounds in…

  4. Analysis of Whiskey by Dispersive Liquid-Liquid Microextraction Coupled with Gas Chromatography/Mass Spectrometry: An Upper Division Analytical Chemistry Experiment Guided by Green Chemistry

    ERIC Educational Resources Information Center

    Owens, Janel E.; Zimmerman, Laura B.; Gardner, Michael A.; Lowe, Luis E.

    2016-01-01

    Analysis of whiskey samples prepared by a green microextraction technique, dispersive liquid-liquid microextraction (DLLME), before analysis by a qualitative gas chromatography-mass spectrometry (GC/MS) method, is described as a laboratory experiment for an upper division instrumental methods of analysis laboratory course. Here, aroma compounds in…

  5. A gold-gold oil microtrench electrode for liquid-liquid anion transfer voltammetry.

    PubMed

    Dale, Sara E C; Chan, Yohan; Bulman Page, Philip C; Barnes, Edward O; Compton, Richard G; Marken, Frank

    2013-07-01

    Two flat gold electrodes are placed vis-à-vis with an epoxy spacer layer that is etched out to give a ca. 100 μm-deep electrochemically active trench. A water-insoluble oil phase, here the redox system N,N-diethyl-N'N'-didodecyl-phenylenediamine (DDPD) in 4-(3-phenylpropyl)-pyridine (PPP), is immobilized into the trench to allow anion transfer upon oxidation of DDPD (oil) to DDP⁺ (oil). In "mono-potentiostatic mode" quantitative transfer/expulsion of anions into the trench oil phase occurs. However, in "bi-potentiostatic mode" feedback currents dominated by rapid plate-to-plate diffusion normal to the electrode surfaces are observed. Comparison of "normal" diffusion and "lateral" diffusion shows that the rate of diffusion-migration charge transport across the oil film is anion hydrophobicity dependent.

  6. Electrochemical Sensing and Imaging Based on Ion Transfer at Liquid/Liquid Interfaces

    PubMed Central

    Amemiya, Shigeru; Kim, Jiyeon; Izadyar, Anahita; Kabagambe, Benjamin; Shen, Mei; Ishimatsu, Ryoichi

    2013-01-01

    Here we review the recent applications of ion transfer (IT) at the interface between two immiscible electrolyte solutions (ITIES) for electrochemical sensing and imaging. In particular, we focus on the development and recent applications of the nanopipet-supported ITIES and double-polymer-modified electrode, which enable the dynamic electrochemical measurements of IT at nanoscopic and macroscopic ITIES, respectively. High-quality IT voltammograms are obtainable using either technique to quantitatively assess the kinetics and dynamic mechanism of IT at the ITIES. Nanopipet-supported ITIES serves as an amperometric tip for scanning electrochemical microscopy to allow for unprecedentedly high-resolution electrochemical imaging. Voltammetric ion sensing at double-polymer-modified electrodes offers high sensitivity and unique multiple-ion selectivity. The promising future applications of these dynamic approaches for bioanalysis and electrochemical imaging are also discussed. PMID:24363454

  7. Accelerated solvent extraction combined with dispersive liquid-liquid microextraction before gas chromatography with mass spectrometry for the sensitive determination of phenols in soil samples.

    PubMed

    Xing, Han-Zhu; Wang, Xia; Chen, Xiang-Feng; Wang, Ming-Lin; Zhao, Ru-Song

    2015-05-01

    A method combining accelerated solvent extraction with dispersive liquid-liquid microextraction was developed for the first time as a sample pretreatment for the rapid analysis of phenols (including phenol, m-cresol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol) in soil samples. In the accelerated solvent extraction procedure, water was used as an extraction solvent, and phenols were extracted from soil samples into water. The dispersive liquid-liquid microextraction technique was then performed on the obtained aqueous solution. Important accelerated solvent extraction and dispersive liquid-liquid microextraction parameters were investigated and optimized. Under optimized conditions, the new method provided wide linearity (6.1-3080 ng/g), low limits of detection (0.06-1.83 ng/g), and excellent reproducibility (<10%) for phenols. Four real soil samples were analyzed by the proposed method to assess its applicability. Experimental results showed that the soil samples were free of our target compounds, and average recoveries were in the range of 87.9-110%. These findings indicate that accelerated solvent extraction with dispersive liquid-liquid microextraction as a sample pretreatment procedure coupled with gas chromatography and mass spectrometry is an excellent method for the rapid analysis of trace levels of phenols in environmental soil samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Dispersive liquid-liquid microextraction combined with capillary electrophoresis and time-of-flight mass spectrometry for urine analysis.

    PubMed

    Kohler, Isabelle; Schappler, Julie; Sierro, Tatiana; Rudaz, Serge

    2013-01-25

    The combination of dispersive liquid-liquid microextraction (DLLME) with capillary electrophoresis (CE) and a time-of-flight mass spectrometer (TOF-MS) was evaluated for the toxicological screening in urine samples. A methodology based on design of experiments (DOE) was implemented to increase the extraction efficiency. Dichloromethane and isopropanol were selected as the extraction and dispersing solvents, respectively. Seven factors for DLLME were screened with the help of a Plackett-Burmann DOE using two model compounds before fine investigation of the important parameters to maximise the compound extraction. These experiments were performed in the CE-UV configuration to overcome potential MS matrix effects. The performance of the entire procedure was then evaluated using CE-ESI-TOF-MS. With a preconcentration factor of more than 130, the highly sensitive DLLME-CE-ESI-TOF-MS method allowed for the detection of 30 toxicological compounds (i.e., amphetamines and their derivatives, opiates, cocaine and its metabolites and pharmaceuticals) in urine with limits of detection in the sub-ng/mL level and was used to analyse real toxicological samples. The combination of DLLME and CE was particularly attractive because of the small amount of organic solvents required.

  9. Determination of Levetiracetam in Human Plasma by Dispersive Liquid-Liquid Microextraction Followed by Gas Chromatography-Mass Spectrometry

    PubMed Central

    2016-01-01

    Levetiracetam (LEV) is an antiepileptic drug that is clinically effective in generalized and partial epilepsy syndromes. The use of this drug has been increasing in clinical practice and intra- or -interindividual variability has been exhibited for special population. For this reason, bioanalytical methods are required for drug monitoring in biological matrices. So this work presents a dispersive liquid-liquid microextraction method followed by gas chromatography-mass spectrometry (DLLME-GC-MS) for LEV quantification in human plasma. However, due to the matrix complexity a previous purification step is required. Unlike other pretreatment techniques presented in the literature, for the first time, a procedure employing ultrafiltration tubes Amicon® (10 kDa porous size) without organic solvent consumption was developed. GC-MS analyses were carried out using a linear temperature program, capillary fused silica column, and helium as the carrier gas. DLLME optimized parameters were type and volume of extraction and dispersing solvents, salt addition, and vortex agitation time. Under chosen parameters (extraction solvent: chloroform, 130 μL; dispersing solvent: isopropyl alcohol, 400 μL; no salt addition and no vortex agitation time), the method was completely validated and all parameters were in agreement with the literature recommendations. LEV was quantified in patient's plasma sample using less than 550 μL of organic solvent. PMID:27830105

  10. Dual dispersive liquid-liquid microextraction for determination of phenylpropenes in oils by gas chromatography-mass spectrometry.

    PubMed

    Tsai, Chia-Ju; Li, Jih-Heng; Feng, Chia-Hsien

    2015-09-04

    A novel, simple and quick sample preparation method was developed and used for pre-concentration and extraction of six phenylpropenes, including anethole, estragole, eugenol, methyl eugenol, safrole and myristicin, from oil samples by dual dispersive liquid-liquid microextraction. Gas chromatography-mass spectrometry was used for determination and separation of compounds. Several experimental parameters affecting extraction efficiency were evaluated and optimized, including forward-extractant type and volume, surfactant type and concentration, water volume, and back-extractant type and volume. For all analytes (10-1000ng/mL), the limits of detection (S/N≧3) ranged from 1.0 to 3.0ng/mL; the limits of quantification (S/N≧10) ranged from 2.5 to 10.0ng/mL; and enrichment factors ranged from 3.2 to 37.1 times. Within-run and between-run relative standard deviations (n=6) were less than 2.61% and less than 4.33%, respectively. Linearity was excellent with determination coefficients (r(2)) above 0.9977. The experiments showed that the proposed method is a simple, effective, and environmentally friendly method of analyzing phenylpropenes in oil samples.

  11. Quantitative determination of methamphetamine in oral fluid by liquid-liquid extraction and gas chromatography/mass spectrometry.

    PubMed

    Bahmanabadi, L; Akhgari, M; Jokar, F; Sadeghi, H B

    2017-02-01

    Methamphetamine abuse is one of the most medical and social problems many countries face. In spite of the ban on the use of methamphetamine, it is widely available in Iran's drug black market. There are many analytical methods for the detection of methamphetamine in biological specimen. Oral fluid has become a popular specimen to test for the presence of methamphetamine. The purpose of the present study was to develop a method for the extraction and detection of methamphetamine in oral fluid samples using liquid-liquid extraction (LLE) and gas chromatography/mass spectrometry (GC/MS) methods. An analytical study was designed in that blank and 50 authentic oral fluid samples were collected to be first extracted by LLE and subsequently analysed by GC/MS. The method was fully validated and showed an excellent intra- and inter-assay precision (reflex sympathetic dystrophy ˂ 10%) for external quality control samples. Recovery with LLE methods was 96%. Limit of detection and limit of quantitation were 5 and 15 ng/mL, respectively. The method showed high selectivity, no additional peak due to interfering substances in samples was observed. The introduced method was sensitive, accurate and precise enough for the extraction of methamphetamine from oral fluid samples in forensic toxicology laboratories.

  12. A 96-well single-pot liquid-liquid extraction, hydrophilic interaction liquid chromatography-mass spectrometry method for the determination of muraglitazar in human plasma.

    PubMed

    Xue, Y-J; Liu, Jane; Unger, Steve

    2006-06-07

    A single-pot liquid-liquid extraction (LLE) with hydrophilic interaction liquid chromatography/tandem mass spectrometry (HILIC/MS/MS) method has been developed and validated for the determination of muraglitazar, a hydrophobic diabetes drug, in human plasma. To 0.050 ml of each plasma sample in a 96-well plate, the internal standard solution in acetonitrile and toluene were added to extract the compound of interest. The plate was vortexed, followed by centrifugation. The organic layer was then directly injected into an LC/MS/MS system. Chromatographic separation was achieved isocratically on a Thermohypersil_Keystone, Hypersil silica column (3 mmx50 mm, 3 microm). The mobile phase contained 85% of methyl t-butyl ether and 15% of 90/10 (v/v) acetonitrile/water with 0.3% trifluoroacetic acid. Post-column mobile phase of 50/50 (v/v) acetonitrile/water containing 0.1% formic acid was added. Detection was by positive ion electrospray tandem mass spectrometry on a Sciex API 4000. The standard curve, ranged from 1 to 1000 ng/ml, was fitted to a 1/x weighted quadratic regression model. This single-pot LLE approach effectively eliminated time-consuming organic layer transfer, dry-down, and sample reconstitution steps, which are essential for a conventional liquid-liquid extraction procedure. The modified mobile phase was more compatible with the direct injection of the commonly used extraction solvents in LLE. Furthermore, the modified mobile phase improved the retention of muraglitazar, a hydrophobic compound, on the normal phase silica column. The validation results demonstrated that this method was rugged and suitable for analyzing muraglitazar in human plasma. In comparison with a revised-phase LC/MS/MS method, this single-pot LLE, HILIC/MS/MS method improved the detection sensitivity by more than four-fold based upon the LLOQ signal to noise ratio. This approach may be applied to other hydrophobic compounds with proper modification of the mobile phase compositions.

  13. Estrogenic compounds determination in water samples by dispersive liquid-liquid microextraction and micellar electrokinetic chromatography coupled to mass spectrometry.

    PubMed

    D'Orazio, Giovanni; Asensio-Ramos, María; Hernández-Borges, Javier; Fanali, Salvatore; Rodríguez-Delgado, Miguel Ángel

    2014-05-30

    In this work, a group of 12 estrogenic compounds, i.e., four natural sexual hormones (estrone, 17β-estradiol, 17α-estradiol and estriol), an exoestrogen (17α-ethynylestradiol), a synthetic stilbene (dienestrol), a mycotoxin (zearalenone) and some of their major metabolites (2-methoxyestradiol, α-zearalanol, β-zearalanol, α-zearalenol and β-zearalenol) have been separated and determined by micellar electrokinetic chromatography (MEKC) coupled to electrospray ion trap mass spectrometry. For this purpose, a background electrolyte containing an aqueous solution of 45 mM of perfluorooctanoic acid (PFOA) adjusted to pH 9.0 with an ammonia solution, as MS friendly surfactant, and methanol (10% (v/v)), as organic modifier, was used. To further increase the sensitivity, normal stacking mode was applied by injecting the sample dissolved in an aqueous solution of 11.5mM of ammonium PFO (APFO) at pH 9.0 containing 10% (v/v) of methanol for 25s. Dispersive liquid-liquid microextraction, using 110 μL of chloroform and 500 μL of acetonitrile as extraction and dispersion solvents, respectively, was employed to extract and preconcentrate the target analytes from different types of environmental water samples (mineral, run-off and wastewater) containing 30% (w/v) NaCl and adjusted to pH 3.0 with 1M HCl. The limits of detection achieved were in the range 0.04-1.10 μg/L. The whole method was validated in terms of linearity, precision, recovery and matrix effect for each type of water, showing determination coefficients higher than 0.992 for matrix-matched calibration and absolute recoveries in the range 43-91%. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Comprehensive Profiling of Phytohormones in Honey by Sequential Liquid-Liquid Extraction Coupled with Liquid Chromatography-Mass Spectrometry.

    PubMed

    Wang, Qing; Cai, Wen-Jing; Yu, Lei; Ding, Jun; Feng, Yu-Qi

    2017-01-25

    Honey exhibits various nutritional and medicinal functions, which are highly related to the active components; thus, the exploration of new compounds in honey is of great importance. Because honey is a byproduct of flower nectar, which is rich in phytohormones, the existence of phytohormones in honey is anticipated. In this research, a method for comprehensive profiling of 49 phytohormones in honey was developed by sequential liquid-liquid extraction (LLE) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Good linearities for 49 phytohormones were obtained with correlation coefficients (R) larger than 0.9913. The limits of detection (LODs) were in the range of 0.2-628.2 pg/mL. Satisfied reproducibility and reliability were achieved by evaluation of the intra- and interday precisions with relative standard deviations (RSDs) less than 15.8% and relative recoveries ranging from 80.4 to 123.7%. The method was further applied to analyze the phytohormones in 14 monofloral raw honey samples and 3 commercial honey samples. The existence of 34 phytohormones was confirmed, including 14 cytokinins (CKs), 8 gibberellins (GAs), 5 brassinosteroids (BRs), indole-3-acetic acid (IAA), indole-3-butyric acid (IBA), abscisic acid (ABA), salicylic acid (SA), jasmonic acid (JA), jasmonoyl-leucine (JA-Leu), and jasmonoyl-phenylalanine (JA-Phe). In addition, the content and species of phytohormones varies in different kinds of honey. The study is beneficial to fully illustrate the phytohormone profile of honey and contributive to elucidate the mechanism of its nutritional and medicinal functions.

  15. Determination of organochlorine pesticides in water samples by dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry.

    PubMed

    Cortada, Carol; Vidal, Lorena; Pastor, Raul; Santiago, Noemi; Canals, Antonio

    2009-09-07

    A rapid and simple dispersive liquid-liquid microextraction (DLLME) has been developed to preconcentrate eighteen organochlorine pesticides (OCPs) from water samples prior to analysis by gas chromatography-mass spectrometry (GC-MS). The studied variables were extraction solvent type and volume, disperser solvent type and volume, aqueous sample volume and temperature. The optimum experimental conditions of the proposed DLLME method were: a mixture of 10 microL tetrachloroethylene (extraction solvent) and 1 mL acetone (disperser solvent) exposed for 30 s to 10 mL of the aqueous sample at room temperature (20 degrees C). Centrifugation of cloudy solution was carried out at 2300 rpm for 3 min to allow phases separation. Finally, 2 microL of extractant was recovered and injected into the GC-MS instrument. Under the optimum conditions, the enrichment factors ranged between 46 and 316. The calculated calibration curves gave a high-level linearity for all target analytes with correlation coefficients ranging between 0.9967 and 0.9999. The repeatability of the proposed method, expressed as relative standard deviation, varied between 5% and 15% (n=8), and the detection limits were in the range of 1-25 ng L(-1). The LOD values obtained are able to detect these OCPs in aqueous matrices as required by EPA methods 525.2 and 625. Analysis of spiked real water samples revealed that the matrix had no effect on extraction for river, surface and tap waters; however, urban wastewater sample shown a little effect for five out of eighteen analytes.

  16. Dispersive liquid-liquid microextraction method based on solidification of floating organic drop combined with gas chromatography with electron-capture or mass spectrometry detection.

    PubMed

    Leong, Mei-I; Huang, Shang-Da

    2008-11-21

    A simple dispersive liquid-liquid microextraction (DLLME) method based on solidification of a floating organic drop (DLLME-SFO) technique combined with gas chromatography/electron-capture detection (GC/ECD) or gas chromatography/mass spectrometry (GC/MS) has been developed. The proposed method is simple, low in cost, and of high precision. It overcomes the most important problem in DLLME, the high-toxic solvent used. Halogenated organic compounds (HOCs) in water samples were determined as the model compounds. The parameters optimized for the DLLME-SFO technique were as follows: A mixture of 0.5 mL acetone, containing 10 microL 2-dodecanol (2-DD-OH), was rapidly injected by syringe into the 5 mL water sample. After centrifugation, the fine 2-DD-OH droplets (8+/-0.5 microL) were floated at the top of the screwcap test tube. The test tube was then cooled in an ice bath. After 5 min the 2-DD-OH solvent had solidified and was then transferred into a conical vial; it melted quickly at room temperature and 3 microL (for GC/ECD) or 2 microL (for GC/MS) of it was injected into a gas chromatograph for analysis. The limit of detection (LOD) for this technique was 0.005-0.05microgL(-1) for GC/ECD and was 0.005-0.047 microgL(-1) for GC/MS, respectively. The linear range of the calibration curve of DLLME-SFO was from 0.01 to 500 microgL(-1) with a coefficient of estimation (r2)>0.996 for GC/ECD and was from 0.02 to 500 microgL(-1) with a coefficient of estimation (r2)>0.996 for GC/MS.

  17. In-syringe magnetic stirring-assisted dispersive liquid-liquid microextraction and silylation prior gas chromatography-mass spectrometry for ultraviolet filters determination in environmental water samples.

    PubMed

    Clavijo, Sabrina; Avivar, Jessica; Suárez, Ruth; Cerdà, Víctor

    2016-04-22

    A novel online approach involving in-syringe magnetic stirring assisted dispersive liquid-liquid microextraction and derivatization coupled to gas chromatography-mass spectrometry has been developed for the determination of seven UV filters extensively used in cosmetic products in environmental water samples. The effect of parameters such as the type and volume of extraction solvent, dispersive solvent and derivatization agent, pH, ionic strength and stirring time, was studied using multivariate experimental design. Extraction, derivatization and preconcentration were simultaneously performed using acetone as dispersive solvent, N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) as derivatization agent and trichloroethylene as extraction solvent. After stirring during 160s, the sedimented phase was transferred to a rotary micro-volume injection valve (3 μL) and introduced by an air stream into the injector of the GC through a stainless-steel tube used as interface. The detection limits were in the range of 0.023-0.16 μg L(-1) and good linearity was observed up to 500 μg L(-1) of the studied UV filters, with R(2) ranging between 0.9829 and 0.9963. The inter-day precision expressed as relative standard deviation (n=5) varied between 5.5 and 16.8%. Finally, the developed method was satisfactorily applied to assess the occurrence of the studied UV filters in seawater and pool water samples. Some of the studied UV filters were found in these samples and an add-recovery test was also successfully performed with recoveries between 82 and 111%. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Determination of benzotriazoles in water samples by concurrent derivatization-dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Casado, J; Nescatelli, R; Rodríguez, I; Ramil, M; Marini, F; Cela, R

    2014-04-04

    Concurrent acetylation-dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography-mass spectrometry (GC-MS) has been proposed for the sensitive determination of five polar benzotriazolic compounds (1H-benzotriazole, BTri; 4 and 5-methyl-1H-benzotriazole, 4-TTri and 5-TTri; 5,6-dimethyl-1H-benzotriazole, XTri; and 5-chloro-1H-benzotriazole, 5-ClBTri) in water samples. Under optimized conditions, samples (10 mL volume) were combined with 1 mL of Na2HPO4 (8%, w/v) and mixed with the ternary acetylation-microextraction mixture, consisting of 100 μL of acetic anhydride, 1.5 mL of acetonitrile and 60 μL of toluene. Thus, analytes were simultaneously acetylated and transferred to the dispersed droplets of toluene. The proposed methodology achieved limits of quantification (LOQs) between 0.007 ng mL(-1) and 0.080 ng mL(-1), enrichment factors between 93 and 172 times, good reproducibility, with relative standard deviations lower than 10%, and linearity with determination coefficients above 0.9991 for all compounds in the range between LOQs and 20 ng mL(-1). Pseudo-external calibration, with fortified ultrapure water samples submitted to the acetylation-DLLME procedure, proved to be adequate for the accurate quantification of complex aqueous matrices such as surface or wastewater, providing recoveries comprised between 86% and 112%. BTri, 4-TTri and 5-TTri were measured in environmental samples up to a concentration of 1.9 ng mL(-1) for BTri in raw wastewater.

  19. Determination of chlorobenzenes in textiles by pressurized hot water extraction followed by vortex-assisted liquid-liquid microextraction and gas chromatography-mass spectrometry.

    PubMed

    Lu, Yang; Zhu, Yan

    2013-12-06

    A method for quantitative determination of chlorobenzenes in textiles is developed, using pressurized hot water extraction (PHWE), vortex-assisted liquid-liquid microextraction (VALLME) and gas chromatography-mass spectrometry (GC-MS). VALLME serves as a trapping step after PHWE. The extraction conditions are investigated, as well as the quantitative features such as linearity, limits of detection (LODs), limits of quantification (LOQs), repeatabilities and reproducibilities between days. LOQs of 0.018-0.032mg/kg were achieved. The present method provides good repeatabilities (RSD<6.9%) and demonstrates that PHWE-VALLME-GC-MS is a simple, rapid and environmentally friendly method for determination of chlorobenzenes in textiles.

  20. [Determination of fatty acid esters of chloropropanediols in diet samples by gas chromatography-mass spectrometry coupled with solid-supported liquid-liquid extraction].

    PubMed

    Gao, Jie; Liu, Qing; Han, Feng; Miao, Hong; Zhao, Yunfeng; Wu, Yongning

    2014-05-01

    To establish a method for the determination of fatty acid esters of 3-monochloropropane-1, 2-diol (3-MCPD) and 2-monochloropropane-1, 3-diol (2-MCPD) in diet samples by gas chromatography-mass spectrometry (GC-MS) with solid-supported liquid-liquid extraction (SLE). Diet samples were ultrasonically extracted by hexane, followed by ester cleavage reaction with sodium methylate in methanol, and then purified by solid-supported liquid-liquid extraction. (SLE) using diatomaceous earth as the sorbent. After derivatization with heptafluorobutyrylimidazole, the analytes were detected by GC-MS and quantified by the deuterated internal standards. The limits of detection (LODs) of 3-MCPD esters and 2-MCPD esters in different diet samples were 0.002 - 0.005 mg/kg and 0.002 - 0.006 mg/kg. The average recoveries of 3-MCPD esters and 2-MCPD esters at the spiking levels of 0.05 and 0.1 mg/kg in the diet samples were in the range of 65.9% - 104.2% and 75.4% - 118.0%, respectively, with the relative standard deviations in the range of 2.2% - 14.2% and 0.8% - .13.9%. The method is simple, accurate and rugged for the determination of fatty acid esters of 3-MCPD and 2-MCPD in diet samples.

  1. Assessment of dispersive liquid-liquid microextraction conditions for gas chromatography time-of-flight mass spectrometry identification of organic compounds in honey.

    PubMed

    Moniruzzaman, M; Rodríguez, I; Rodríguez-Cabo, T; Cela, R; Sulaiman, S A; Gan, S H

    2014-11-14

    The suitability of the dispersive liquid-liquid microextraction (DLLME) technique for gas chromatography (GC) characterization of minor organic compounds in honey samples is evaluated. Under optimized conditions, samples were pre-treated by liquid-liquid extraction with acetonitrile followed by DLLME using carbon tetrachloride (CCl4, 0.075 mL) as extractant. The yielded settled phase was analyzed by GC using high resolution time-of-flight (TOF) mass spectrometry (MS). The whole sample preparation process is completed in approximately 10 min, with a total consumption of organic solvents below 4 mL, relative standard deviations lower than 12% and with more than 70 organic compounds, displaying linear retention index in the range from 990 to 2900, identified in the obtained extracts. In comparison with HS SPME extraction, higher peak intensities were attained for most volatile and semi-volatile compounds amenable to both extraction techniques. Furthermore, other species such as highly polar and water soluble benzene acids, long chain fatty acids, esters and flavonoids, which are difficult to concentrate by HS SPME, could be identified in DLLME extracts. Some of the compounds identified in DLLME extracts have been proposed as useful for samples classification and/or they are recognized as markers of honeys from certain geographic areas. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Dispersive liquid-liquid microextraction and injection-port derivatization for the determination of free lipophilic compounds in fruit juices by gas chromatography-mass spectrometry.

    PubMed

    Marsol-Vall, Alexis; Balcells, Mercè; Eras, Jordi; Canela-Garayoa, Ramon

    2017-04-28

    A method consisting of dispersive liquid-liquid microextraction (DLLME) followed by injection-port derivatization and gas chromatography-mass spectrometry (GC-MS) for the analysis of free lipophilic compounds in fruit juices is described. The method allows the analysis of several classes of lipophilic compounds, such as fatty acids, fatty alcohols, phytosterols and triterpenes. The chromatographic separation of the compounds was achieved in a chromatographic run of 25.5min. The best conditions for the dispersive liquid-liquid microextraction were 100μL of CHCl3 in 1mL of acetone. For the injection-port derivatization, the best conditions were at 280°C, 1min purge-off, and a 1:1 sample:derivatization reagent ratio (v/v) using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA):pyridine (1:1) as reagent. Quality parameters were assessed for the target compounds, giving a limits of detection (LODs) ranging from 1.1 to 5.7ng/mL and limits of quantification (LOQs) from 3.4 to 18.7ng/mL for linoleic and stearic acid, respectively. Repeatability (%RSD, n=5) was below 11.51% in all cases. In addition, the method linearity presented an r(2) ≥0.990 for all ranges applied. Finally, the method was used to test the lipophilic fraction of various samples of commercial fruit juice.

  3. Optimization of two different dispersive liquid-liquid microextraction methods followed by gas chromatography-mass spectrometry determination for polycyclic aromatic hydrocarbons (PAHs) analysis in water.

    PubMed

    Tseng, Wan-Chi; Chen, Pai-Shan; Huang, Shang-Da

    2014-03-01

    Novel sample preparation methods termed "up-and-down shaker-assisted dispersive liquid-liquid microextraction (UDSA-DLLME)" and "water with low concentration of surfactant in dispersed solvent-assisted emulsion dispersive liquid-liquid microextraction (WLSEME)" coupled with gas chromatography-mass spectrometry (GC-MS) have been developed for the analysis of 11 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. For UDSA-DLLME, an up-and-down shaker-assisted emulsification was employed. Extraction was complete in 3min. Only 14 μL of 1-heptanol was required, without a dispersive solvent. Under the optimum conditions, the linear range was 0.08-100 µg L(-1), and the LODs were in the range 0.022-0.060 µg L(-1). The enrichment factors (EFs) ranged from 392 to 766. Relative recoveries were between 84% and 113% for river, lake, and field water. In WLSEME, 9 μL of 1-nonanol as extraction solvent and 240 μL of 1 mg L(-1) Triton X-100 as surfactant were mixed in a microsyringe to form a cloudy emulsified solution, which was then injected into the samples. Compared with other surfactant-assisted emulsion methods, WLSEME uses much less surfactant. The linear range was 0.08-100 µg L(-1), and the LODs were 0.022-0.13 µg L(-1). The EFs ranged from 388 to 649. The relative recoveries were 86-114% for all three water specimens.

  4. Determination of atranol and chloroatranol in perfumes using simultaneous derivatization and dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    López-Nogueroles, Marina; Chisvert, Alberto; Salvador, Amparo

    2014-05-15

    A new analytical method based on simultaneous derivatization and dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography-mass spectrometry (GC-MS), for the determination of the allergenic compounds atranol and chloroatranol in perfumes, is presented. Derivatization of the target analytes by means of acetylation with anhydride acetic in carbonate buffer was carried out. Thereby volatility and detectability were increased for improved GC-MS sensitivity. In addition, extractability by DLLME was also enhanced due to a less polar character of the solutes. A liquid-liquid extraction was performed before DLLME to clean up the sample and to obtain an aqueous sample solution, free of the low polar matrix from the essential oils, as donor phase. Different parameters, such as the nature and volume of both the extraction and disperser solvents, the ionic strength of the aqueous donor phase or the effect of the derivatization reagent volume, were optimized. Under the selected conditions (injection of a mixture of 750μL of acetone as disperser solvent, 100μL of chloroform as extraction solvent and 100μL of anhydride acetic as derivatization reagent) the figures of merit of the proposed method were evaluated. Limits of detection in the low ngmL(-1) range were obtained. Matrix effect was observed in real perfume samples and thus, standard addition calibration is recommended.

  5. Suitability of dispersive liquid-liquid microextraction for the in situ silylation of chlorophenols in water samples before gas chromatography with mass spectrometry.

    PubMed

    Saraji, Mohammad; Ghambari, Hoda

    2015-10-01

    Trace analysis of chlorophenols in water was performed by simultaneous silylation and dispersive liquid-liquid microextraction followed by gas chromatography with mass spectrometry. Dispersive liquid-liquid microextraction was carried out using an organic solvent lighter than water (n-hexane). The effect of different silylating reagents on the method efficiency was investigated. The influence of derivatization reagent volume, presence of catalyst and derivatization/extraction time on the yield of the derivatization reaction was studied. Different parameters affecting extraction efficiency such as kind and volume of extraction and disperser solvents, pH of the sample and addition of salt were also investigated and optimized. Under the optimum conditions, the calibration graphs were linear in the range of 0.05-100 ng/mL and the limit of detection was 0.01 ng/mL. The enrichment factors were 242, 351, and 363 for 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol, respectively. The values of intra- and inter-day relative standard deviations were in the range of 3.0-6.4 and 6.1-9.9%, respectively. The applicability of the method was investigated by analyzing water and wastewater samples.

  6. PREFACE: Functionalized Liquid Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Girault, Hubert; Kornyshev, Alexei A.; Monroe, Charles W.; Urbakh, Michael

    2007-09-01

    Most natural processes take place at interfaces. For this reason, surface science has been a focal point of modern research. At solid-liquid interfaces one can induce various species to adsorb or react, and thus may study interactions between the substrate and adsorbates, kinetic processes, optical properties, etc. Liquid-liquid interfaces, formed by immiscible liquids such as water and oil, have a number of distinctive features. Both sides of the interface are amenable to detailed physical and chemical analysis. By chemical or electrochemical means, metal or semiconductor nanoparticles can be formed or localised at the interface. Surfactants can be used to tailor surface properties, and also to place organic molecular or supermolecular constructions at the boundary between the liquids. Electric fields can be used to drive ions from one fluid to another, or even change the shape of the interface itself. In many cases, both liquids are optically transparent, making functionalized liquid-liquid interfaces promising for various optical applications based on the transmission or reflection of light. An advantage common to most of these systems is self-assembly; because a liquid-liquid interface is not mechanically constrained like a solid-liquid interface, it can easily access its most stable state, even after it has been driven far from equilibrium. This special issue focuses on four modes of liquid-liquid interfacial functionalization: the controlled adsorption of molecules or nanoparticles, the formation of adlayers or films, electrowetting, and ion transfer or interface-localized reactions. Interfacial adsorption can be driven electrically, chemically, or mechanically. The liquid-liquid interface can be used to study how anisotropic particles orient at a surface under the influence of a field, how surfactants interact with other adsorbates, and how nanoparticles aggregate; the transparency of the interface also makes the chirality of organic adsorbates amenable to

  7. Determination of Macrolide Antibiotics Using Dispersive Liquid-Liquid Microextraction Followed by Surface-Assisted Laser Desorption/Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chen, Kuan-Yu; Yang, Thomas C.; Chang, Sarah Y.

    2012-06-01

    A novel method for the determination of macrolide antibiotics using dispersive liquid-liquid microextraction coupled to surface-assisted laser desorption/ionization mass spectrometric detection was developed. Acetone and dichloromethane were used as the disperser solvent and extraction solvent, respectively. A mixture of extraction solvent and disperser solvent were rapidly injected into a 1.0 mL aqueous sample to form a cloudy solution. After the extraction, macrolide antibiotics were detected using surface-assisted laser desorption/ionization mass spectrometry (SALDI/MS) with colloidal silver as the matrix. Under optimum conditions, the limits of detection (LODs) at a signal-to-noise ratio of 3 were 2, 3, 3, and 2 nM for erythromycin (ERY), spiramycin (SPI), tilmicosin (TILM), and tylosin (TYL), respectively. This developed method was successfully applied to the determination of macrolide antibiotics in human urine samples.

  8. Hyphenating size-exclusion chromatography with electrospray mass spectrometry; using on-line liquid-liquid extraction to study the lipid composition of lipoprotein particles.

    PubMed

    Osei, Michael; Griffin, Julian L; Koulman, Albert

    2015-11-15

    Lipoproteins belong to the most commonly measured clinical biochemical parameters. Lipidomics is an orthogonal approach and aims to profile the individual lipid molecules that jointly form the lipoprotein particles. However, in the first step of the extraction of lipid molecules from serum, an organic solvent is used leading to dissociation of the lipoproteins. Thus far it has been impossible to combine lipidomics and lipoprotein analysis in one analytical system. Human plasma was diluted in phosphate-buffered saline (PBS) and injected onto a Superose 6 PC 3.2 column with PBS as a mobile phase to separate lipoproteins. The eluent was led to a Syrris FLLEX module, which also received CHCl3 /MeOH (3:1). The two phases were mixed and subsequently separated using a Teflon membrane in an especially designed pressurized flow chamber. The organic phase was led to a standard electrospray source of an Orbitrap mass spectrometer. Size-exclusion chromatography (SEC) has been commonly applied to separate lipoproteins and is considered a practical alternative to ultracentrifugation. Through the on-line liquid-liquid extraction method it becomes possible to obtained detailed mass spectra of lipids across different lipoprotein fractions. The extracted ion chromatograms of specific lipid signals showed their distribution against the size of lipoprotein particles. The application of on-line liquid-liquid extraction allows for the continuous electrospray-based mass spectral analysis of SEC eluent, providing the detailed lipid composition of lipoprotein particles separated by size. This approach provides new possibilities for the study of the biochemistry of lipoproteins. © 2015 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd.

  9. Sonication effect on the reaction of 4-bromo-1-methylbenzene with sodium sulfide in liquid-liquid multi-site phase-transfer catalysis condition - kinetic study.

    PubMed

    Abimannan, Pachaiyappan; Selvaraj, Varathan; Rajendran, Venugopal

    2015-03-01

    The synthesis of di-p-tolylsulfane from the reaction of 4-bromo-1-methylbenzene (BMB) with sodium sulfide was carried out using a multi-site phase-transfer catalyst (MPTC) viz., 1,4-dihexyl-1,4-diazoniabicyclo[2.2.2]octanium dibromide and ultrasonic irradiation in a liquid-liquid reaction condition. The overall reaction rate is greatly enhanced when catalyzed by multi-site phase-transfer catalyst (MPTC) combined with sonication (40 kHz, 300 W) in a batch reactor than catalyzed by MPTC without sonication. Effects on the reaction due to various operating conditions, such as agitation speed, different ultrasound frequencies, different phase-transfer catalysts, different organic solvents, the amount of MPTC, temperature, amount of sodium sulfide, effect of sodium hydroxide, volume of n-hexane and the concentration of 4-bromo-1-methylbenzene. The reaction obeys a pseudo first-order rate law and a suitable mechanism was proposed based on the experimental observation. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Monitoring pesticide residues in greenhouse tomato by combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by gas-chromatography-mass spectrometry.

    PubMed

    Melo, Armindo; Cunha, Sara C; Mansilha, Catarina; Aguiar, Ana; Pinho, Olívia; Ferreira, Isabel M P L V O

    2012-12-01

    A multiclass and multiresidue method for pesticide analysis in tomato was validated. Extraction and pre-concentration of the pesticide residues from acetonitrile extracts was performed by using dispersive liquid-liquid microextraction (DLLME) technique, followed by gas chromatography-mass detection. DLLME was performed using carbon tetrachloride as extractive solvent and acetonitrile extract as dispersive solvent, in order to increase enrichment factor of the extraction procedure. Validation parameters indicated the suitability of the method for routine analyses of thirty pesticides in a large number of samples. In general, pesticide recoveries ranged between 70% and 110% and repeatability ranged between 1% and 20%. The proposed method was applied to the monitoring of pesticides in tomatoes grown during winter in greenhouses. Among the compounds considered in this work, cyprodinil was found in tomato at concentrations of 0.33mg/kg, other pesticides like azoxystrobin, fenhexanid, tolyfluanid, λ-cyhalothrin and trifloxystrobin were also detected, but, not quantified.

  11. Detection of digoxin in urine samples by surface-assisted laser desorption/ionization mass spectrometry with dispersive liquid-liquid microextraction.

    PubMed

    Cheng, Mei-Ching; Chi, Kai-Ming; Chang, Sarah Y

    2013-10-15

    A novel method for the detection of digoxin using dispersive liquid-liquid microextraction (DLLME) coupled to the surface-assisted laser desorption/ionization mass spectrometric detection (SALDI/MS) was developed. Acetone and chloroform were used as the disperser solvent and extraction solvents, respectively. After the extraction, digoxin was detected using SALDI/MS with colloidal palladium as the matrix. Under optimal extraction and detection conditions, the calibration curve, which ranged from 0.01 to 0.50 μM, was observed to be linear. The limit of detection (LOD) at a signal-to-noise ratio of 3 was 2 nM for digoxin. With a sample-to-extract volume ratio of 400, the enrichment factor for digoxin was calculated to be 252. This novel method was successfully applied for the determination of digoxin in human urine samples.

  12. Determination of spirocyclic tetronic/tetramic acid derivatives and neonicotinoid insecticides in fruits and vegetables by liquid chromatography and mass spectrometry after dispersive liquid-liquid microextraction.

    PubMed

    Pastor-Belda, Marta; Garrido, Isabel; Campillo, Natalia; Viñas, Pilar; Hellín, Pilar; Flores, Pilar; Fenoll, José

    2016-07-01

    Dispersive liquid-liquid microextraction was used to preconcentrate three spirocyclic tetronic/tetramic acid derivatives (spirotetramat, spiromesifen and spirodiclofen) and five neonicotinoid (thiamethoxam, chlotianidin, imidacloprid, acetamiprid and thiacloprid) insecticides previously extracted from fruit and vegetable matrices with acetonitrile. The organic enriched phase was evaporated, reconstituted in 25μL acetonitrile and analyzed by reversed-phase liquid chromatography with tandem mass spectrometry using a triple quadrupole in selected reaction monitoring mode. Enrichment factors in the 15-100 range were obtained. A matrix effect was observed, the detection limits varying between 0.025 and 0.5ngg(-1), depending on the compound and the sample matrix. The developed method was applied to the analysis of 25 samples corresponding to five different fruit and vegetable matrices. Only thiamethoxam was detected in a lemon sample at a concentration close to the quantification limit, and spiromesifen and spirotetramat at concentrations between 11.6 and 54.5ngg(-1).

  13. Vortex-assisted surfactant-enhanced emulsification liquid-liquid microextraction for the determination of carbamates in juices by micellar electrokinetic chromatography tandem mass spectrometry.

    PubMed

    Moreno-González, David; Huertas-Pérez, José F; García-Campaña, Ana M; Gámiz-Gracia, Laura

    2015-07-01

    A new method based on vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction has been developed for the extraction of carbamate pesticides in juice samples prior to their determination by micellar electrokinetic chromatography coupled to tandem mass spectrometry. This sample treatment allowed the satisfactory extraction and the extract clean-up of 25 carbamates from different fruit and vegetal juices (banana, tomato, and peach). In this study, the addition of ammonium perfluorooctanoate in the aqueous sample in combination with vortex agitation, provided very clean extracts with short extraction times. Under optimized conditions, recoveries of the proposed method for these pesticides from fortified juice samples ranged from 81% to 104%, with relative standard deviations lower than 15%. Limits of quantification were between 2.3µgkg(-)(1) and 4.7µgkg(-)(1), showing the high sensitivity of this fast and simple method.

  14. Solvent-based de-emulsification dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry for determination of trace organochlorine pesticides in environmental water samples.

    PubMed

    Zacharis, Constantinos K; Tzanavaras, Paraskevas D; Roubos, Konstantinos; Dhima, Kico

    2010-09-17

    In this work, we propose solvent-based de-emulsification dispersive liquid-liquid microextraction (SD-DLLME) as a simple, rapid and efficient sample pretreatment technique for the extraction and preconcentration of organochlorine pesticides (OCPs) from environmental water samples. Separation and analysis of fifteen OCPs was carried out by gas chromatography-mass spectrometry (GC/MS). Parameters affecting the extraction efficiency were systematically investigated. The detection limits were in the range of 2-50 ng L(-1) using selective ion monitoring (SIM). The precision of the proposed method, expressed as relative standard deviation, varied between 3.5 and 10.2% (n=5). Results from the analysis of spiked environmental water samples at the low-ppb level met the acceptance criteria set by the EPA.

  15. Chiral separation by enantioselective liquid-liquid extraction.

    PubMed

    Schuur, Boelo; Verkuijl, Bastiaan J V; Minnaard, Adriaan J; de Vries, Johannes G; Heeres, Hero J; Feringa, Ben L

    2011-01-07

    The literature on enantioselective liquid-liquid extraction (ELLE) spans more than half a century of research. Nonetheless, a comprehensive overview has not appeared during the past few decades. Enantioselective liquid-liquid extraction is a technology of interest for a wide range of chemists and chemical engineers in the fields of fine chemicals, pharmaceuticals, agrochemicals, fragrances and foods. In this review the principles and advances of resolution through enantioselective liquid-liquid extraction are discussed, starting with an introduction on the principles of enantioselective liquid-liquid extraction including host-guest chemistry, extraction and phase transfer mechanisms, and multistage liquid-liquid extraction processing. Then the literature on enantioselective liquid-liquid extraction systems is reviewed, structured on extractant classes. The following extractant classes are considered: crown ether based extractants, metal complexes and metalloids, extractants based on tartrates, and a final section with all other types of chiral extractants.

  16. Recombination, dissociation, and transport of ion pairs across the liquid/liquid interface. implications for phase transfer catalysis.

    PubMed

    Benjamin, Ilan

    2013-04-25

    Molecular dynamics simulations are used to calculate several free energy profiles relevant to the recombination/dissociation and transport of individual ions and ion pairs across the water/chloroform interface. Tetra methyl ammonium (TMA(+)) and tetra butyl ammonium (TBA(+)) (typically used as phase transfer catalysts) and a chloride ion (as an example of a transferred nucleophile) are considered. The free-energy profiles for the transfer of the three ions and the two ion pairs (TMA(+)Cl(-) and TBA(+)Cl(-)) across the interface, as well as the potential of mean force for the dissociation of these two ion pairs at different interface locations, are calculated and correlated with structural and energetic changes at the interface. These equilibrium calculations, together with nonequilibrium trajectory calculations, provide molecular insight into the mechanism of phase transfer catalysis. In particular, water surface fluctuations are strongly coupled to the ion-pair location along the interface normal and the ion-pair bond length.

  17. Determination of ultraviolet filters in water samples by vortex-assisted dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Zhang, Yufeng; Lee, Hian Kee

    2012-08-03

    For the first time, a simple solvent microextraction method termed vortex-assisted liquid-liquid microextraction (VADLLME) coupled with gas chromatography-mass spectrometry (GC-MS) has been developed and used for the analysis of six benzophenone ultraviolet (UV) filters (i.e. benzhydrol, 2,4-dihydroxybenzophenone, benzophenone, 2-hydroxy-4-methoxybenzophenone, ethylhexyl salicylate and homosalate) in water samples. The most favorable extraction variables in the VADLLME process were determined. In the extraction procedure, 40 μL of tetrachloroethene as extraction solvent were directly injected into a 15-mL centrifuge tube containing 10 mL of aqueous sample, adjusted to pH 4 for VADLLME. After VADLLME, the extract was evaporated under a gentle nitrogen gas stream and then reconstituted with N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA), thus allowing the target analytes to be converted into their trimethylsilyl derivatives to optimize the GC-MS analysis. No centrifugation and disperser solvent were required in this microextraction procedure. Significantly, short extraction time and high extraction efficiency were achieved. This method opens up a potentially new horizon for on-site dispersive liquid-liquid microextraction. Under the optimum conditions, the proposed method provided good enrichment factors up to 310, with relative standard deviations ranging from 6.1 to 12.9%. The limits of quantification were in the range of 20-100 ng/L, depending on the analytes. The linearities were between 0.05 and 10 μg/L and 0.1 and 10 μg/L for different UV filters. Finally, the proposed method was successfully applied to the determination of UV filters from spiked genuine water samples and acceptable recoveries over the range of 71.0-120.0% were obtained.

  18. Analyses of polychlorinated biphenyls in waters and wastewaters using vortex-assisted liquid-liquid microextraction and gas chromatography-mass spectrometry.

    PubMed

    Ozcan, Senar

    2011-03-01

    A method was developed for viable and rapid determination of seven polychlorinated biphenyls (PCBs) in water samples with vortex-assisted liquid-liquid microextraction (VALLME) using gas chromatography-mass spectrometry (GC-MS). At first, the most suitable extraction solvent and extraction solvent volume were determined. Later, the parameters affecting the extraction efficiency such as vortex extraction time, rotational speed of the vortex, and ionic strength of the sample were optimized by using a 2(3) factorial experimental design. The optimized extraction conditions for 5 mL water sample were as follows: extractant solvent 200 μL of chloroform; vortex extraction time of 2 min at 3000 rpm; centrifugation 5 min at 4000 rpm, and no ionic strength. Under the optimum condition, limits of detection (LOD) ranged from 0.36 to 0.73 ng/L. Mean recoveries of PCBs from fortified water samples are 96% for three different fortification levels and RSDs of the recoveries are below 5%. The developed procedure was successfully applied to the determination of PCBs in real water and wastewater samples such as tap, well, surface, bottled waters, and municipal, treated municipal, and industrial wastewaters. The performance of the proposed method was compared with traditional liquid-liquid extraction (LLE) of real water samples and the results show that efficiency of proposed method is comparable to the LLE. However, the proposed method offers several advantages, i.e. reducing sample requirement for measurement of target compounds, less solvent consumption, and reducing the costs associated with solvent purchase and waste disposal. It is also viable, rapid, and easy to use for the analyses of PCBs in water samples by using GC-MS.

  19. Quantification of candidate prostate cancer metabolite biomarkers in urine using dispersive derivatization liquid-liquid microextraction followed by gas and liquid chromatography-mass spectrometry.

    PubMed

    Shamsipur, Mojtaba; Naseri, Mohammad Taghi; Babri, Mehran

    2013-01-01

    A simple, rapid and sensitive method based on dispersive derivatization liquid-liquid microextraction (DDLLME) combined with gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS) was developed and validated for the determination of prostate cancer metabolite biomarkers, including sarcosine, alanine, leucine and proline, in human urine samples. Dispersive derivatization using isobutyl chloroformate has been successfully employed to identify the amino acids of interest in ng mL(-1) concentrations. Under the optimum experimental conditions, the detection limits of the amino acids were in the range of 0.05-0.1 ng mL(-1). The enrichment factor and relative recovery for the target amino acids were in the range of 140-155 and 93.8-106%, respectively. The proposed method showed good linearity (correlation coefficients >0.997), and good intra-day (below 7%) and inter-day precision (below 10%). This protocol provides a rapid, simple, selective and sensitive tool to quantify sarcosine and endogenous urinary metabolite for prostate cancer diagnosis and for a screening test. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Dispersive liquid-liquid microextraction for the determination of flavonoid aglycone compounds in honey using liquid chromatography with diode array detection and time-of-flight mass spectrometry.

    PubMed

    Campillo, Natalia; Viñas, Pilar; Férez-Melgarejo, Gema; Hernández-Córdoba, Manuel

    2015-01-01

    A rapid approach for the determination of eight flavonoid aglycone compounds, baicalein, hesperitin, fisetin, naringenin, chrysin, myricetin, quercetin and kaempferol, in honey samples and related products has been optimized and validated. The enriched extracts obtained by dispersive liquid-liquid microextraction (DLLME) were analyzed by liquid chromatography with diode array detection coupled to electrospray ionization and time-of-flight mass spectrometry (LC-DAD-ESI-ToFMS). For DLLME, using acetonitrile and chloroform as disperser and extractant solvents, respectively, a Taguchi experimental method was applied to find the optimal combination of following six factors: disperser and extractant solvent volumes, sodium chloride concentration, pH of the aqueous phase, honey mass and centrifugation time. The sedimented organic phase obtained after centrifugation was evaporated, reconstituted in acetonitrile and submitted to LC. The matrix effect was evaluated, and it was concluded that sample quantification can be carried out against aqueous external standards when using DAD and by matrix-matched calibration in the case of ToFMS. Detection limits in the ranges of 0.4-4 and 0.01-0.5 ng g(-1) were obtained for DAD and ToFMS, respectively. Satisfactory recovery values between 80 and 111% were obtained for three spiked samples. Honeys and related products were analyzed and flavonoids were found within a wide range.

  1. Simultaneous determination of plant hormones in peach based on dispersive liquid-liquid microextraction coupled with liquid chromatography-ion trap mass spectrometry.

    PubMed

    Lu, Qiaomei; Zhang, Wenmin; Gao, Jia; Lu, Minghua; Zhang, Lan; Li, Jianrong

    2015-06-15

    Fruit development is influenced greatly by endogenous hormones including salicylic acid (SA) and abscisic acid (ABA). Mass spectrometry with high sensitivity has become a routine technology to analyze hormones. However, pretreatment of plant samples remains a difficult problem. Thus, dispersive liquid-liquid microextraction (DLLME) was used to concentrate trace plant hormones before liquid chromatography-ion trap mass spectrometry (LC-ITMS) analysis. Standard curves were linear within the ranges of 0.5-50, 0.2-20ng/mL for SA and ABA, respectively. The correlation coefficients were greater than 0.9995 with recoveries above 87.5%. The limits of detection were 0.2ng/mL for SA and 0.1ng/mL for ABA in spiked water solution, respectively (injection 20μL). The successful analysis of SA and ABA in fruit samples indicated our DLLME-LC-ITMS approach was efficient, allowing reliable quantification of both two compounds from very small amounts of plant material. Moreover, this research revealed the relationship between SA and ABA content and development of peach fruit at different growth stages. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Determination of cannabinoid and synthetic cannabinoid metabolites in wastewater by liquid-liquid extraction and ultrahigh performance supercritical fluid chromatography-tandem mass spectrometry.

    PubMed

    González-Mariño, Iria; Thomas, Kevin V; Reid, Malcolm J

    2017-03-31

    For the first time, ultrahigh performance supercritical fluid chromatography (UHPSFC) coupled to tandem mass spectrometry has been used to determine cannabinoid and synthetic cannabinoid residues in wastewater. Combined with a downscaled version of the classical liquid-liquid extraction, the proposed method allows for the quantification of ∆9-tetrahydrocannabinol, three of its major metabolites (the monohydroxylated, the dihydroxylated and the carboxylated species) and four synthetic cannabinoid metabolites (from the JWH-series) at low ng L(-1) levels. Limits of quantification are in the 1-59 ng L(-1) range, with recovery between 62 and 122% in ultrapure water and between 59 and 138% in wastewater. The applicability of the developed methodology was confirmed by the analysis of real wastewater, where cannabis metabolites could be positively quantified in all the samples analyzed. It is, therefore, a fast and simple alternative to common solid-phase extraction-liquid chromatography-mass spectrometry procedures for the determination of these low polar substances in water.

  3. Ceria nanocubic-ultrasonication assisted dispersive liquid-liquid microextraction coupled with matrix assisted laser desorption/ionization mass spectrometry for pathogenic bacteria analysis.

    PubMed

    Abdelhamid, Hani Nasser; Bhaisare, Mukesh L; Wu, Hui-Fen

    2014-03-01

    A new ceria (CeO2) nanocubic modified surfactant is used as the basis of a novel nano-based microextraction technique for highly sensitive detection of pathogenic bacteria (Pseudomonas aeruginosa and Staphylococcus aureus). The technique uses ultrasound enhanced surfactant-assisted dispersive liquid-liquid microextraction (UESA-DLLME) with and without ceria (CeO2) followed by matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS). In order to achieve high separation efficiency, we investigated the influential parameters, including extraction time of ultrasonication, type and volume of the extraction solvent and surfactant. Among various surfactants, the cationic surfactants can selectively offer better extraction efficiency on bacteria analysis than that of the anionic surfactants due to the negative charges of bacteria cell membranes. Extractions of the bacteria lysate from aqueous samples via UESA-DLLME-MALDI-MS were successfully achieved by using cetyltrimethyl ammonium bromide (CTAB, 10.0 µL, 1.0×10(-3) M) as surfactants in chlorobenzene (10.0 µL) and chloroform (10.0 µL) as the optimal extracting solvent for P. aeruginosa and S. aureus, respectively. Ceria nanocubic was synthesized, and functionalized with CTAB (CeO2@CTAB) and then characterized using transmission electron microscopy (TEM) and optical spectroscopy (UV and FTIR). CeO2@CTAB demonstrates high extraction efficiency, improve peaks ionization, and enhance resolution. The prime reasons for these improvements are due to the large surface area of nanoparticles, and its absorption that coincides with the wavelength of MALDI laser (337 nm, N2 laser). CeO2@CTAB-based microextraction offers lowest detectable concentrations tenfold lower than that of without nanoceria. The present approach has been successfully applied to detect pathogenic bacteria at low concentrations of 10(4)-10(5) cfu/mL (without ceria) and at 10(3)-10(4) cfu/mL (with ceria) from bacteria suspensions. Finally, the

  4. Determination of Wastewater Compounds in Whole Water by Continuous Liquid-Liquid Extraction and Capillary-Column Gas Chromatography/Mass Spectrometry

    USGS Publications Warehouse

    Zaugg, Steven D.; Smith, Steven G.; Schroeder, Michael P.

    2006-01-01

    A method for the determination of 69 compounds typically found in domestic and industrial wastewater is described. The method was developed in response to increasing concern over the impact of endocrine-disrupting chemicals on aquatic organisms in wastewater. This method also is useful for evaluating the effects of combined sanitary and storm-sewer overflow on the water quality of urban streams. The method focuses on the determination of compounds that are indicators of wastewater or have endocrine-disrupting potential. These compounds include the alkylphenol ethoxylate nonionic surfactants, food additives, fragrances, antioxidants, flame retardants, plasticizers, industrial solvents, disinfectants, fecal sterols, polycyclic aromatic hydrocarbons, and high-use domestic pesticides. Wastewater compounds in whole-water samples were extracted using continuous liquid-liquid extractors and methylene chloride solvent, and then determined by capillary-column gas chromatography/mass spectrometry. Recoveries in reagent-water samples fortified at 0.5 microgram per liter averaged 72 percent ? 8 percent relative standard deviation. The concentration of 21 compounds is always reported as estimated because method recovery was less than 60 percent, variability was greater than 25 percent relative standard deviation, or standard reference compounds were prepared from technical mixtures. Initial method detection limits averaged 0.18 microgram per liter. Samples were preserved by adding 60 grams of sodium chloride and stored at 4 degrees Celsius. The laboratory established a sample holding-time limit prior to sample extraction of 14 days from the date of collection.

  5. Determination of cyclic and linear siloxanes in wastewater samples by ultrasound-assisted dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Cortada, Carol; dos Reis, Luciana Costa; Vidal, Lorena; Llorca, Julio; Canals, Antonio

    2014-03-01

    A fast, simple and environmentally friendly ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) procedure has been developed to preconcentrate eight cyclic and linear siloxanes from wastewater samples prior to quantification by gas chromatography-mass spectrometry (GC-MS). A two-stage multivariate optimization approach has been developed employing a Plackett-Burman design for screening and selecting the significant factors involved in the USA-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were: extractant solvent volume, 13 µL; solvent type, chlorobenzene; sample volume, 13 mL; centrifugation speed, 2300 rpm; centrifugation time, 5 min; and sonication time, 2 min. Under the optimized experimental conditions the method gave levels of repeatability with coefficients of variation between 10 and 24% (n=7). Limits of detection were between 0.002 and 1.4 µg L(-1). Calculated calibration curves gave high levels of linearity with correlation coefficient values between 0.991 and 0.9997. Finally, the proposed method was applied for the analysis of wastewater samples. Relative recovery values ranged between 71 and 116% showing that the matrix had a negligible effect upon extraction. To our knowledge, this is the first time that combines LLME and GC-MS for the analysis of methylsiloxanes in wastewater samples.

  6. Determination of bisphenol A in water by micro liquid-liquid extraction followed by silylation and gas chromatography-mass spectrometry analysis.

    PubMed

    González-Casado, A; Navas, N; del Olmo, M; Vílchez, J L

    1998-11-01

    A method for the determination of bisphenol A according to the European Union guideline, which establishes a limit of 0.1 ng/mL for organic pollutants in water, is proposed. The method involves a micro liquid-liquid extraction using dichloromethane followed by a silylation step. Identification and quantitation are performed with gas chromatography-mass spectrometry, using an HP-5MS column. The retention time is 7.02 min. Quantitation is carried out using single-ion monitoring (SIM) at m/z 73, 357, and 372. A clean-up is not necessary using SIM mode. Deuterated anthracene (2H10-anthracene) is used as an internal standard. The method is applied to the determination of bisphenol A at very low concentration levels (10.0-250.0 ng/L) in different types of natural water samples. The detection limit obtained is 0.4 ng/L. Recovery efficiencies are close to 100% in all cases.

  7. Trace analysis of herbicides in wastewaters by a dispersive liquid-liquid microextraction approach and liquid chromatography with quadrupole linear ion trap mass spectrometry: evaluation of green parameters.

    PubMed

    del Mar Parrilla Vázquez, Maria; Martínez Galera, Maria; Parrilla Vázquez, Piedad; Uclés Moreno, Ana

    2014-06-01

    An analytical method for determining phenylureas (monuron, isoproturon, diuron, linuron and neburon) and propanil herbicides in wastewater has been developed and validated, and the most significant parameters were compared with the corresponding ones found in the literature, thus showing the method performance. The method involves pre-concentration by a simple, rapid, sensitive and low environmental toxicity temperature-controlled ionic liquid dispersive liquid-liquid microextraction procedure. The herbicides were identified and determined by liquid chromatography with a hybrid triple quadrupole linear ion trap mass spectrometer. Data acquisition in selected-reaction monitoring mode allowed the simultaneous identification and quantification of the analytes using two transitions. The information dependent acquisition scan was performed to carry out the identification of those analytes whose second transition was present at low intensity, also providing extra confirmation for the other analytes. Limits of quantification were in the range 1.0-5.0 ng/L. Good recoveries (95-103%) were obtained for the extraction of the target analytes in wastewater samples. The methodology developed was applied to analyze effluent wastewater samples from a wastewater treatment plant located in an agricultural zone of Almería (Spain) and the results indicated the presence of diuron at mean concentration levels of 73.5 ng/L.

  8. Membrane-assisted liquid-liquid extraction coupled with gas chromatography-mass spectrometry for determination of selected polycyclic musk compounds and drugs in water samples.

    PubMed

    Einsle, T; Paschke, H; Bruns, K; Schrader, S; Popp, P; Moeder, M

    2006-08-18

    Selected polycyclic musk compounds and drugs were extracted from water samples by membrane-assisted micro liquid-liquid extraction. The two-phase extraction system consisted of polyethylene membrane bags filled with an organic solvent. Chloroform proved to be most suited as acceptor phase to extract caffeine, Galaxolide, Tonalide, phenazone and carbamazepine from aqueous samples. The compounds were enriched from 50 mL sample into a volume of 500 microL of chloroform. Gas chromatography-mass spectrometry (GC-MS) was applied for analysis. The extraction procedure was optimised in regard to membrane material, extraction time and temperature. The evaluation of the entire analysis protocol found limits of detection that ranged from 20 to 200 ng/L. The linear range of calibration covered one magnitude with standard deviations between 4 and 12%. Method comparison with standard analysis techniques such as solid-phase extraction (SPE) combined with GC-MS as well as LC-MS-MS confirmed this method as an easy and reliable protocol, even for the monitoring of matrix-loaded wastewater. The analysis of real samples established the feasibility of the technique.

  9. Combination of solvent extractants for dispersive liquid-liquid microextraction of fungicides from water and fruit samples by liquid chromatography with tandem mass spectrometry.

    PubMed

    Pastor-Belda, Marta; Garrido, Isabel; Campillo, Natalia; Viñas, Pilar; Hellín, Pilar; Flores, Pilar; Fenoll, José

    2017-10-15

    A multiresidue method was developed to determine twenty-five fungicides belonging to three different chemical families, oxazoles, strobilurins and triazoles, in water and fruit samples, using dispersive liquid-liquid microextraction (DLLME) and liquid chromatography/tandem mass spectrometry (LC-MS(2)). Solid-liquid extraction with acetonitrile was used for the analysis in fruits, the extract being used as dispersant solvent in DLLME. Since some of the analytes showed high affinity for chloroform and the others were more efficiently extracted with undecanol, a mixture of both solvents was used as extractant in DLLME. After evaporation of CHCl3, the enriched phase was analyzed. Enrichment factors in the 23-119 and 12-60 ranges were obtained for waters and fruits, respectively. The approach was most sensitive for metominostrobin with limits of quantification of 1ngL(-1) and 5ngkg(-1) in waters and fruits, respectively, while a similar sensitivity was attained for tebuconazole in fruits. Recoveries of the fungicides varied between 86 and 116%. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Determination of Fusarium toxins in functional vegetable milks applying salting-out-assisted liquid-liquid extraction combined with ultra-high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Hamed, Ahmed M; Arroyo-Manzanares, Natalia; García-Campaña, Ana M; Gámiz-Gracia, Laura

    2017-09-06

    Vegetable milks are considered as functional foods due to their physiological benefits. Although the consumption of these products has significantly increased, they have received little attention in legislation with regard to contaminants. However, they may contain mycotoxins resulting from the use of contaminated raw materials. In this work, ultra-high-performance liquid chromatography tandem mass spectrometry has been proposed for the determination of the most relevant Fusarium toxins (fumonisin B1 and B2, HT-2 and T-2 toxins, zearalenone, deoxynivalenol and fusarenon-X) in different functional beverages based on cereals, legumes and seeds. Sample treatment consisted of a simple salting-out-assisted liquid-liquid extraction with no further clean-up. The method provided limits of quantification between 3.2 and 57.7 µg L(-1), recoveries above 80% and precision with RSD lower than 12%. The method was also applied for studying the occurrence of these mycotoxins in market samples of vegetable functional beverages and deoxynivalenol was found in three oat-based commercial drinks.

  11. Rapid screening of haloacetamides in water using salt-assisted liquid-liquid extraction coupled injection-port silylation gas chromatography-mass spectrometry.

    PubMed

    Chen, Tzu-Ling; Tzing, Shin-Hwa; Ding, Wang-Hsien

    2015-11-27

    The rapid screening of trace amounts of the nitrogenous disinfection by-products, haloacetamides (HAcAms), in drinking and swimming pool water was performed by a simple and reliable procedure based on salt-assisted liquid-liquid extraction (SALLE) combined with injection-port silylation gas chromatography-mass spectrometry (IPS-GC-MS) method. The optimal SALLE conditions involved the injection of 4-mL of ethyl acetate into a 10-mL water sample (pH 7) containing 3-g of sodium sulfate. After vortex extraction for 1min and centrifugation, 10μL of the extract (mixed with 1μL of MTBSTFA) was directly determined by IPS-GC-MS. The limits of quantitation (LOQs) were determined to be 0.03-0.3μg/L. Precision, as indicated by relative standard deviations (RSDs), was less than 10% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 76% and 94%. The SALLE plus IPS-GC-MS was successfully applied to quantitatively determine HAcAms from drinking and swimming pool water samples, and the total concentrations of the compounds ranged from 0.43 to 4.03μg/L. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Simultaneous determination of dextromethorphan, dextrorphan, and guaifenesin in human plasma using semi-automated liquid/liquid extraction and gradient liquid chromatography tandem mass spectrometry.

    PubMed

    Eichhold, Thomas H; McCauley-Myers, David L; Khambe, Deepa A; Thompson, Gary A; Hoke, Steven H

    2007-01-17

    A method for the simultaneous determination of dextromethorphan (DEX), dextrorphan (DET), and guaifenesin (GG) in human plasma was developed, validated, and applied to determine plasma concentrations of these compounds in samples from six clinical pharmacokinetic (PK) studies. Semi-automated liquid handling systems were used to perform the majority of the sample manipulation including liquid/liquid extraction (LLE) of the analytes from human plasma. Stable-isotope-labeled analogues were utilized as internal standards (ISTDs) for each analyte to facilitate accurate and precise quantification. Extracts were analyzed using gradient liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Use of semi-automated LLE with LC-MS/MS proved to be a very rugged and reliable approach for analysis of more than 6200 clinical study samples. The lower limit of quantification was validated at 0.010, 0.010, and 1.0 ng/mL of plasma for DEX, DET, and GG, respectively. Accuracy and precision of quality control (QC) samples for all three analytes met FDA Guidance criteria of +/-15% for average QC accuracy with coefficients of variation less than 15%. Data from the thorough evaluation of the method during development, validation, and application are presented to characterize selectivity, linearity, over-range sample analysis, accuracy, precision, autosampler carry-over, ruggedness, extraction efficiency, ionization suppression, and stability. Pharmacokinetic data are also provided to illustrate improvements in systemic drug and metabolite concentration-time profiles that were achieved by formulation optimization.

  13. Determination of Earthy-musty Odorous Compounds in Drinking Water by Vortex Assisted Dispersive Liquid-Liquid Microextraction Combined with Gas Chromatography Tandem Mass Spectrometry.

    PubMed

    Lu, Jian; Wu, Zhong-Ping; Che, Wen-Jun; Xian, Yan-Ping; Guo, Xin-Dong; Lv, Jia-Xin; Li, He

    2016-01-01

    A new method was developed for the determination of eight earthy-musty compounds in drinking water by gas chromatography tandem mass spectrometry (GC-MS/MS) combined with dispersive liquid-liquid microextraction (DLLME). In this work, the type and volume of extraction solvent and dispersion agent, and the amount of NaCl were optimized; the linearity, detection limit, recovery and precision of method were investigated. The results indicated that the target analytes were in the range of 0.2 - 100 μg/L with correlation coefficient (r) ranging from 0.9991 to 0.9999, the limit of detection (LOD, S/N = 3) of the analytes ranged from 0.2 to 1.0 ng/L with the enrichment factor of 320. The mean recoveries for drinking water at three spiked concentrations levels of 0.6 - 32 ng/L were in the range of 91.3 to 103%, the precision ranged from 3.1 to 7.5% (n = 6), and the inter-day precision was from 6.1 to 11.1% (n = 5). Only one of 15 selected real samples tested positive for GSM, and the concentration was 3 ng/L. This method was confirmed to be simple, fast, efficient, and accurate for the determination of earthy-musty compounds in aqueous samples.

  14. Dispersive Liquid-Liquid Microextraction Combined with Ultrahigh Performance Liquid Chromatography/Tandem Mass Spectrometry for Determination of Organophosphate Esters in Aqueous Samples

    PubMed Central

    Luo, Haiying; Xian, Yanping; Guo, Xindong; Luo, Donghui; Lu, Yujing; Yang, Bao

    2014-01-01

    A new technique was established to identify eight organophosphate esters (OPEs) in this work. It utilised dispersive liquid-liquid microextraction in combination with ultrahigh performance liquid chromatography/tandem mass spectrometry. The type and volume of extraction solvents, dispersion agent, and amount of NaCl were optimized. The target analytes were detected in the range of 1.0–200 µg/L with correlation coefficients ranging from 0.9982 to 0.9998, and the detection limits of the analytes were ranged from 0.02 to 0.07 µg/L (S/N = 3). The feasibility of this method was demonstrated by identifying OPEs in aqueous samples that exhibited spiked recoveries, which ranged between 48.7% and 58.3% for triethyl phosphate (TEP) as well as between 85.9% and 113% for the other OPEs. The precision was ranged from 3.2% to 9.3% (n = 6), and the interprecision was ranged from 2.6% to 12.3% (n = 5). Only 2 of the 12 selected samples were tested to be positive for OPEs, and the total concentrations of OPEs in them were 1.1 and 1.6 µg/L, respectively. This method was confirmed to be simple, fast, and accurate for identifying OPEs in aqueous samples. PMID:24616613

  15. Simple field-based automated dispersive liquid-liquid microextraction of trace level phthalate esters in natural waters with gas chromatography and mass spectrometric analysis.

    PubMed

    Leng, Geng; Chen, Wenjin; Wang, Yong

    2016-09-01

    A small, simple, and field-based automated dispersive liquid-liquid microextraction method followed by gas chromatography mass spectrometric analysis was developed for trace level phthalate esters analysis in natural waters. With a single syringe pump that is coupled with a multiposition valve, the whole extraction procedure including cleaning, sampling, mixing of extractant and disperser solvents, extraction, phase separation, and analytes collection was carried out in a totally automated way with a sample throughput of 21 h(-1) . Key factors, such as type and ratio of the extractant and disperser solvent, aspiration flow rate, extraction time, and matrix effect, were thoroughly investigated. Under the optimum conditions, linearity was found in the range from 0.03 to 60 μg/L. Limits of detection ranged from 0.0015 to 0.003 μg/L. Enrichment factors were in a range of 106-141. Reproducibility and recoveries were assessed by testing a series of three natural water samples that were spiked with different concentration levels. Finally, the proposed method was successfully applied in analysis of real surface waters. The developed system is inexpensive, light (2.6 kg), simple to use, applicable in the field, with high sample throughput, and sensitive enough for trace level phthalate esters analysis in natural waters.

  16. Dispersive liquid-liquid microextraction for the determination of new generation pesticides in soils by liquid chromatography and tandem mass spectrometry.

    PubMed

    Pastor-Belda, Marta; Garrido, Isabel; Campillo, Natalia; Viñas, Pilar; Hellín, Pilar; Flores, Pilar; Fenoll, José

    2015-05-15

    A sensitive method for the determination of five new generation pesticides (chlorantraniliprole, spirotetramat, spiromesifen, spirodiclofen and flubendiamide) in soil samples has been developed using liquid chromatography and tandem mass spectrometry (LC-MS(2)) with a triple-quadrupole in the multiple reaction monitoring mode. The target analytes are released from the solid matrix by single-phase extraction in acetonitrile (SLE), this organic phase being used as dispersant solvent in the dispersive liquid-liquid microextraction (DLLME) step. The different parameters affecting the extraction efficiency in DLLME were carefully studied, being 1.5mL of acetonitrile extract (disperser solvent), 125μL carbon tetrachloride (extraction solvent) and 10mL aqueous solution, the selected conditions. The enriched organic phase was evaporated, reconstituted with 50μL acetonitrile and injected into a liquid chromatograph with a mobile phase composed of acetonitrile and 0.1% (v/v) formic acid under gradient elution and a C8 stationary phase. Detection limits in the 0.0015-0.0090ngg(-1) range were obtained. Insecticide concentrations ranging from 0.03 to 197ngg(-1), depending on the compound, were found in the soil samples analysed. The recovery values obtained by SLE-DLLME-LC-ESI-MS(2) for three spiked soils at three concentration levels varied between 87 and 114%, with RSDs of between 5.5 and 14%.

  17. [Simultaneous determination of 23 ester compounds in cigarette water-borne adhesives by liquid-liquid extraction and gas chromatography-mass spectrometry].

    PubMed

    Gong, Shuguo; Kong, Bo; Tuo, Suxing; Dai, Yunhui; Wu, Mingjian; Tan, Liquan; Liu, Wei

    2013-10-01

    A method of gas chromatography-mass spectrometry (GC-MS) with liquid-liquid extraction has been developed for the simultaneous determination of 23 ester compounds including acetate esters, acrylic esters, metacrylic acid esters and phthalate acid esters in cigarette water-borne adhesives. After dispersed in water, the sample was extracted by n-hexane solution containing phenyl ethyl propionate as internal standard substance. Then, the solution was centrifuged and filtrated through a 0.45 microm organic membrane filter. Finally, the solution was separated on a DB-WAXETR column (60 m x 0.25 mm x 0.25 microm), and detected with MS in selected ion monitoring mode, and quantified by internal standard method. The results showed a good linear correlation in the range of 0.4-50.0 mg/L. The recoveries of the ester compounds spiked in the sample were 81.8%-109.1%, and the relative standard deviations (RSDs, n = 5) were less than 4%. The limits of detection (LODs) and limits of quantification (LOQs were in the ranges of 0.02-0.76 mg/kg and 0.04-2.52 mg/kg, respectively. The method is simple, time-saving, and has high sensitivity and good reproducibility. It can be applied to the determination of the 23 ester compounds in cigarette water-borne adhesives.

  18. A novel aeration-assisted homogenous liquid-liquid microextration for determination of thorium and uranium in water and hair samples by inductively coupled plasma-mass spectroscopy.

    PubMed

    Veyseh, Somayeh; Niazi, Ali

    2016-01-15

    A novel method based on aeration-assisted homogeneous liquid-liquid microextraction using high density solvent is presented, which is combined with inductively coupled plasma-mass spectroscopy in which simultaneous preconcentration and determination of thorium and uranium with arsenazo III as the chelating reagent is carried out. To achieve optimum conditions, several parameters such as pH, concentration of arsenazo III, extraction and homogenous solvent types and their volumes, salt concentration and extraction time were investigated. Under which, the calibration graphs were linear in the range of 0.5-600.0ng L(-1) for thorium and 0.3-550.0ng L(-1) for uranium. Good linearities were obtained for both analytes with R(2) values larger than 0.9990. The limits of detection (LOD, 3Sb/m, n=5) of this method were 0.12 and 0.09ng L(-1), and the enrichment factors were estimated to be 370 and 410 for thorium and uranium, respectively. The proposed method was applied to determine the thorium and uranium in human hair and different environmental water samples. Acceptable recoveries ranged from 99.4% to 100.7% with standard deviation of 0.05 to 0.17. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Determination of 13 Organic Toxicants in Human Blood by Liquid-Liquid Extraction Coupling High-Performance Liquid Chromatography Tandem Mass Spectrometry.

    PubMed

    Song, Aiying

    2016-01-01

    Pesticides and antidepressants are frequently misused in drug-facilitated crime because of their toxicological effect and easy-availability. Therefore, it is essential for the development of a simple and reliable method for the determination of these organic toxicants in biological fluids. Here, we report on an applicable method by the combination of optimized liquid-liquid extraction (LLE) procedure and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to identify and quantify dimethoate, omethoate, dichlorvos, carbofuran, fenpropathrin, diazepam, estazolam, alprazolam, triazolamm, chlorpromazine, phenergan, barbitone and phenobarbital in human blood. The method demonstrated a linear calibration curve in range of 20 - 500 μg/L (r > 0.994). The accuracy evaluated by recovery spiked at three different concentrations (50, 100 and 200 μg/L) was in the range of 58.8 - 83.1% with a relative standard deviations (RSD) of 3.7 - 7.4%. The limits of quantification ranged over 6.7 - 33.3 μg/L. This method was proved to be simple and reliable, and was thus successfully applied to forensic toxicology.

  20. Speciation of mercury in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Jia, Xiaoyu; Han, Yi; Liu, Xinli; Duan, Taicheng; Chen, Hangting

    2011-01-01

    The dispersive liquid-liquid microextraction (DLLME) combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry for the speciation of mercury in water samples was described. Firstly methylmercury (MeHg +) and mercury (Hg 2+) were complexed with sodium diethyldithiocarbamate, and then the complexes were extracted into carbon tetrachloride by using DLLME. Under the optimized conditions, the enrichment factors of 138 and 350 for MeHg + and Hg 2+ were obtained from only 5.00 mL sample solution. The detection limits of the analytes (as Hg) were 0.0076 ng mL -1 for MeHg + and 0.0014 ng mL -1 for Hg 2+, respectively. The relative standard deviations for ten replicate measurements of 0.5 ng mL -1 MeHg + and Hg 2+ were 6.9% and 4.4%, respectively. Standard reference material of seawater (GBW(E)080042) was analyzed to verify the accuracy of the method and the results were in good agreement with the certified values. Finally, the developed method was successfully applied for the speciation of mercury in three environmental water samples.

  1. Simultaneous determination of hypericin and hyperforin in human plasma and serum using liquid-liquid extraction, high-performance liquid chromatography and liquid chromatography-tandem mass spectrometry.

    PubMed

    Pirker, R; Huck, C W; Bonn, G K

    2002-09-25

    A method for the simultaneous extraction of hypericin and hyperforin from a St. John's Wort extract, which is used in case of moderate depressions and skin injuries, from human plasma and serum by liquid-liquid extraction (LLE) with n-hexane-ethylacetate (70:30, w/w) was developed. A reversed-phase high-performance liquid chromatographic (RP-HPLC) method with UV, fluorescence (FLD) and mass spectrometric (MS) detection using electrospray ionization (ESI) was used to identify and quantify hypericin and hyperforin in the extracts from blood samples. Linearity was obtained in the ranges 8.4-28.7 ng/ml (hypericin) and 21.6-242.6 ng/ml (hyperforin). Recoveries were between 32.2 and 35.6% for hypericin and 100.1 and 89.9% for hyperforin. Intra-day accuracy and precision for this method ranged between 3.2 and 4.3% and 2.6 and 2.8%, respectively. After validation of the LLE, the method was tested on real plasma samples which were obtained by ingestion of St. John's Wort extract capsules. Blood samples were taken 2, 4, and 6 h after ingestion. Finally, this method proved to be highly suitable for clinical and pharmacologically relevant studies.

  2. Monitoring trihalomethanes in chlorinated waters using a dispersive liquid-liquid microextraction method with a non-chlorinated organic solvent and gas chromatography-mass spectrometry.

    PubMed

    Pacheco-Fernández, Idaira; Herrera-Fuentes, Ariadna; Delgado, Bárbara; Pino, Verónica; Ayala, Juan H; Afonso, Ana M

    2017-03-01

    The environmental monitoring of trihalomethanes (THMs) has been performed by setting up a dispersive liquid-liquid microextraction method in combination with gas chromatography (GC)-mass spectrometry (MS). The optimized method only requires ∼26 µL of decanol as extractant solvent, dissolved in ∼1 mL of acetone (dispersive solvent) for 5 mL of the environmental water containing THMs. The mixture is then subjected to vortex for 1 min and then centrifuged for 2 min at 3500 rpm. The microdroplet containing the extracted THMs is then sampled with a micro-syringe, and injected (1 µL) in the GC-MS. The method is characterized for being fast (3 min for the entire sample preparation step) and environmentally friendly (low amounts of solvents required, being all non-chlorinated), and also for getting average relative recoveries of 90.2-106% in tap waters; relative standard deviation values always lower than 11%; average enrichment factors of 48-49; and detection limits down to 0.7 µg·L-1. Several waters: tap waters, pool waters, and wastewaters were successfully analyzed with the method proposed. Furthermore, the method was used to monitor the formation of THMs in wastewaters when different chlorination parameters, namely temperature and pH, were varied.

  3. Dispersive liquid-liquid microextraction for the determination of nitrophenols in soils by microvial insert large volume injection-gas chromatography-mass spectrometry.

    PubMed

    Cacho, J I; Campillo, N; Viñas, P; Hernández-Córdoba, M

    2016-07-22

    A rapid and sensitive procedure for the determination of six NPs in soils by gas chromatography and mass spectrometry (GC-MS) is proposed. Ultrasound assisted extraction (UAE) is used for NP extraction from soil matrices to an organic solvent, while the environmentally friendly technique dispersive liquid-liquid microextraction (DLLME) is used for the preconcentration of the resulting UAE extracts. NPs were derivatized by applying an "in-situ" acetylation procedure, before being injected into the GC-MS system using microvial insert large volume injection (LVI). Several parameters affecting UAE, DLLME, derivatization and injection steps were investigated. The optimized procedure provided recoveries of 86-111% from spiked samples. Precision values of the procedure (expressed as relative standard deviation, RSD) lower than 12%, and limits of quantification ranging from 1.3 to 2.6ngg(-1), depending on the compound, were obtained. Twenty soil samples, obtained from military, industrial and agricultural areas, were analyzed by the proposed method. Two of the analytes were quantified in two of the samples obtained from industrial areas, at concentrations in the 4.8-9.6ngg(-1) range.

  4. Rapid determination of polycyclic aromatic hydrocarbons in grilled meat using microwave-assisted extraction and dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry.

    PubMed

    Kamankesh, Marzieh; Mohammadi, Abdorreza; Hosseini, Hedayat; Modarres Tehrani, Zohreh

    2015-05-01

    A simple and rapid analytical tech nique for the simultaneous determination of 16 polycyclic aromatic hydrocarbons (PAHs) in grilled meat was developed using microwave-assisted extraction and dispersive liquid-liquid microextraction (MAE-DLLME) followed by gas chromatography-mass spectrometry (GC-MS). The effective parameters in DLLME process were optimized. Good linear relationships were obtained for 16 PAHs in a range of 1-200 ng g(-1), with a correlation coefficient (R(2)) higher than 0.98. Limits of detection and limits of quantification were 0.15-0.3 ng g(-1) and 0.47-1 ng g(-1), respectively. The relative standard deviations (RSD%) for seven analyses were less than 9%. The recoveries of those compounds in grilled meat were obtained from 85% to 104%. Low consumption of the solvent, high recovery, short extraction time, no matrix interference and good merit figures compared to other methods are advantages of the proposed method. The performance of the present method was evaluated for the determination of PAHs in various types of real grilled meat samples, and satisfactory results were obtained.

  5. Determination of endocrine-disrupting compounds in water samples by magnetic nanoparticle-assisted dispersive liquid-liquid microextraction combined with gas chromatography-tandem mass spectrometry.

    PubMed

    Pérez, Rosa Ana; Albero, Beatriz; Tadeo, José Luis; Sánchez-Brunete, Consuelo

    2016-11-01

    A rapid extraction procedure is presented for the determination of five endocrine-disrupting compounds, estrone, ethinylestradiol, bisphenol A, triclosan, and 2-ethylhexylsalicylate, in water samples. The analysis involves a two-step extraction procedure that combines dispersive liquid-liquid microextraction (DLLME) with dispersive micro-solid phase extraction (D-μ-SPE), using magnetic nanoparticles, followed by in situ derivatization in the injection port of a gas chromatograph coupled to triple quadrupole mass spectrometry. The use of uncoated or oleate-coated Fe3O4 nanoparticles as sorbent in the extraction process was evaluated and compared. The main parameters involved in the extraction process were optimized applying experimental designs. Uncoated Fe3O4 nanoparticles were selected in order to simplify and make more cost-effective the procedure. DLLME was carried out at pH 3, during 2 min, followed by the addition of the nanoparticles for D-μ-SPE employing 1 min in the extraction. Analysis of spiked water samples of different sources gave satisfactory recovery results for all the compounds with detection limits ranging from 7 to 180 ng l(-1). Finally, the procedure was applied in tap, well, and river water. Graphical abstract Diagram of the extraction method using magnetic nanoparticles (MNPs).

  6. Ultrasound-assisted dispersive liquid-liquid microextraction for the determination of seven recreational drugs in human whole blood using gas chromatography-mass spectrometry.

    PubMed

    Lin, Zebin; Li, Jiaolun; Zhang, Xinyu; Qiu, Meihong; Huang, Zhibin; Rao, Yulan

    2017-03-01

    Recreational drugs have large impact on public health and security, and to monitor them is of urgent demand. In the present study, ultrasound-assisted dispersive liquid-liquid microextraction combined with the detection of gas chromatography-mass spectrometry was applied to the determination of seven common recreational drugs, including amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, meperidine, methadone and ketamine in 200μL of human whole blood. A series of factors which would affect the extraction efficiency were systematically investigated, including the nature and the volume of extraction and dispersing solvents, ultrasonication time, salting-out effect and pH value. The method consumed small amount of sample. The limits of detection and limits of quantification for each analyte were 10 and 40ng/mL, respectively, and the linearity was in the range of 0.04-25μg/mL (R(2) higher than 0.99). Good specificity, precision (1.5-8.2% for the intra-day study and 2.6-12.8% for the inter-day study), satisfactory accuracy (85.0-117.1%) and extraction recovery (77.0-92.4%) were obtained, which makes it a high performance method for the determination of recreational drugs in human whole blood samples.

  7. Up-and-down-shaker-assisted dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry for the determination of fungicides in wine.

    PubMed

    Chu, Shang-Ping; Tseng, Wan-Chi; Kong, Po-Hsin; Huang, Chun-Kai; Chen, Jung-Hsuan; Chen, Pai-Shan; Huang, Shang-Da

    2015-10-15

    An up-and-down-shaker-assisted dispersive liquid-liquid microextraction (UDSA-DLLME) method coupled with gas chromatography-mass spectrometry was developed for the determination of fungicides (cyprodinil, procymidone, fludioxonil, flusilazole, benalaxyl, and tebuconazole) in wine. The developed method requires 11 μL of 1-octanol without the need for dispersive solvents. The total extraction time was approximately 3 min. Under optimum conditions, the linear range of the method was 0.05-100 μg L(-1) for all fungicides and the limit of detection was 0.007-0.025 μg L(-1). The absolute and relative recoveries were 31-83% and 83-107% for white wine, respectively, and 32-85% and 83-108% for red wine, respectively. The intra-day and inter-day precision were 0.5-7.5% and 0.7-6.1%, respectively. Our developed method had good sensitivity and high extraction efficiency. UDSA-DLLME is a desirable method in terms of performance and speed.

  8. Determination of volatile components of saffron by optimised ultrasound-assisted extraction in tandem with dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Sereshti, Hassan; Heidari, Reza; Samadi, Soheila

    2014-01-15

    In the present research, a combined extraction method of ultrasound-assisted extraction (UAE) in conjunction with dispersive liquid-liquid microextraction (DLLME) was applied to isolation and enrichment of saffron volatiles. The extracted components of the saffron were separated and determined by gas chromatography-mass spectrometry (GC-MS) technique. The mixture of methanol/acetonitrile was chosen for the extraction of the compounds and chloroform was used at the preconcentration stage. The important parameters, such as composition of extraction solvent, volume of preconcentration solvent, ultrasonic applying time, and salt concentration were optimised by using a half-fraction factorial central composite design (CCD). Under the optimal conditions, the linear dynamic ranges (LDRs) were 10-10,000mgL(-)(1). The determination coefficients (R(2)) were from 0.9990 to 0.9997. The limits of detection (LODs) and limits of quantification (LOQs) for the extracted compounds were 6-123mgL(-)(1) and 20-406mgL(-)(1), respectively. The relative standard deviations (RSDs) were 2.48-9.82% (n=3). The enhancement factors (EFs) were 3.6-41.3.

  9. Rapid and highly sensitive protein extraction via cobalt oxide nanoparticle-based liquid-liquid microextraction coupled with MALDI mass spectrometry.

    PubMed

    Shrivas, Kamlesh; Wu, Hui-Fen

    2012-02-21

    A new approach for rapid and highly sensitive protein extraction using cobalt oxide nanoparticles modified with cetyltrimethylammonium (Co(3)O(4)/CTA(+) NP) using nanoparticle-based liquid-liquid microextraction (NP-LLME) coupled with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has been successfully demonstrated. For the first time, the metal oxide NPs (Co(3)O(4)/CTA(+) NP) prepared in the organic phase (toluene) have been successfully applied for the extraction and preconcentration of proteins from sample solutions and complex samples via electrostatic forces involved between the metal oxide NP and proteins. Lysozyme was used as the model protein to investigate the optimal extraction parameters of the current approach. The optimal conditions were obtained at pH > pI for 10 min of incubation time (extraction time) with 3% salt (NaCl) addition. The Co(3)O(4)/CTA(+) NP was successfully applied for the highly sensitive analysis of an array proteins such as insulin, chymotrypsinogen and lysozyme from aqueous solution, protein mixture and milk samples in nanoparticle-based liquid-phase microextraction coupled with MALDI-MS. The potentiality of the NP-LLME using Co(3)O(4)/CTA(+) NP for the extraction of proteins was also compared with other types of NP-liquid phase microextraction (LPME) methods. The current approach offers distinct advantages including rapidity, straightforwardness, high sensitivity for washing- and separation-free MALDI-MS analysis of proteins.

  10. Dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry for the rapid and sensitive determination of UV filters in environmental water samples.

    PubMed

    Negreira, N; Rodríguez, I; Rubí, E; Cela, R

    2010-09-01

    The performance of the dispersive liquid-liquid microextraction (DLLME) technique for the determination of eight UV filters and a structurally related personal care species, benzyl salicylate (BzS), in environmental water samples is evaluated. After extraction, analytes were determined by gas chromatography combined with mass spectrometry detection (GC-MS). Parameters potentially affecting the performance of the sample preparation method (sample pH, ionic strength, type and volume of dispersant and extractant solvents) were systematically investigated using both multi- and univariant optimization strategies. Under final working conditions, analytes were extracted from 10 mL water samples by addition of 1 mL of acetone (dispersant) containing 60 μL of chlorobenzene (extractant), without modifying either the pH or the ionic strength of the sample. Limits of quantification (LOQs) between 2 and 14 ng L(-1), inter-day variability (evaluated with relative standard deviations, RSDs) from 9% to 14% and good linearity up to concentrations of 10,000 ng L(-1) were obtained. Moreover, the efficiency of the extraction was scarcely affected by the type of water sample. With the only exception of 2-ethylhexyl-p-dimethylaminobenzoate (EHPABA), compounds were found in environmental water samples at concentrations between 6 ± 1 ng L(-1) and 26 ± 2 ng mL(-1).

  11. Determination of phthalate esters in cleaning and personal care products by dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry.

    PubMed

    Viñas, Pilar; Campillo, Natalia; Pastor-Belda, Marta; Oller, Ainhoa; Hernández-Córdoba, Manuel

    2015-01-09

    Phthalic acid esters (PEs) were preconcentrated from cleaning products, detergents and cosmetics using ultrasound assisted extraction (UAE) in the presence of acetonitrile, and then submitted to dispersive liquid-liquid microextraction (DLLME). For DLLME, 3mL of acetonitrile extract, 150μL carbon tetrachloride and 10mL aqueous solution were used. The enriched organic phase was evaporated, reconstituted with 25μL acetonitrile and injected into a liquid chromatograph with a mobile phase (acetonitrile:10mM ammonium acetate, pH 4) under gradient elution. Detection was carried out using both diode-array (DAD) and electrospray-ion trap-tandem mass spectrometry (ESI-IT-MS/MS) in the multiple reaction monitoring mode (MRM) of the positive fragment ions. Quantification was carried out using matrix-matched standards. Detection limits were in the range 0.04-0.45ngmL(-1) for the six PEs considered. The recoveries obtained were in the 84-124% range, with RSDs lower than 10%. Thirty three different cleaning products were analyzed. The most frequently found compound was diethyl phthalate.

  12. Fast automated dual-syringe based dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry for the determination of polycyclic aromatic hydrocarbons in environmental water samples.

    PubMed

    Guo, Liang; Tan, Shufang; Li, Xiao; Lee, Hian Kee

    2016-03-18

    An automated procedure, combining low density solvent based solvent demulsification dispersive liquid-liquid microextraction (DLLME) with gas chromatography-mass spectrometry analysis, was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Capitalizing on a two-rail commercial autosampler, fast solvent transfer using a large volume syringe dedicated to the DLLME process, and convenient extract collection using a small volume microsyringe for better GC performance were enabled. Extraction parameters including the type and volume of extraction solvent, the type and volume of dispersive solvent and demulsification solvent, extraction and demulsification time, and the speed of solvent injection were investigated and optimized. Under the optimized conditions, the linearity ranged from 0.1 to 50 μg/L, 0.2 to 50 μg/L, and 0.5 to 50 μg/L, depending on the analytes. Limits of detection were determined to be between 0.023 and 0.058 μg/L. The method was applied to determine PAHs in environmental water samples.

  13. Liquid-liquid extraction of strongly protein bound BMS-299897 from human plasma and cerebrospinal fluid, followed by high-performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Xue, Y J; Pursley, Janice; Arnold, Mark

    2007-04-11

    BMS-299897 is a gamma-secretase inhibitor that is being developed for the treatment of Alzheimer's disease. Liquid-liquid extraction (LLE), chromatographic/tandem mass spectrometry (LC/MS/MS) methods have been developed and validated for the quantitation of BMS-299897 in human plasma and cerebrospinal fluid (CSF). Both methods utilized (13)C6-BMS-299897, the stable label isotope analog, as the internal standard. For the human plasma extraction method, two incubation steps were required after the addition of 5 mM ammonium acetate and the internal standard in acetonitrile to release the analyte bound to proteins prior to LLE with toluene. For the human CSF extraction method, after the addition of 0.5 N HCl and the internal standard, CSF samples were extracted with toluene and no incubation was required. The organic layers obtained from both extraction methods were removed and evaporated to dryness. The residues were reconstituted and injected into the LC/MS/MS system. Chromatographic separation was achieved isocratically on a MetaChem C18 Hypersil BDS column (2.0 mm x 50 mm, 3 microm). The mobile phase contained 10 mM ammonium acetate pH 5 and acetonitrile. Detection was by negative ion electrospray tandem mass spectrometry. The standard curves ranged from 1 to 1000 ng/ml for human plasma and 0.25-100 ng/ml for human CSF. Both standard curves were fitted to a 1/x weighted quadratic regression model. For both methods, the intra-assay precision was within 8.2% CV, the inter-assay precision was within 5.4% CV, and assay accuracy was within +/-7.4% of the nominal values. The validation and sample analysis results demonstrated that both methods had acceptable precision and accuracy across the calibration ranges.

  14. Simultaneous determination of polycyclic musks in blood and urine by solid supported liquid-liquid extraction and gas chromatography-tandem mass spectrometry.

    PubMed

    Liu, Hongtao; Huang, Liping; Chen, Yuxin; Guo, Liman; Li, Limin; Zhou, Haiyun; Luan, Tiangang

    2015-06-15

    A rapid, precise and accurate method for the simultaneous determination of 5 polycyclic musks (PCMs) in biological fluids was developed by solid supported liquid-liquid extraction (SLE) coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS). All parameters influencing SLE-GC-MS performance, including electron energy of electron-impact ionization source, collision energy for tandem mass spectrometer when operated in selected-reaction monitoring (SRM) mode, type and volume of elution reagent, nitrogen evaporation time, pH and salinity of sample have been carefully optimized. Eight milliliter of n-hexane was finally chosen as elution reagent. Blood and urine sample could be loaded into SLE cartridge without adjusting pH and salinity. Deuterated tonalide (AHTN-d3) was chosen as internal standard. The correlation coefficient (r(2)) of the calibration curves of target compounds ranged from 0.9996 to 0.9998. The dynamic range spanned over two orders of magnitude. The limit of detection (LOD) of target compounds in blood and urine ranged from 0.008 to 0.105μgL(-1) and 0.005 to 0.075μgL(-1), respectively. The developed procedure was successfully applied to the analysis of PCMs in human blood and urine obtaining satisfying recoveries on low, medium and high levels. The method was compared with SLE-GC-MS and shown one to two orders of magnitude improvement in sensitivity. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Fast screening of perfluorooctane sulfonate in water using vortex-assisted liquid-liquid microextraction coupled to liquid chromatography-mass spectrometry.

    PubMed

    Papadopoulou, Aikaterini; Román, Iván P; Canals, Antonio; Tyrovola, Konstantina; Psillakis, Elefteria

    2011-04-08

    Fast screening of trace amounts of the perfluorooctane sulfonate anion (PFOS) in water samples was performed following a simple, fast and efficient sample preparation procedure based on vortex-assisted liquid-liquid microextraction (VALLME) prior to liquid chromatography-mass spectrometry. VALLME initially uses vortex agitation, a mild emulsification procedure to disperse microvolumes of octanol, a low density extractant solvent, in the aqueous sample. Microextraction under equilibrium conditions is thus achieved within few minutes. Subsequently, centrifugation separates the two phases and restores the initial microdrop shape of the octanol acceptor phase, which can be collected and used for liquid chromatography-single quadrupole mass spectrometry analysis. Several experimental parameters were controlled and the optimum conditions found were: 50 μL of octanol as the extractant phase; 20 mL aqueous donor samples (pH=2); a 2 min vortex extraction time with the vortex agitator set at a 2500 rpm rotational speed; no ionic strength adjustment. Centrifugation for 2 min at 3500 rpm yielded separation of the two phases throughout this study. Enhanced extraction efficiencies were observed at low pH which was likely due to enhanced electrostatic interaction between the negatively PFOS molecules and the positively charged octanol/water interface. The effect of pH was reduced in the presence of sodium chloride, likely due to electrical double layer compression. The linear response range for PFOS was from 5 to 500 ng L(-1) (coefficient of determination, r(2), 0.997) and the relative standard deviation for aqueous solutions containing 10 and 500 ng L(-1) PFOS were 7.4% and 6.5%, respectively. The limit of detection was 1.6 ng L(-1) with an enrichment factor of approximately 250. Analysis of spiked tap, river and well water samples revealed that matrix did not affect extraction.

  16. Liquid-liquid extraction procedure for trace determination of cyclophosphamide in human urine by high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Sottani, C; Turci, R; Perbellini, L; Minoia, C

    1998-01-01

    A sensitive, specific and accurate high performance liquid chromatography/ionspray-tandem mass spectrometry procedure (HPLC/MS/MS) has been developed to quantify cyclophosphamide in human urine from hospital personnel involved in drug preparation and administration of antineoplastic alkylating agents. This methodology, which includes liquid-liquid extraction with ethylacetate, requires no derivatization procedures, preventing cyclophosphamide (CP) from possible thermal and chemical decomposition reactions. We detected the excretion of this unmetabolized alkylating drug in 50% of all the study participants. The amount of CP ranged from 0.1 ng microL-1 to 1.9 ng microL-1 urine. This methodology was validated by the use of ifosfamide as internal standard. The assay was linear over the range 0 to 3.2 ng microL-1 urine, with a lower limit of quantification of 0.2 microL-1. The limit of detection was assessed at 0.05 ng microL-1 urine. This method is characterized by a coefficient of variation < 10%. Standard calibration curves, obtained on three different days, had correlation coefficients always greater than 0.998. The intra and interday precision were within 11%, and accuracy was in the range 99-103%. The mean extracted recovery assessed at three different concentrations (0.5, 0.8, 3.2 ng microL-1) was always more than 85%. The extraction efficiency of cyclophosphamide from urine samples was also studied at six different pH values (pH 4, 5, 6, 7, 8, 10). The maximum extraction efficiency was obtained when the pH of urine solutions was adjusted to 7.0

  17. Analysis of hydrazine in drinking water by isotope dilution gas chromatography/tandem mass spectrometry with derivatization and liquid-liquid extraction.

    PubMed

    Davis, William E; Li, Yongtao

    2008-07-15

    A new isotope dilution gas chromatography/chemical ionization/tandem mass spectrometric method was developed for the analysis of carcinogenic hydrazine in drinking water. The sample preparation was performed by using the optimized derivatization and multiple liquid-liquid extraction techniques. Using the direct aqueous-phase derivatization with acetone, hydrazine and isotopically labeled hydrazine-(15)N2 used as the surrogate standard formed acetone azine and acetone azine-(15)N2, respectively. These derivatives were then extracted with dichloromethane. Prior to analysis using methanol as the chemical ionization reagent gas, the extract was dried with anhydrous sodium sulfate, concentrated through evaporation, and then fortified with isotopically labeled N-nitrosodimethylamine-d6 used as the internal standard to quantify the extracted acetone azine-(15)N2. The extracted acetone azine was quantified against the extracted acetone azine-(15)N2. The isotope dilution standard calibration curve resulted in a linear regression correlation coefficient (R) of 0.999. The obtained method detection limit was 0.70 ng/L for hydrazine in reagent water samples, fortified at a concentration of 1.0 ng/L. For reagent water samples fortified at a concentration of 20.0 ng/L, the mean recoveries were 102% with a relative standard deviation of 13.7% for hydrazine and 106% with a relative standard deviation of 12.5% for hydrazine-(15)N2. Hydrazine at 0.5-2.6 ng/L was detected in 7 out of 13 chloraminated drinking water samples but was not detected in the rest of the chloraminated drinking water samples and the studied chlorinated drinking water sample.

  18. Determination of geosmin and 2-methylisoborneol in water and wine samples by ultrasound-assisted dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry.

    PubMed

    Cortada, Carol; Vidal, Lorena; Canals, Antonio

    2011-01-07

    A fast, simple and environmentally friendly ultrasound-assisted dispersive liquid-liquid microextraction (USADLLME) procedure has been developed to preconcentrate geosmin and 2-methylisoborneol (MIB) from water and wine samples prior to quantification by gas chromatography-mass spectrometry (GC-MS). A two-stage multivariate optimization approach was developed by means of a Plackett-Burman design for screening and selecting the significant variables involved in the USADLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were: solvent volume, 8μL; solvent type: tetrachloroethylene; sample volume, 12 mL; centrifugation speed, 2300 rpm; extraction temperature 20 °C; extraction time, 3 min; and centrifugation time, 3 min. Under the optimized experimental conditions the method gave good levels of repeatability with coefficient of variation under 11% (n=10). Limits of detection were 2 and 9 ng L⁻¹ for geosmin and MIB, respectively. Calculated calibration curves gave high levels of linearity with correlation coefficient values of 0.9988 and 0.9994 for geosmin and MIB, respectively. Finally, the proposed method was applied to the analysis of two water (reservoir and tap) samples and three wine (red, rose and white) samples. The samples were previously analyzed and confirmed free of target analytes. Recovery values ranged between 70 and 113% at two spiking levels (0.25 μg L⁻¹ and 30 ng L⁻¹) showing that the matrix had a negligible effect upon extraction. Only red wine showed a noticeable matrix effect (70-72% recovery). Similar conclusions have been obtained from an uncertainty budget evaluation study.

  19. Ultra-trace determination of gold nanoparticles in environmental water by surfactant assisted dispersive liquid liquid microextraction coupled with electrothermal vaporization-inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Liu, Ying; He, Man; Chen, Beibei; Hu, Bin

    2016-08-01

    A new method by coupling surfactant assisted dispersive liquid liquid microextraction (SA-DLLME) with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) was proposed for the analysis of gold nanoparticles (AuNPs) in environmental water samples. Effective separation of AuNPs from ionic gold species was achieved by using sodium thiosulphate as a complexing agent. Various experimental parameters affecting SA-DLLME of AuNPs, such as the organic solvent, organic solvent volume, pH of the sample, the kind of surfactant, surfactant concentration, vortex time, speed of centrifugation, centrifugation time, and different coating as well as sizes of AuNPs were investigated carefully. Furthermore, the interference of coexisting ions, dissolved organic matter (DOM) and other metal nanoparticles (NPs) were studied. Under the optimal conditions, a detection limit of 2.2 ng L- 1 and an enrichment factor of 152-fold was achieved for AuNPs, and the original morphology of the AuNPs could be maintained during the extraction process. The developed method was successfully applied for the analysis of AuNPs in environmental water samples, including tap water, the East Lake water, and the Yangtze River water, with recoveries in the range of 89.6-102%. Compared with the established methods for metal NPs analysis, the proposed method has the merits of simple and fast operation, low detection limit, high selectivity, good tolerance to the sample matrix and no digestion or dilution required. It provides an efficient quantification methodology for monitoring AuNPs' pollution in the environmental water and evaluating its toxicity.

  20. A validated method for the analysis of cannabinoids in post-mortem blood using liquid-liquid extraction and two-dimensional gas chromatography-mass spectrometry.

    PubMed

    Andrews, Rebecca; Paterson, Sue

    2012-10-10

    A validated method for the identification and quantification of Δ(9)-tetrahydrocannabinol (THC), cannabidiol (CBD), cannabinol (CBN), 11-hydroxy-Δ(9)-tetrahydrocannabinol (11-OH-THC) and 11-nor-Δ(9)-tetrahydrocannabinol-9-carboxylic acid (THC-COOH) in post-mortem blood specimens is described. Liquid-liquid extraction was used to extract the cannabinoids from 1 mL of post-mortem blood. The extracts were derivatized with N-methyl-N-(trimethylsilyl)trifluoroacetamide. The final derivatized extracts were analyzed using two-dimensional gas chromatography-mass spectrometry. The limit of detection was 0.25 ng/mL for all analytes and the limit of quantification of the assay was 0.25 ng/mL for THC, CBN, 11-OH-THC and 0.5 ng/mL for CBD and THC-COOH. The assay was linear across the concentration range 0.25-50 ng/mL (determined with a low and a high calibration range) with correlation coefficients ≥0.992 for all analytes. Inter-day and intra-day accuracy was within ±15% of the target concentration for all analytes. The co-efficients of variation (%CV) for inter-day and intra-day precision were ≤12% for all analytes. The extraction efficiency was >73% for all analytes. The method has successfully been applied to 54 post-mortem blood specimens to date. To the authors knowledge this is the first validated 2D GC-MS method for the analysis of THC, CBD, CBN, 11-OH-THC and THC-COOH following LLE and its application to post-mortem specimens.

  1. Salting-out assisted liquid-liquid extraction combined with gas chromatography-mass spectrometry for the determination of pyrethroid insecticides in high salinity and biological samples.

    PubMed

    Niu, Zongliang; Yu, Chunwei; He, Xiaowen; Zhang, Jun; Wen, Yingying

    2017-09-05

    A salting-out assisted liquid-liquid extraction (SALLE) combined with gas chromatography-mass spectrometry (GC-MS) method was developed for the determination of four pyrethroid insecticides (PYRs) in high salinity and biological samples. Several parameters including sample pH, salting-out solution volume and salting-out solution pH influencing the extraction efficiency were systematically investigated with the aid of orthogonal design. The optimal extraction conditions of SALLE were: 4mL of salting-out solution with pH=4 and the sample pH=3. Under the optimum extraction and determination conditions, good responses for four PYRs were obtained in a range of 5-5000ng/mL, with linear coefficients greater than 0.998. The recoveries of the four PYRs ranged from 74% to 110%, with standard deviations ranging from 1.8% to 9.8%. The limits of detection based on a signal-to-noise ratio of 3 were between 1.5-60.6ng/mL. The method was applied to the determination of PYRs in urine, seawater and wastewater samples with a satisfactory result. The results demonstrated that this SALLE-GC-MS method was successfully applied to determine PYRs in high salinity and biological samples. SALLE avoided the need for the elimination of salinity and protein in the sample matrix, as well as clean-up of the extractant. Most of all, no centrifugation or any special apparatus are required, make this a promising method for rapid sample preparation procedure. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Simultaneous determination of 14 sulfonamides and tetracyclines in biogas plants by liquid-liquid-extraction and liquid chromatography tandem mass spectrometry.

    PubMed

    Spielmeyer, Astrid; Ahlborn, Jenny; Hamscher, Gerd

    2014-04-01

    A new method for the analysis of sulfonamides and tetracyclines in heterogenic biogas plant input samples and fermentation residues is introduced. Veterinary antibiotics are only partially absorbed in the animal gut; therefore, animal manure can contain high loads of these substances. Animal manure is used for biogas generation, so antibiotics can enter the anaerobic fermentation process this way. However, only little is known about the fate of antibiotics within this process, also due to the lack of suitable analytical methods for this complex sample matrix. Therefore, we developed a method for the analysis of ten sulfonamides (sulfachloropyridazine, sulfadiazine, sulfadimethoxine, sulfaguanidine, sulfamerazine, sulfamethazine, sulfamethoxazol, sulfamethoxypyridazin, sulfapyridine, sulfathiazole) and four tetracyclines (chlortetracycline, doxycycline, oxytetracycline, tetracycline) in biogas plant input and output samples, including a single liquid-liquid-extraction step and analysis via liquid chromatography (LC) and triple quadrupole mass spectrometry. The detection limit of this method ranges from 0.01 to 0.08 mg kg(-1). Matrix calibration using antibiotic-free cattle feces and isotopic-labeled internal standards enables quantification of antibiotics in different matrices such as animal manure, dung, or fermenter outputs with recovery rates between 70 and 130 %. This makes the method suitable for investigating the fate of antibiotics in animal manure and fermentation processes. A screening of 15 German biogas plants revealed the presence of several antibiotics up to 9 mg kg(-1) (201 mg kg(-1) dry matter). During the fermentation process, elimination occurs; however, with the exception of chlortetracycline, the antibiotic content remains in the same order of magnitude.

  3. Simultaneous determination of pyrethroids and pyrethrins by dispersive liquid-liquid microextraction and liquid chromatography triple quadrupole mass spectrometry in environmental samples.

    PubMed

    Ccanccapa-Cartagena, Alexander; Masiá, Ana; Picó, Yolanda

    2017-08-01

    A simple and environmentally friendly dispersive liquid-liquid microextraction (DLLME) method coupled with electrospray ionization liquid chromatography triple quadrupole mass spectrometry (LC-QqQ-MS/MS) was developed for the simultaneous determination of 17 synthetic and natural pyrethroids. A comparison of solid-phase extraction (SPE) versus DLLME for water samples and only "dilute and shoot" versus the additional extract cleanup by DLLME for sediment samples is reported. Chloroform was the extracting solvent in the DLLME technique for both water and sediment samples. Ultrasonic energy was applied to fully extract the analytes into fine droplets, providing high recoveries in short times. Method detection limits (MDLs) ranged from 0.12 to 0.62 ng L(-1) and recoveries from 70 to 119% with RSD values 2-15% (n = 5) for water samples. In sediment samples, MDLs ranged from 0.50 to 2.50 ng g(-1) and recoveries from 71 to 112% with RSDs 2-16% (n = 5). The proposed method showed a good linearity within the range of 10-500 ng mL(-1), with coefficients of determination (R (2)) higher than 0.99. Matrix effects were observed for most compounds in water and sediment (ME% < -10%). The proposed methodology was applied for the analysis of water and sediment samples from Albufera wetland and Turia River. Acrinathrin (48 ng g(-1)) and etofenprox (16 ng g(-1)) were detected in sediment samples. Graphical abstract Pyrethrins and pyrethroid determination in water and sediments by DLLME and LC-MS/MS.

  4. Salt-assisted dispersive liquid-liquid microextraction coupled with programmed temperature vaporization gas chromatography-mass spectrometry for the determination of haloacetonitriles in drinking water.

    PubMed

    Ma, Huilian; Li, Yun; Zhang, Haijun; Shah, Syed Mazhar; Chen, Jiping

    2014-09-05

    We report here a new analytical method for the simultaneous determination of seven haloacetonitriles (HANs) in drinking water by coupling salt-assisted dispersive liquid-liquid microextraction (SADLLME) with programmed temperature vaporizer-gas chromatography-mass spectrometry (PTV-GC-MS). The newly developed method involves the dispersion of the extractant in aqueous sample by addition of a few grams of salt and no dispersion liquid was required as compared to the traditional DLLME methods. The extractant (CH2Cl2, 50μL) and the salt (Na2SO4, 2.4g) were successively added to water (8mL) in a conical centrifuge tube that was shaken for 1min and centrifuged (3500rpm, 3min). The aliquot of sedimented phase (4μL) was then directly injected into the PTV-GC-MS system. The limits of detection and quantification for the HANs were 0.4-13.2ngL(-1) and 1.2-43.9ngL(-1), respectively. The calibration curves showed good linearity (r(2)≥0.9904) over 3 orders of magnitude. The repeatability of the method was investigated by evaluating the intra- and inter-day precisions. The relative standard deviations (RSDs) obtained were lower than 10.2% and 7.8% at low and high concentration levels. The relative recoveries ranged from 79.3% to 105.1%. The developed methodology was applied for the analysis of seven HANs in several drinking water samples in coastal and inland cities of China. It was demonstrated to be a simple, sensible, reproducible and environment friendly method for the determination of trace HANs in drinking water samples. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Determination of hormones in milk by hollow fiber-based stirring extraction bar liquid-liquid microextraction gas chromatography mass spectrometry.

    PubMed

    Xu, Xu; Liang, Fanghui; Shi, Jiayuan; Zhao, Xin; Liu, Zhuang; Wu, Lijie; Song, Ying; Zhang, Hanqi; Wang, Ziming

    2013-08-06

    The hollow fiber-based stirring extraction bar liquid-liquid microextraction was applied to the extraction of hormones, including 17-α-ethinylestradiol, 17-α-estradiol, estriol, 17-β-estradiol, estrone, 17-α-hydroxyprogesterone, medroxyprogesterone, progesterone and norethisterone acetate, in milk. The present method has the advantages of both hollow fiber-liquid phase microextraction and stirring bar sorptive extraction. The stirring extraction bar was used as both the stirring bar of microextraction, and extractor of the analytes, which can make extraction, clean-up and concentration be carried out in one step. When the extraction was completed, the stirring extraction bar was easy isolated from the extraction system with the magnet. Several experimental parameters, including the type of extraction solvent, the number of hollow stirring extraction bar, extraction time, stirring speed, ionic strength, and desorption conditions were investigated and optimized. The analytes in the extract were derived and determined by gas chromatography mass spectrometry. Under optimal experimental conditions, good linearity was observed in the range of 0.20-20.00ng mL(-1). The limits of detection and quantification were in the range of 0.02-0.06ng mL(-1) and 0.07-0.19ng mL(-1), respectively. The present method was applied to the analysis of milk samples, and the recoveries of analytes were in the range of 93.6-104.6% with the relative standard deviations ranging from 1.6% to 6.2% (n=5). The results showed that the present method was a rapid and feasible method for the determination of hormones in milk samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Simultaneous determination of amphetamine and methamphetamine enantiomers in urine by simultaneous liquid-liquid extraction and diastereomeric derivatization followed by gas chromatographic-isotope dilution mass spectrometry.

    PubMed

    Wang, Sheng-Meng; Wang, Ting-Cheng; Giang, Yun-Seng

    2005-02-25

    A simple, rapid, reliable, and economic analytical scheme starting with in situ liquid-liquid extraction and asymmetric (or diastereomeric) chemical derivatization (ChD) followed by gas chromatography (GC)-isotope dilution mass spectrometry (MS) is described for the simultaneous determination of D- and L-amphetamine (AP) and methamphetamine (MA) in urine which could have resulted from the administration of various forms of questioned amphetamines or amphetamines-generating drugs. By using L-N-trifluoroacetyl-1-prolyl chloride (L-TPC) as chiral derivatizing agent, resolutions of 2.2 and 2.0 were achieved for the separation of AP and MA enantiomeric pairs, respectively, on an ordinary HP-5MS capillary column. The GC-MS quantitation was carried out in the selected ion monitoring (SIM) mode using m/z 237 and 251 as the quantifier ions for the respective diastereomeric pairs of AP-L-TPC and MA-L-TPC. The calibration curves plotted for the two pairs of analytes stretch with good linearity down to 45 ng/mL, and the limits of detection and quantitation determined were as low as 40 and 45 ng/mL, respectively. Also, a comparative study using 10 real-case urine specimens previously screened as positive for MA administration showed mostly tolerable biases between the two sums (of concentration) of D- and L-MA obtained via an asymmetric L-TPC-ChD approach and via an ordinary pentafluoropropionylation (PFPA-ChD) approach, respectively, as well as between the two sums of D- and L-AP obtained thereupon, thus validating the proposed analytical scheme as a promising forensic protocol for the detailed analysis of enantiomeric amphetamines in urine.

  7. Method development for the quantitation of ABT-578 in rabbit artery tissue by 96-well liquid-liquid extraction and liquid chromatography/tandem mass spectrometric detection.

    PubMed

    Ji, Qin C; Zhang, Jun; Rodila, Ramona; Watson, Pamela; El-Shourbagy, Tawakol

    2004-01-01

    Quantitative determination of drug concentrations in tissue samples can provide critical information for drug metabolism, kinetics, and toxicity evaluations. For analysis of tissue samples using liquid chromatography/tandem mass spectrometric (LC/MS/MS) detection, homogenization is a critical step in achieving good assay performance. Assay performance can be closely evaluated by spiking the drug directly into tissue samples prior to homogenization. It is especially important to include this assay evaluation for the analysis of artery tissue samples because artery tissue is very elastic, making it quite a challenge to develop an effective procedure for homogenization. An LC/MS/MS assay in 96-well format using liquid-liquid extraction was developed for analyzing ABT-578 in rabbit artery samples. Tissue quality control samples were prepared by spiking ABT-578 stock solutions directly into the tissue before homogenization. The usage of the tissue control samples gives a thorough evaluation of the sample preparation process that includes both homogenization and sample extraction. A 20% blood in saline solution was used as a homogenization solution. Calibration standards were made by spiking ABT-578 into rabbit whole blood. Blood quality control samples were also prepared by spiking ABT-578 into rabbit whole blood. These blood QC samples were used to confirm the validity of the calibration curve. A lower limit of quantitation of 0.050 ng/mL was achieved. The linear dynamic range of blood standards was from 0.050-30.3 ng/mL with the correlation coefficient (r) ranging from 0.9969-0.9996. Overall %CV was between 1.3 and 7.0%, and analytical recovery was between 98.2 and 105.8% for blood QC samples. The %CVs for tissue QC samples were between 6.7 and 13.0%, and analytical recovery after correction was between 93.5 and 114.3%.

  8. Fast analysis of multiple pesticide residues in apple juice using dispersive liquid-liquid microextraction and multidimensional gas chromatography-mass spectrometry.

    PubMed

    Cunha, S C; Fernandes, J O; Oliveira, M B P P

    2009-12-18

    A method for the rapid trace analysis of 24 residual pesticides in apple juice by multidimensional gas chromatography-mass spectrometry (MD-GC/MS) using dispersive liquid-liquid microextraction (DLLME) was developed and optimized. Several parameters of the extraction procedure such as type and volume of extraction solvent, type and volume of dispersive solvent and salt addition were evaluated to achieve the highest yield and to attain the lowest detection limits. The DLLME procedure optimized consists in the formation of a cloudy solution promoted by the fast addition to the sample (5 ml) of a mixture of carbon tetrachloride (extraction solvent, 100 microl) and acetone (dispersive solvent, 400 microl). The tiny droplets formed and dispersed among the aqueous sample solution are further joined and sedimented (85 microl) in the bottom of the conical test tube by centrifugation. Once extracted, all the 24 pesticides were directly injected and separated by a dual GC column system, comprising a short wide-bore DB-5 capillary column with low film thickness connected by a Deans switch system to a second chromatographic narrower column, with identical stationary phase. The instrumental setting used, in combination with carefully optimized operational fast GC and MS parameters, markedly decreased the retention times of the targeted analytes. The total chromatographic run was 8 min. Mean recoveries for apple juice spiked at three concentrations ranged from 60% to 105% and the intra-repeatability ranged from 1% to 21%. The limits of detection of the 24 pesticides ranged from 0.06 to 2.20 microg/L. In 2 of a total of 28 analysed samples were found residues of captan, although at levels below the maximum limit legal established.

  9. Dispersive liquid-liquid microextraction for the determination of organochlorine pesticides residues in honey by gas chromatography-electron capture and ion trap mass spectrometric detection.

    PubMed

    Zacharis, Constantinos K; Rotsias, Ilias; Zachariadis, Petros G; Zotos, Anastasios

    2012-10-01

    A simple dispersive liquid-liquid microextraction (DLLME) protocol for the determination of 15 organochlorine pesticides residues in honey is proposed. The selected pesticides were separated using gas chromatography and detected by electron capture (ECD) or ion trap mass spectrometry (GC-IT/MS). Several parameters affecting the extraction efficiency namely type and volume of organic extraction solvent, type and volume of disperser solvent, sample pH, ionic strength, extraction time and centrifugation speed were systematically investigated. The final DLLME protocol involved the addition of 750 μL acetonitrile (disperser) and 50 μL chloroform (extraction solvent) into a 5 mL aqueous honey solution followed by centrifugation. The sedimented organic phase (chloroform) were analysed directly by GC-IT/MS or evaporated and reconstituted in acetonitrile prior to the GC-ECD analysis. The analytical performance of the GC-ECD and GC-IT/MS methods was compared and discussed. Under the selected experimental conditions, the enrichment factors varied between of 36 and 114. The limits of detection (LOD) were in the range of 0.02-0.15 μg L(-1) (0.4-3 ng g(-1)) for GC-ECD and 0.01-0.2 μg L(-1) (0.2-4 ng g(-1)) for GC-IT/MS which is adequate to verify compliance of products to legal tolerances. The proposed method was applied to the analysis of the selected organochlorine pesticides residues in various honey samples obtained from Greek region. Mean recoveries were ranged from 75% to 119% while the precision was better than 20% in both methodologies.

  10. Determination of nitroaromatic explosives in water samples by direct ultrasound-assisted dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Cortada, Carol; Vidal, Lorena; Canals, Antonio

    2011-10-15

    A fast, simple, inexpensive, sensitive, efficient and environmental friendly direct ultrasound-assisted dispersive liquid-liquid microextraction (DUSA-DLLME) procedure has been developed to concentrate five nitroaromatic explosives from water samples prior to quantification by gas chromatography-mass spectrometry (GC-MS). An efficient ultrasonic probe has been used to radiate directly the samples producing very fine emulsions from immiscible liquids. A D-optimal design was used for optimizing the factors and to evaluate their influential upon extraction. The optimum experimental conditions were: sample volume, 10 mL; extraction time, 60s; cycles, 0.6s(s(-1)); power of ultrasound energy, 40% (70 W); and, extractant solvent (chlorobenzene) volume, 20 μL. Under the optimized experimental conditions the method presents good level of repeatability with coefficients of variation under 6% (n=8; spiking level 10 μg L(-1)). Calculated calibration curves gave high level of linearity with correlation coefficient values between 0.9949 and 0.9992. Limits of detection were ranged between 0.03 and 0.91 μg L(-1). Finally, the proposed method was applied to the analysis of two types of water samples, reservoir and effluent wastewater. The samples were previously analysed and confirmed free of target analytes. At 5 μg L(-1) spiking level recovery values ranged between 75 and 96% for reservoir water sample showing that the matrix had a negligible effect upon extraction. However, a noticeable matrix effect (around 50% recovery) was observed for effluent wastewater sample. In order to alleviate this matrix effect, the standard addition calibration method was used for quantitative determination. This calibration method supplied recovery values ranged between 71 and 79%. The same conclusions have been obtained from an uncertainty budget evaluation study.

  11. Large volume of water samples introduced in dispersive liquid-liquid microextraction for the determination of 15 triazole fungicides by gas chromatography-tandem mass spectrometry.

    PubMed

    Nie, Jing; Chen, Fujiang; Song, Zhiyu; Sun, Caixia; Li, Zuguang; Liu, Wenhan; Lee, Mawrong

    2016-10-01

    A novel method of large volume of water samples directly introduced in dispersive liquid-liquid microextraction was developed, which is based on ultrasound/manual shaking-synergy-assisted emulsification and self-generating carbon dioxide gas (CO2) breaking down the emulsion for the determination of 15 triazole fungicides by gas chromatography-tandem mass spectrometry. This technique makes low-density extraction solvent toluene (180 μL) dissolve in 200 mL of samples containing 0.05 mol L(-1) of HCl and 5 % of NaCl (w/v) to form a well emulsion by synergy of ultrasound and manual shaking, and injects NaHCO3 solution (1.0 mol L(-1)) to generate CO2 achieving phase separation with the assistance of ultrasound. The entire process is accomplished within 8 min. The injection of NaHCO3 to generate CO2 achieves phase separation that breaks through the centrifugation limited large volume aqueous samples. In addition, the device could be easily cleaned, and this kind of vessel could be reconfigured for any volume of samples. Under optimal conditions, the low limits of detection ranging from 0.7 to 51.7 ng L(-1), wide linearity, and enrichment factors obtained were in the range 924-3669 for different triazole fungicides. Southern end of the Beijing-Hangzhou Grand Canal water (Hangzhou, China) was used to verify the applicability of the developed method. Graphical Abstract Flow chart of ultrasound/manual shaking-synergy-assisted emulsification and self-generating carbon dioxide gas breaking down the emulsion.

  12. Ultrasound-assisted dispersive liquid-liquid microextraction for the determination of synthetic musk fragrances in aqueous matrices by gas chromatography-mass spectrometry.

    PubMed

    Homem, Vera; Alves, Alice; Alves, Arminda; Santos, Lúcia

    2016-01-01

    A rapid and simple method for the simultaneous determination of twelve synthetic musks in water samples, using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) was successfully developed. The influence of seven factors (volume of the extraction solvent and disperser solvent, sample volume, extraction time, ionic strength, type of extraction and disperser solvent) affecting the UA-DLLME extraction efficiency was investigated using a screening design. The significant factors were selected and optimised employing a central composite design: 80 μL of chloroform, 880 μL of acetonitrile, 6 mL of sample volume, 3.5% (wt) of NaCl and 2 min of extraction time. Under the optimised conditions, this methodology was successfully validated for the analysis of 12 synthetic musk compounds in different aqueous samples (tap, sea and river water, effluent and influent wastewater). The proposed method showed enrichment factors between 101 and 115 depending on the analyte, limits of detection in the range of 0.004-54 ng L(-1) and good repeatability (most relative standard deviation values below 10%). No significant matrix effects were found, since recoveries ranged between 71% and 118%. Finally, the method was satisfactorily applied to the analysis of five different aqueous samples. Results demonstrated the existence of a larger amount of synthetic musks in wastewaters than in other water samples (average concentrations of 2800 ng L(-1) in influent and 850 ng L(-1) in effluent). Galaxolide, tonalide and exaltolide were the compounds most detected.

  13. Determination of UV filters in both soluble and particulate fractions of seawaters by dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Benedé, J L; Chisvert, A; Salvador, A; Sánchez-Quiles, D; Tovar-Sánchez, A

    2014-02-17

    An analytical method to determine the total content (i.e., not only in the soluble fraction but also in the particulate one) of eight commonly used UV filters in seawater samples is presented for the first time. Dispersive liquid-liquid microextraction (DLLME) is used as microextraction technique to pre-concentrate the target analytes before their determination by gas chromatography-mass spectrometry (GC-MS). In order to release the UV filters from the suspended particles an ultrasound treatment is performed before DLLME. The ultrasound treatment time was studied in order to achieve a quantitative lixiviation of the target analytes. The type and volume of both disperser and extraction solvent, the sample volume, the pH and the ionic strength involved in the DLLME have been optimized to provide the best enrichment factors. Under the optimized conditions, the method was successfully validated showing good linearity, enrichment factors between 112 and 263 depending on the analyte, limits of detection and quantification in the low ng L(-1) range (10-30 ng L(-1) and 33-99 ng L(-1), respectively) and good intra- and inter-day repeatability (RSD <15%). No significant matrix effects were found. Finally, the method was satisfactorily applied to the analysis of three seawater samples from different origin. Results showed significant amounts of UV filters in the particulate fraction that would have been ignored if only the soluble fraction had been considered. This fact shows that the UV filters are also accumulated in the suspended particles contained in water, what should be taken into account from an environmental standpoint.

  14. Analysis of 30 synthetic cannabinoids in serum by liquid chromatography-electrospray ionization tandem mass spectrometry after liquid-liquid extraction.

    PubMed

    Kneisel, Stefan; Auwärter, Volker

    2012-07-01

    The analysis of synthetic cannabinoids in human matrices is of particular importance in the fields of forensic and clinical toxicology since cannabis users partly shift to the consumption of 'herbal mixtures' as a legal alternative to cannabis products in order to circumvent drug testing. However, comprehensive methods covering the majority of synthetic cannabinoids already identified on the drug market are still lacking. In this article, we present a fully validated method for the analysis of 30 synthetic cannabinoids in human serum utilizing liquid-liquid extraction and liquid chromatography-electrospray ionization tandem mass spectrometry. The method proved to be suitable for the quantification of 27 substances. The limits of detection ranged from 0.01 to 2.0 ng/mL, whereas the lower limits of quantification were in the range from 0.1 to 2.0 ng/mL. The presented method was successfully applied to 833 authentic serum samples during routine analysis between August 2011 and January 2012. A total of 227 (27%) samples was tested positive for at least one of the following synthetic cannabinoids: JWH-018, JWH-019, JWH-073, JWH-081, JWH-122, JWH-200, JWH-203, JWH-210, JWH-307, AM-2201 and RCS-4. The most prevalent compounds in positive samples were JWH-210 (80%), JWH-122 (63%) as well as AM-2201 (29%). Median serum concentrations were all below 1.0 ng/mL. These findings demonstrate a significant shift of the market of synthetic cannabinoids towards substances featuring a higher CB(1) binding affinity and clearly emphasize that the analysis of synthetic cannabinoids in serum or blood samples requires highly sensitive analytical methods covering a wide spectrum of substances. Copyright © 2012 John Wiley & Sons, Ltd.

  15. Indacaterol determination in human urine: validation of a liquid-liquid extraction and liquid chromatography-tandem mass spectrometry analytical method.

    PubMed

    Ammari, Wesam G; Al-Qadhi, Zainab; Khalil, Mohammad; Tayyem, Rabab; Qammaz, Samir; Oriquat, Ghaleb; Basheti, Iman A; Chrystyn, Henry

    2015-06-01

    Indacaterol is a novel once-a-day inhaled ultra-long-acting β2-agonist. Quantitative bioanalysis supports pharmacokinetic and clinical research. The aim of the current work was to validate an in-house developed high performance liquid chromatography (HPLC)-tandem mass spectrometry (MS/MS) analytical method for indacaterol determination in human urine samples. A liquid-liquid extraction method has been developed to extract indacaterol from human urine samples using ethyl acetate. Indacaterol dry extract was reconstituted with 200 μL of the mobile phase (acidified water:methanol (30:70, v/v)) of which 5 μL was needed for the HPLC-MS/MS analysis. Indacaterol was eluted on a reversed C18 stationary phase with an isocratic mobile phase at a flow of 1 mL/min. Formoterol was the internal standard (IS). The MS/MS detection was employed with a turbo-ion spray ionization in the positive ion mode. A consensus of the international Guidelines for Bioanalytical Method Validation was followed. Indacaterol was detected at a mass to charge ratio (m/z) of 393.3 and its MS/MS daughter at 173.2. The retention times of indacaterol and IS were 1.60 and 1.20 min, respectively. Validated calibration curves were linear over a range of 0.075-100 ng/mL with correlation coefficients (r)≥0.990. The curves' regression weighting factor was 1/x. Method specificity was established in six different human urine batches. No matrix interference was observed. The intra- and inter-batch precision and accuracy within±20% (at lower limit) and±15% (other quality control (QC) levels) were confirmed. The indacaterol mean recovery (precision) percentages at Low, Mid, and High QC levels were 93.5 (3.84), 89.8 (2.15), and 92.2 (2.17), respectively. Short-term, long-term, freeze-thaw, and auto-sampler stability results were accepted. A specific, accurate and precise HPLC-MS/MS method has been validated for indacaterol quantification in human urine. This simple method is reproducible and robust

  16. Geochemical Speciation Mass Transfer

    SciTech Connect

    1985-12-01

    PHREEQC is designed to model geochemical reactions. Based on an ion association aqueous model, PHREEQC can calculate pH, redox potential, and mass transfer as a function of reaction progress. It can be used to describe geochemical processes for both far-field and near-field performance assessment and to evaluate data acquisition needs and test data. It can also calculate the composition of solutions in equilibrium with multiple phases. The data base, including elements, aqueous species, and mineral phases, is independent of the program and is completely user-definable. PHREEQC requires thermodynamic data for each solid, gaseous, or dissolved chemical species being modeled. The two data bases, PREPHR and DEQPAK7, supplied with PHREEQC are for testing purposes only and should not be applied to real problems without first being carefully examined. The conceptual model embodied in PHREEQC is the ion-association model of Pearson and Noronha. In this model a set of mass action equations are established for each ion pair (and controlling solid phases when making mass transfer calculations) along with a set of mass balance equations for each element considered. These sets of equations are coupled using activity coefficient values for each aqueous species and solved using a continued fraction approach for the mass balances combined with a modified Newton-Raphson technique for all other equations. The activity coefficient expressions in PHREEQC include the extended Debye-Huckel, WATEQ Debye-Huckel, and Davies equations from the original United States Geological Survey version of the program. The auxiliary preprocessor program PHTL, which is derived from EQTL, converts EQ3/6 thermodynamic data to PHREEQC format so that the two programs can be compared. PHREEQC can be used to determine solubility limits on the radionuclides present in the waste form. These solubility constraints may be input to the WAPPA leach model.

  17. Optimization of an accelerated solvent extraction dispersive liquid-liquid microextraction method for the separation and determination of essential oil from Ligusticum chuanxiong Hort by gas chromatography with mass spectrometry.

    PubMed

    Yang, Guang; Sun, Qiushi; Hu, Zhiyan; Liu, Hua; Zhou, Tingting; Fan, Guorong

    2015-10-01

    In this study, an accelerated solvent extraction dispersive liquid-liquid microextraction coupled with gas chromatography and mass spectrometry was established and employed for the extraction, concentration and analysis of essential oil constituents from Ligusticum chuanxiong Hort. Response surface methodology was performed to optimize the key parameters in accelerated solvent extraction on the extraction efficiency, and key parameters in dispersive liquid-liquid microextraction were discussed as well. Two representative constituents in Ligusticum chuanxiong Hort, (Z)-ligustilide and n-butylphthalide, were quantitatively analyzed. It was shown that the qualitative result of the accelerated solvent extraction dispersive liquid-liquid microextraction approach was in good agreement with that of hydro-distillation, whereas the proposed approach took far less extraction time (30 min), consumed less plant material (usually <1 g, 0.01 g for this study) and solvent (<20 mL) than the conventional system. To sum up, the proposed method could be recommended as a new approach in the extraction and analysis of essential oil. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Mass Transfer with Chemical Reaction.

    ERIC Educational Resources Information Center

    DeCoursey, W. J.

    1987-01-01

    Describes the organization of a graduate course dealing with mass transfer, particularly as it relates to chemical reactions. Discusses the course outline, including mathematics models of mass transfer, enhancement of mass transfer rates by homogeneous chemical reaction, and gas-liquid systems with chemical reaction. (TW)

  19. Mass Transfer with Chemical Reaction.

    ERIC Educational Resources Information Center

    DeCoursey, W. J.

    1987-01-01

    Describes the organization of a graduate course dealing with mass transfer, particularly as it relates to chemical reactions. Discusses the course outline, including mathematics models of mass transfer, enhancement of mass transfer rates by homogeneous chemical reaction, and gas-liquid systems with chemical reaction. (TW)

  20. Simultaneous speciation of inorganic arsenic, selenium and tellurium in environmental water samples by dispersive liquid liquid microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry.

    PubMed

    Liu, Ying; He, Man; Chen, Beibei; Hu, Bin

    2015-09-01

    A new method based on dispersive liquid liquid microextraction (DLLME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) was developed for the simultaneous speciation of inorganic arsenic (As), selenium (Se) and tellurium (Te) with sodium diethyldithiocarbamate (DDTC) as both chelating reagent and chemical modifier. As(III), Se(IV) and Te(IV) were transformed into DDTC-chelates at pH 7 and extracted into the fine droplets formed by injecting the binary solution of bromobenzene (extraction solvent) and methanol (dispersive solvent) into the sample solution. After phase separation by centrifugation, As(III), Se(IV) and Te(IV) preconcentrated in the organic phase were determined by ETV-ICP-MS. Total inorganic As, Se and Te were obtained by reducing As(V), Se(VI) and Te(VI) to As(III), Se(IV) and Te(IV) with L-cysteine, which were then subjected to the same DLLME-ETV-ICP-MS process. The concentration of As(V), Se(VI), Te(VI) were calculated by subtracting the concentration of As(III), Se(IV) and Te(IV) from the total inorganic As, Se and Te, respectively. The main factors affecting the microextraction efficiency and the vaporization behavior of target species were investigated in detail. Under the optimal conditions, the limits of detection were 2.5, 8.6 and 0.56 ng L(-1) for As(III), Se(IV) and Te(IV), respectively, with the relative standard deviations (n=7) of 8.5-9.7%. The developed method was applied to the speciation of inorganic As, Se and Te in Certified Reference Materials of GSBZ50004-88, GBW(E)080395 and GBW(E)080548 environmental waters, and the determined values are in good agreement with the certified values. The method was also successfully applied to the simultaneous speciation of inorganic As, Se and Te in different environmental water samples with the recoveries in the range of 86.3-107% for the spiked samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Development and application of a dispersive liquid-liquid microextraction method for the determination of tetracyclines in beef by liquid chromatography mass spectrometry.

    PubMed

    Mookantsa, S O S; Dube, S; Nindi, M M

    2016-02-01

    A rapid, cost effective and environmentally friendly extraction method, based on dispersive liquid-liquid microextraction (DLLME) was developed for the determination of six tetracyclines in meat destined for human consumption. Meat extracts were analysed for tetracyclines using liquid chromatography tandem mass spectrometry (LC-MS/MS), a sensitive and selective analytical technique. Various factors influencing the pre-concentration of tetracyclines such as sample pH, type and volume of both disperser solvent and extraction solvent were optimized. Validation parameters such as calibration function, limit of detection (LOD), limit of quantification (LOQ), detection capability (CCα), decision limit (CCβ), accuracy and precision were established according to Commission Decision 2002/657/EC. Linearity in the range of 25-200 µg kg(-1) was obtained with regression coefficients ranging from 0.9991 to 0.9998. Recoveries of spiked blank muscle samples at three levels (50, 100 and 150 µg kg(-1)) ranged from 80% to 105% and reproducibility was between 2% and 7%. LODs and LOQs ranged from 2.2 to 3.6 µg kg(-1) and from 7.4 to 11.5 µg kg(-1) respectively while CCα ranged from 105 to 111 µg kg(-1) and CCβ ranged from 107 to 122 µg kg(-1). The proposed method compared well with the existing accepted dispersive solid phase extraction method and was successfully applied to the pre-concentration and determination of tetracyclines in meat samples. Eleven of the thirty bovine muscle samples obtained from local abattoirs and butcheries were found to contain residues of two tetracycline antibiotics (chlortetracycline and oxytetracycline), with oxytetracycline being the most detected. Concentration levels of the tetracycline residues detected in bovine muscle samples were lower (12.4 and 68.9 µg kg(-1)) than the stipulated European Union maximum residue level (MRL) of 100 µg kg(-1), hence the meat was fit for human consumption. From this work it can be concluded that the DLLME

  2. Simultaneous determination of total fatty acid esters of chloropropanols in edible oils by gas chromatography-mass spectrometry with solid-supported liquid-liquid extraction.

    PubMed

    Liu, Qing; Han, Feng; Xie, Ke; Miao, Hong; Wu, Yongning

    2013-11-01

    This study aimed to establish a novel robust method for the simultaneous determination of total fatty acid esters of 4 chloropropanols including fatty acid esters of 3-monochloropropane-1,2-diol (3-MCPD esters), 2-monochloropropane-1,3-diol (2-MCPD esters), 1,3-dichloropropan-2-ol (1,3-DCP esters) and 2,3-dichloropropan-1-ol (2,3-DCP esters) in edible oils. In this method, sodium methylate in methanol was used as the reagent for the ester cleavage reaction of chloropropanols esters. The reaction products were extracted by a sodium sulfate solution, and then purified by solid-supported liquid-liquid extraction (SLE) using diatomaceous earth (Hydromatrix™) as the sorbent. Finally, the extracts were derivatized with heptafluorobutyrylim idazole (HFBI) and analyzed by gas chromatography-mass spectrometry (GC-MS). Quantification was achieved using deuterated chloropropanols as their respective internal standards, including 3-MCPD-d5, 2-MCPD-d5, 1,3-DCP-d5 and 2,3-DCP-d5. A good linear relationship between peak area and concentrations was obtained within the range of 0.025-2.000mgL(-1) with a correlation coefficients not less than 0.999 for all the chloropropanols esters. The limits of detection (LODs) of esters of 3-MCPD, 2-MCPD, 1,3-DCP and 2,3-DCP (calculated as corresponding chloropropanols) were 30, 30, 100 and 30μgkg(-1), respectively. The average recoveries of the 3-MCPD esters and the 4 chloropropanols spiked at 0.1, 0.5 and 2mgkg(-1) into blank oil matrix were typically in a range from 70.7% to 113.3%. The robust method validation data including calibration, LOD/LOQ, accuracy and repeatability and proficiency test results (Z-score: -0.5) of the official Food Analysis Performance Assessment Scheme (FAPAS) indicated that the present quantitative method could be successfully applied to the determination of total chloropropanols esters in various edible oils. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

  3. Simultaneous derivatization and ultrasound-assisted dispersive liquid-liquid microextraction of chloropropanols in soy milk and other aqueous matrices combined with gas-chromatography-mass spectrometry.

    PubMed

    Carro, A M; González, P; Lorenzo, R A

    2013-12-06

    A novel approach involving ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) and derivatization combined with gas chromatography-mass spectrometry was developed for the determination of chloropropanols in water and beverages. UA-DLLME was optimized as less solvent-consuming and cost-effective extraction method for water, fruit juice, milk and soy milk samples. The effect of parameters such as the type and volume of extraction solvent, the type and volume of dispersive solvent, amount of derivatization agent, temperature, pH of sample and ionic strength was investigated and optimized for each specimen, using experimental designs. By adding acetonitrile as dispersive solvent, N-heptafluorobutyrylimizadole (HFBI) as derivatization agent and chloroform as extraction solvent, the extraction-derivatization and preconcentration were simultaneously performed. The analytical concentration range was investigated in detail for each analyte in the different samples, obtaining linearity with R(2) ranging between 0.9990 and 0.9999. The method detection limits were in the range of 0.2-1.8μgL(-1) (water), 0.5-15μgL(-1) (fruit juices) and 0.9-3.6μgkg(-1) (milk) and 0.1-1.0μgkg(-1) (soy milk). The method was applied to the analysis of a variety of specimens, with recoveries of 98-101% from water, 97-102% from juices, 99-103% from milk and 97-105% from soy beverage. The relative standard deviation (precision, n=6) varied between 1.3 and 4.9%RSD in water, 2.3 and 5.8%RSD in juices, 1.0 and 5.7%RSD in milk and 3.9 and 9.3%RSD in soy milk. The proposed method was applied to analysis of twenty-eight samples. 1,3-Dichloro-2-propanol was found in an influent water sample from urban wastewater treatment plant (WWTP) (2.1±0.04mgL(-1)) but no chloropropanols were found in the corresponding effluent water sample. This result suggests that the purification system used in the WWTP has been effective for this compound. Moreover, the results revealed the presence of 3

  4. Dispersive liquid liquid microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry for the speciation of inorganic selenium in environmental water samples.

    PubMed

    Zhang, Yuan; Duan, Jiankun; He, Man; Chen, Beibei; Hu, Bin

    2013-10-15

    A novel method based on dispersive liquid liquid microextraction (DLLME) followed by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) determination was proposed for the speciation of inorganic selenium by using 5-mercapto-3-phenyl-1,3,4-thiadiazole-2-thione potassium salt (Bismuthiol II) as both chelating reagent and chemical modifier. In this method, 500 μL ethanol (as disperser solvent) containing 70 μL chloroform (as extraction solvent) and 0.2 g L(-1) Bismuthiol II (as chelating reagent) was rapidly injected into a sample solution to form cloudy solution. The complex of Se(IV) with Bismuthiol II was rapidly extracted into the extraction solvent at pH 2.0, while Se(VI) was remained in the aqueous solutions. Thus, the separation of Se(IV) and Se(VI) could be realized. After centrifugation, the complex of Se(IV) and Bismuthiol II concentrated in the extraction solvent was introduced into the ETV-ICP-MS for determination of Se(IV). Se(VI) was reduced to Se(IV) prior to determination of total selenium, and its assay was based on subtracting Se(IV) from total selenium. The main factors influencing the DLLME and the vaporization behavior of selenium in ETV were investigated systematically. Under the optimal conditions, the limit of detection (LOD) for Se(IV) was 0.047 ng mL(-1). The relative standard deviation (RSD) was 7.2% (CSe(IV)=1.0 ng mL(-1), n=8) with an enhancement factor of 64.8-fold from only 5 mL of water sample. The proposed method was successfully applied to the speciation of inorganic selenium in different environmental water samples with recoveries ranging from 94.8 to 108% for the spiking samples. In order to validate the proposed method, a Certified Reference Material of Environment Water (GBW(E)080395) was analyzed, and the determined value obtained was in good agreement with the certified value. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Fundamental Study on Enhancement of Liquid-Liquid Direct Contact Heat Transfer of Descending Water Insoluble High Density Liquid Droplets in a Heat Source Water Layer by Using Wire Mesh as Dispersion Material

    NASA Astrophysics Data System (ADS)

    Inaba, Hideo; Horibe, Akihiko; Yokoyama, Naoki; Haruki, Naoto

    This paper has dealt with liquid-liquid direct contact heat transfer characteristics by means of water insoluble heat transfer medium. In the present study, Perfluorocarbon(PFC, density of 1830kg/m3)was injected from above into a hot water layer, which was mounted by stainless steel wire net in order to make PFC droplets finer. The measuring result of the drop let diameter revealed that the droplet size distribution exerted an influence on the temperature effectiveness between PFC droplets and the hot water layer. It was observed that PFC droplets were dispersed by collision with stainless steel wire nets during falling in the hot water layer. Finally correlations equations of the temperature effectiveness and average diameter of PFC droplets had been derived as a function of some parameters.

  6. Salting-out assisted liquid/liquid extraction with acetonitrile: a new high throughput sample preparation technique for good laboratory practice bioanalysis using liquid chromatography-mass spectrometry.

    PubMed

    Zhang, Jun; Wu, Huaiqin; Kim, Elaine; El-Shourbagy, Tawakol A

    2009-04-01

    Acetonitrile, an organic solvent miscible with aqueous phase, has seen thousands of publications in the literature as an efficient deproteinization reagent. The use of acetonitrile for liquid-liquid extraction (LLE), however, has seen very limited application due to its miscibility with aqueous phase. The interest in LLE with acetonitrile has been pursued and reported in the literature by significantly lowering the temperature of the mixture or increasing the salt concentration in the mixture of acetonitrile and aqueous phase, resulting in the separation of the acetonitrile phase from aqueous phase, as observed in conventional LLE. However, very limited application of these methods has been reported. The throughput was limited. In this report, we report a new sample preparation technique, salting-out assisted liquid-liquid extraction with acetonitrile, for high-throughput good laboratory practice sample analysis using LCMS, Two compounds from an approved drug, Kaletra, were used to demonstrate the extractability of drugs from human plasma matrix. Magnesium sulfate was used as the salting-out reagent. Extracts were diluted and then injected into a reversed phase LC-MS/MS system directly. One 96-well plate was extracted with this new approach to evaluate multiple parameters of a good laboratory practice analytical method. Results indicate that the method is rapid, reliable and suitable for regulated bioanalysis. With minimal modification, this approach has been used for high-throughput good laboratory practice analysis of a number of compounds under development at Abbott.

  7. Analysis of triazine herbicides using an up-and-down-shaker-assisted dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry.

    PubMed

    Chen, Pai-Shan; Haung, Wan-Yun; Huang, Shang-Da

    2014-04-01

    In dispersive liquid-liquid microextraction, a few hundred microliters to a few milliliters of water-miscible dispersive solvent are commonly used to assist emulsification in aqueous samples. In the present study, a consistent and automatic up-and-down-shaker-assisted dispersive liquid-liquid microextraction (UDSA-DLLME) that does not require a dispersive solvent was developed. The enrichment factors (EFs) of the targets obtained using the automatic shaker were 361-1391 for UDSA-DLLME, 51-77 for ultrasonication, and 298-922 for vortexing. The linearity of the method was in the range 0.2-200μgL(-1), and its limit of detections was within 0.02-0.04μgL(-1). The intraday and interday relative standard deviations ranged from 5.7 to 10.0% and 5.5 to 10.3%, respectively. The relative recoveries of river and lake samples spiked with 2.0μgL(-1) of triazines were 94.2-102.2% and 98.5-104.1%, respectively. The technique provided high repeatability and recovery. No matrix interference from river and lake water was observed. The method also achieved high EFs compared with those obtained through other emulsification methods such as vortexing and ultrasonication. UDSA-DLLME is an alternative sample preparation technique with good performance.

  8. Comparison of two ionic liquid dispersive liquid-liquid microextraction approaches for the determination of benzoylurea insecticides in wastewater using liquid chromatography-quadrupole-linear ion trap-mass spectrometry: evaluation of green parameters.

    PubMed

    Vázquez, M M Parrilla; Vázquez, P Parrilla; Galera, M Martínez; Moreno, A Uclés

    2014-08-22

    Two dispersive liquid-liquid microextraction (DLLME) approaches including temperature-controlled ionic liquid dispersive liquid-liquid microextraction (TCIL-DLLME) and ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (US-IL-DLLME) were compared for the extraction of six benzoylurea insecticides (diflubenzuron, triflumuron, hexaflumuron, teflubenzuron, lufenuron and flufenoxuron) from wastewater samples prior to their determination by high-performance liquid chromatography with a hybrid triple quadrupole-linear ion trap-mass spectrometer (LC-QqLIT-MS/MS). Influential parameters affecting extraction efficiency were systematically studied and optimized and the most significant green parameters were quantified and compared. The best results were obtained using the US-IL-DLLME procedure, which employed the IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) and methanol (MeOH) as extraction and disperser solvent, respectively. US-IL-DLLME procedure was fast, easy, low environmental toxicity and, it was also able to successfully extract all selected benzoylureas. This method was extensively validated with satisfactory results: limits of detection and quantification were in the range 0.5-1.0 ng L(-1) and 1.5-3.5 ng L(-1), respectively, whereas recovery rates ranged from 89 to 103% and the relative standard deviations were lower than 13.4%. The applicability of the method was assessed with the analysis of effluent wastewater samples from a wastewater treatment plant located in an agricultural zone of Almería (Spain) and the results indicated the presence of teflubenzuron at mean concentration levels of 11.3 ng L(-1). US-IL-DLLME sample treatment in combination with LC-QqLIT-MS/MS has demonstrated to be a sensitive, selective and efficient method to determine benzoylurea insecticides in wastewaters at ultra-trace levels.

  9. Simultaneous Determination of 13 Priority Polycyclic Aromatic Hydrocarbons in Tehran's Tap Water and Water for Injection Samples Using Dispersive Liquid-Liquid Micro Extraction Method and Gas Chromatography-Mass Spectrometry.

    PubMed

    Sadeghi, Ramezan; Kobarfard, Farzad; Yazdanpanah, Hassan; Eslamizad, Samira; Bayate, Mitra

    2016-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are classified as persistent and carcinogenic organic pollutants. PAHs contamination has been reported in water. Many of relevant regulatory bodies such as EU and EPA have regulated the limit levels for PAHs in drinking water. In this study, 13 priority polycyclic aromatic hydrocarbons (PAHs) were determined in tap water samples of Tehran and water for injection. Dispersive liquid-liquid microextraction procedure combined with gas chromatography-mass spectrometry was used for the extraction and determination of PAHs in the samples. Under the optimized conditions, the range of extraction recoveries and relative standard deviations (RSDs) of PAHs in water using internal standard (anthracene-d10) were in the range of 71-90% and 4-16%, respectively. Limit of detection for different PAHs were between 0.03 and 0.1 ngmL(-1). The concentration of PAHs in all tap water as well as water for injection samples were lower than the limit of quantification of PAHs. This is the first study addressing the occurrence of PAHs in water for injection samples in Iran using dispersive liquid-liquid micro extraction procedure combined with gas chromatography-mass spectrometry.

  10. Simultaneous Determination of 13 Priority Polycyclic Aromatic Hydrocarbons in Tehran’s Tap Water and Water for Injection Samples Using Dispersive Liquid-Liquid Micro Extraction Method and Gas Chromatography-Mass Spectrometry

    PubMed Central

    Sadeghi, Ramezan; Kobarfard, Farzad; Yazdanpanah, Hassan; Eslamizad, Samira; Bayate, Mitra

    2016-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are classified as persistent and carcinogenic organic pollutants. PAHs contamination has been reported in water. Many of relevant regulatory bodies such as EU and EPA have regulated the limit levels for PAHs in drinking water. In this study, 13 priority polycyclic aromatic hydrocarbons (PAHs) were determined in tap water samples of Tehran and water for injection. Dispersive liquid-liquid microextraction procedure combined with gas chromatography-mass spectrometry was used for the extraction and determination of PAHs in the samples. Under the optimized conditions, the range of extraction recoveries and relative standard deviations (RSDs) of PAHs in water using internal standard (anthracene-d10) were in the range of 71-90% and 4-16%, respectively. Limit of detection for different PAHs were between 0.03 and 0.1 ngmL-1. The concentration of PAHs in all tap water as well as water for injection samples were lower than the limit of quantification of PAHs. This is the first study addressing the occurrence of PAHs in water for injection samples in Iran using dispersive liquid-liquid micro extraction procedure combined with gas chromatography-mass spectrometry. PMID:27642318

  11. Saponification reaction system: a detailed mass transfer coefficient determination.

    PubMed

    Pečar, Darja; Goršek, Andreja

    2015-01-01

    The saponification of an aromatic ester with an aqueous sodium hydroxide was studied within a heterogeneous reaction medium in order to determine the overall kinetics of the selected system. The extended thermo-kinetic model was developed compared to the previously used simple one. The reaction rate within a heterogeneous liquid-liquid system incorporates a chemical kinetics term as well as mass transfer between both phases. Chemical rate constant was obtained from experiments within a homogeneous medium, whilst the mass-transfer coefficient was determined separately. The measured thermal profiles were then the bases for determining the overall reaction-rate. This study presents the development of an extended kinetic model for considering mass transfer regarding the saponification of ethyl benzoate with sodium hydroxide within a heterogeneous reaction medium. The time-dependences are presented for the mass transfer coefficient and the interfacial areas at different heterogeneous stages and temperatures. The results indicated an important role of reliable kinetic model, as significant difference in k(L)a product was obtained with extended and simple approach.

  12. Low-density solvent-based vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction combined with gas chromatography-mass spectrometry for the fast determination of phthalate esters in bottled water.

    PubMed

    Zhang, Yufeng; Lee, Hian Kee

    2013-01-25

    For the first time, a novel low-density solvent-based vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction (LDS-VSLLME) was developed for the fast, simple and efficient determination of six phthalate esters (PEs) in bottled water samples followed by gas chromatography-mass spectrometry (GC-MS). In the extraction procedure, the aqueous sample solution was injected into a mixture of extraction solvent (toluene) and surfactant (cetyltrimethyl ammonium bromide), which were placed in a glass tube with conical bottom, to form an emulsion by the assistance of vortex agitation. After extraction and phase separation by centrifugation, and removal of the spent sample, the toluene extract was collected and analyzed by GC-MS. The addition of surfactant enhanced the dispersion of extraction solvent in aqueous sample and was also favorable for the mass transfer of the analytes from the aqueous sample to the extraction solvent. Moreover, using a relatively less toxic surfactant as the emulsifier agent overcame the disadvantages of traditional organic dispersive solvents that are usually highly toxic and expensive and might conceivably decrease extraction efficiency to some extent since they are not as effective as surfactants themselves in generating an emulsion. With the aid of surfactant and vortex agitation to achieve good organic extraction solvent dispersion, extraction equilibrium was achieved within 1 min, indicating it was a fast sample preparation technique. Another prominent feature of the method was the simple procedure to collect a less dense than water solvent by a microsyringe. After extraction and phase separation, the aqueous sample was removed using a 5-mL syringe, thus leaving behind the extract, which was retrieved easily. This novel method simplifies the use of low-density solvents in DLLME. Under the optimized conditions, the proposed method provided good linearity in the range of 0.05-25 μg/L, low limits of detection (8-25 ng

  13. Solid-based disperser liquid-liquid microextraction for the preconcentration of phthalate esters and di-(2-ethylhexyl) adipate followed by gas chromatography with flame ionization detection or mass spectrometry.

    PubMed

    Farajzadeh, Mir Ali; Khorram, Parisa; Nabil, Ali Akbar Alizadeh

    2014-05-01

    A new approach for the development of a dispersive liquid-liquid microextraction followed by GC with flame ionization detection was proposed for the determination of phthalate esters and di-(2-ethylhexyl) adipate in aqueous samples. In the proposed method, solid and liquid phases were used as the disperser and extractant, respectively, providing a simple and fast mode for the extraction of the analytes into a small volume of an organic solvent. In this method, microliter levels of an extraction solvent was added onto a sugar cube and it was transferred into the aqueous phase containing the analytes. By manual shaking, the sugar was dissolved and the extractant was released into the aqueous phase as very tiny droplets to provide a cloudy solution. Under optimized conditions, the proposed method showed good precision (RSD less than 5.2%), high enrichment factors (266-556), and low LODs (0.09-0.25 μg/L). The method was successfully applied for the determination of the target analytes in different samples, and good recoveries (71-103%) were achieved for the spiked samples. No need for a disperser solvent and higher enrichment factors compared with conventional dispersive liquid-liquid microextraction and low cost and short sample preparation time are other advantages of the method. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. A simultaneous study of kinetics and thermodynamics of anion transfer across the liquid/liquid interface by means of Fourier transformed large-amplitude square-wave voltammetry at three-phase electrode.

    PubMed

    Deng, Haiqiang; Huang, Xinjian; Wang, Lishi

    2010-12-21

    This paper describes a novel application of Fourier transformed large-amplitude square-wave voltammetry (FT-SWV) in combination with three-phase edge plane pyrolytic graphite (EPPG) electrode to investigate both the kinetics and thermodynamics of anion transfer across the liquid/liquid interface using a conventional three-electrode arrangement. The transfer of anion from aqueous phase to organic phase was electrochemically driven by reversible redox transformation of confined redox probe in the organic phase. The kinetics and thermodynamics of anion transfer were inspected by a so-called "quasi-reversible maximum" (QRM) emerged in the profile of even harmonic components of power spectrum obtained by Fourier transformation (FT) of time-domain total current response and formal potential E(f) of first harmonic voltammogram obtained by application of inverse FT on the power spectrum. Besides, a systematic study of patterns of behavior of a variety of anions at the same concentration and a specific anion at different concentrations on kinetics and thermodynamics and the effect of amplitude ΔE on QRM were also conducted, aiming to optimize the measurement conditions. The investigation mentioned above testified that the ion transfer across the liquid/liquid interface controls the kinetics of overall electrochemical process, regardless of either FT-SWV or traditional SWV investigation. Moreover, either the kinetic probe f(max) or the thermodynamic probe E(f) can be served as a way for analytical applications. Interestingly, a linear relationship between peak currents of the first harmonic components and concentrations of perchlorate anion in the aqueous solutions can be observed, which is somewhat in accordance with a finding obtained by Fourier transformed alternating current voltammetry (FT-ACV) [Bond, A. M.; Duffy, N. W.; Elton, D. M.; Fleming, B. D. Anal. Chem. 2009, 81, 8801-8808]. This may open a new door for analytical detection of a wide spectrum of

  15. Residue analysis of kresoxim-methyl and boscalid in fruits, vegetables and soil using liquid-liquid extraction and gas chromatography-mass spectrometry.

    PubMed

    Liu, Xingang; Dong, Fengshou; Qin, Dongmei; Zheng, Yongquan

    2010-04-01

    A GC-MS procedure for simultaneously determining and validating kresoxim-methyl and boscalid has been developed in fruit, vegetable and soil matrices. The method was based on one-step liquid-liquid extraction with acetone and dichloromethane solvents. Estimated limits of detection (LODs) for kresoxim-methyl and boscalid were 0.006 and 0.015 mg/kg, and limits of quantification (LOQs) were 0.02 and 0.05 mg/kg, respectively. The intra- and inter- precision were achieved with RSD better than 13.8 and 14.5%, and recoveries were in the range of 77.1-98.7% for kresoxim-methyl and 72.8-105.1% for boscalid. The expanded uncertainties calculated at 0.1 mg/kg were below 18%. Concentration levels for residues of the two fungicides in melon samples from field trials collected 7 days after the last application were clearly below the established MRL values.

  16. Determination of phthalate esters in distillates by ultrasound-vortex-assisted dispersive liquid-liquid micro-extraction (USVADLLME) coupled with gas chromatography/mass spectrometry.

    PubMed

    Montevecchi, Giuseppe; Masino, Francesca; Zanasi, Luca; Antonelli, Andrea

    2017-04-15

    A method for the extraction of phthalate esters (PAEs) by Ultrasound-Vortex-Assisted Dispersive Liquid-Liquid Micro-Extraction (USVADLLME) approach was optimised and applied for the first time to a historical series of brandies. These contaminants are widely spread in the environment as a consequence of about half century of use in different fields of applications. The concern about these substances and the recent legal restrictions of China in distillates import need a quick and sensitive method for their quantification. The proposed method, moreover, is environmentally oriented due to the disposal of micro-quantities of solvent required. In fact, sub-ppm-limits of detection were achieved with a solvent volume as low as 160μL. The analysed samples were within the legal limits, except for some very ancient brandies whose contamination was probably due to a PAEs concentration effect as a consequence of long ageing and for the use of plastic pipelines no more operative. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Pre-concentration of phenolic compounds in water samples by novel liquid-liquid microextraction and determination by gas chromatography-mass spectrometry.

    PubMed

    Faraji, Hakim; Tehrani, Mohammad Saber; Husain, Syed Waqif

    2009-12-04

    Pre-concentration and determination of 8 phenolic compounds in water samples has been achieved by in situ derivatization and using a new liquid-liquid microextraction coupled GC-MS system. Microextraction efficiency factors have been investigated and optimized: 9 microL 1-undecanol microdrop exposed for 15 min floated on surface of a 10 mL water sample at 55 degrees C, stirred at 1200 rpm, low pH level and saturated salt conditions. Chromatographic problems associated with free phenols have been overcome by simultaneous in situ derivatization utilizing 40 microL of acetic anhydride and 0.5% (w/v) K(2)CO(3). Under the selected conditions, pre-concentration factor of 235-1174, limit of detection of 0.005-0.68 microg/L (S/N=3) and linearity range of 0.02-300 microg/L have been obtained. A reasonable repeatability (RSD< or =10.4%, n=5) with satisfactory linearity (0.9995> or =r(2)> or =0.9975) of results illustrated a good performance of the present method. The relative recovery of different natural water samples was higher than 84%.

  18. Vortex-assisted liquid-liquid microextraction combined with gas chromatography-mass spectrometry for the determination of organophosphate pesticides in environmental water samples and wines.

    PubMed

    Zacharis, Constantinos K; Christophoridis, Christophoros; Fytianos, Konstantinos

    2012-09-01

    A simple vortex-assisted liquid-liquid microextraction protocol followed by GC-MS is proposed for the determination of 12 organophosphate pesticides residues in environmental water samples and wines. The sample pretreatment employs the usage of low-density organic solvent. The parameters affecting the extraction efficiency (type and volume of organic extraction solvent, sample pH, ionic strength, extraction time, and centrifugation speed) were carefully examined. A mild emulsification process was involved by the addition of 40 μL toluene into 10 mL sample followed by sequential vortex-based agitation and manual shaking for 3 min. Following the extraction, the pesticide-rich organic solvent was recovered by centrifugation at 4000 rpm for 5 min. A fraction of the floated toluene was then collected and analyzed by GC-MS in SIM mode. Under the optimized conditions, the enrichment factor ranged between 65 and 389. Satisfactory linearity was observed for all pesticides tested with correlation coefficients higher than 0.9945 while the LODs were in the range of 2-11 ng L(-1) . The main advantages of the proposed method are the simplicity of operation, rapidity, low cost, and high sensitivity.

  19. A simple 96-well liquid-liquid extraction with a mixture of acetonitrile and methyl t-butyl ether for the determination of a drug in human plasma by high-performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Xue, Y-J; Pursley, Janice; Arnold, Mark E

    2004-02-04

    A simple 96-well plate liquid-liquid extraction (LLE), liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed and validated for the determination of a basic drug candidate in human plasma. Against the wisdom of conventional approaches, an aqueous/organic miscible solvent, acetonitrile, was used for liquid-liquid extraction along with methyl t-butyl ether. The use of acetonitrile effectively eliminated the formation of the irregular emulsion between aqueous/organic interfaces and modulated the polarity of the extraction solvents to achieve the desired recovery. This approach, which solved the emulsion problem, permitted the method to be automated using standard 96-well plate technology. A practical application was demonstrated through the use of this technique in the measurement of a novel drug in human plasma samples by LC/MS/MS. Chromatographic separation was achieved isocratically on a Phenomenox C18(2) Luna column (2 mm x 50 mm, 5 microm). The mobile phase contained 60% of 0.1% formic acid and 40% acetonitrile. Detection was by positive ion electrospray tandem mass spectrometry. The standard curve, which ranged from 1.22 to 979ng/ml, was fitted to a 1/x2 weighted quadratic regression model. The validation results show that this method was very rugged and had excellent precision and accuracy. The actual sample analysis results further demonstrated that this extraction procedure is well suited for real life applications. It is expected that with some modifications, this approach can be applied for the extraction of similar compounds from various biological fluids.

  20. Determination of 13 endocrine disrupting chemicals in sediments by gas chromatography-mass spectrometry using subcritical water extraction coupled with dispersed liquid-liquid microextraction and derivatization.

    PubMed

    Yuan, Ke; Kang, Haining; Yue, Zhenfeng; Yang, Lihua; Lin, Li; Wang, Xiaowei; Luan, Tiangang

    2015-03-25

    In this study, a sample pretreatment method was developed for the determination of 13 endocrine disrupting chemicals (EDCs) in sediment samples based on the combination of subcritical water extraction (SWE) and dispersed liquid-liquid microextraction (DLLME). The subcritical water that provided by accelerated solvent extractor (ASE) was the sample solution (water) for the following DLLME and the soluble organic modifier that spiked in the subcritical water was also used as the disperser solvent for DLLME in succession. Thus, several important parameters that affected both SWE and DLLME were investigated, such as the extraction solvent for DLLME (chlorobenzene), extraction time for DLLME (30s), selection of organic modifier for SWE (acetone), volume of organic modifier (10%) and extraction temperature for SWE (150 °C). In addition, good chromatographic behavior was achieved for GC-MS after derivatisation by using N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA). As a result, proposed method sensitive and reliable with the limits of detection (LODs) ranging from 0.006 ng g(-1) (BPA) to 0.639 ng g(-1) (19-norethisterone) and the relative standard deviations (RSDs) between 1.5% (E2) and 15.0% (DES). Moreover, the proposed method was compared with direct ASE extraction that reported previously, and the results showed that SWE-DLLME was more promising with recoveries ranging from 42.3% (dienestrol) to 131.3% (4,5α-dihydrotestosterone), except for diethylstilbestrol (15.0%) and nonylphenols (29.8%). The proposed method was then successfully applied to determine 13 EDCs sediment of Humen outlet of the Pearl River, 12 of target compounds could be detected, and 10 could be quantitative analysis with the total concentration being 39.6 ng g(-1), and which indicated that the sediment of Humen outlet was heavily contaminated by EDCs.

  1. Multi-residue method for determination of selected neonicotinoid insecticides in honey using optimized dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry.

    PubMed

    Jovanov, Pavle; Guzsvány, Valéria; Franko, Mladen; Lazić, Sanja; Sakač, Marijana; Šarić, Bojana; Banjac, Vojislav

    2013-07-15

    The objective of this study was to develop analytical method based on optimized dispersive liquid-liquid microextraction (DLLME) as a pretreatment procedure combined with reversed phase liquid chromatographic separation on C18 column and isocratic elution for simultaneous MS/MS determination of selected neonicotinoid insecticides in honey. The LC-MS/MS parameters were optimized to unequivocally provide good chromatographic separation, low detection (LOD, 0.5-1.0 μg kg(-1)) and quantification (LOQ, 1.5-2.5 μg kg(-1)) limits for acetamiprid, clothianidin, thiamethoxam, imidacloprid, dinotefuran, thiacloprid and nitenpyram in honey samples. Using different types (chloroform, dichloromethane) and volumes of extraction (0.5-3.0 mL) and dispersive (acetonitrile; 0.0-1.0 mL) solvent and by mathematical modeling it was possible to establish the optimal sample preparation procedure. Matrix-matched calibration and blank honey sample spiked in the concentration range of LOQ-100.0 μg kg(-1) were used to compensate the matrix effect and to fulfill the requirements of SANCO/12495/2011 for the accuracy (R 74.3-113.9%) and precision (expressed in terms of repeatability (RSD 2.74-11.8%) and within-laboratory reproducibility (RSDs 6.64-16.2%)) of the proposed method. The rapid (retention times 1.5-9.9 min), sensitive and low solvent consumption procedure described in this work provides reliable, simultaneous, and quantitative method applicable for the routine laboratory analysis of seven neonicotinoid residues in real honey samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Dispersive Liquid-Liquid Microextraction Using Low-Toxic Solvent for the Determination of Heavy Metals in Water Samples by Inductively Coupled Plasma-Mass Spectrometry.

    PubMed

    Peng, Guilong; Lu, Ying; He, Qiang; Mmereki, Daniel; Zhou, Guangming; Chen, Junhua; Tang, Xiaohui

    2016-01-01

    A low-toxic dispersive liquid-liquid microextraction (DLLME) combined with inductively coupled plasma-MS was used for preconcentration and determination of Cu, Cr, Cd, Ni, Mn, and Pb in real-water samples. In traditional DLLME analysis, chlorinated solvents have been widely used as extraction solvents. However, these solvents are not environmentally friendly. To overcome this problem, we used a low-toxic bromosolvent (1-bromo-3-methylbutane; lethal concentration, 50%, 6150 mg/kg) as the extraction solvent. To study the effects of different parameters on the extraction efficiency, an orthogonal array experimental design with an L16(4(5)) matrix was used. Under the best experimental conditions (i.e., concentration of complexing reagent 1-(2-pyridylazo)-2-naphthol, 1.5 × 10(-3) mol/L; pH, 7.0; volume of acetone, 0.5 mL; volume of 1-bromo-3 methylbutane, 30 μL; and without salt addition), the enhancement factor ranged from 34 to 40. The linear dynamic range was 1-1000 μg/L with r(2) values of 0.9984-0.9999, and the LODs were between 0.042 and 0.53 μg/L. RSDs (at metal ion concentrations of 20 μg/L, n = 6) were 2.12 to 3.42%. The developed method was successfully applied to the extraction and determination of the mentioned metal ions in real-water samples, and satisfactory results were obtained.

  3. An evaporation-assisted dispersive liquid-liquid microextraction technique as a simple tool for high performance liquid chromatography tandem-mass spectrometry determination of insecticides in wine.

    PubMed

    Timofeeva, Irina; Kanashina, Daria; Moskvin, Leonid; Bulatov, Andrey

    2017-08-25

    A sample pre-treatment technique based on evaporation-assisted dispersive liquid-liquid microextraction (EVA-DLLME), followed by HPLC-MS/MS has been developed for the determination of organophosphate insecticides (malathion, diazinon, phosalone) in wine samples. The procedure includes the addition of mixture of organic solvents (with density higher than water), consisting of the extraction (low density) and volatile (high density) solvents, to aqueous sample followed by heating of the mixture obtained, what promotes the volatile solvent evaporation and moving extraction solvent droplets from down to top of the aqueous sample and, as a consequence, microextraction of target analytes. To initiate the evaporation process an initiator is required. It was established that hexanol (extraction solvent) and dichloromethane (volatile solvent) mixture (1:1, v/v) provides effective microextraction of the insecticides from wine samples with recovery from 92 to 103%. The conditions of insecticides' microextraction such as selection of extraction solvent, ratio of hexanol/dichloromethane and hexanol/sample, type and concentration of initiator, and effect of ethanol as one of the main components of wine have been studied. Under optimal experimental conditions the linear detection ranges were found to be 10(-7)-10(-3)gL(-1) for malathion, 10(-9)-10(-4)gL(-1) for diazinon, and 10(-6)-10(-2)gL(-1) for phosalone. The LODs, calculated from a blank test, based on 3σ, found to be 3×10(-8)gL(-1) for malathion, 3×10(-10)gL(-1) for diazinon and 3×10(-7)gL(-1) for phosalone. The advantages of EVA-DLLME are the rapidity, simplicity, high sample throughput and low cost. As an outcome, the analytical results agreed fairly well with the results obtained by a reference GC-MS method. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Solid-phase extraction in combination with dispersive liquid-liquid microextraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis: the ultra-trace determination of 10 antibiotics in water samples.

    PubMed

    Liang, Ning; Huang, Peiting; Hou, Xiaohong; Li, Zhen; Tao, Lei; Zhao, Longshan

    2016-02-01

    A novel method, solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME), was developed for ultra-preconcentration of 10 antibiotics in different environmental water samples prior to ultra-high performance liquid chromatography-tandem mass spectrometry detection. The optimized results were obtained as follows: after being adjusted to pH 4.0, the water sample was firstly passed through PEP-2 column at 10 mL min(-1), and then methanol was used to elute the target analytes for the following steps. Dichloromethane was selected as extraction solvent, and methanol/acetonitrile (1:1, v/v) as dispersive solvent. Under optimal conditions, the calibration curves were linear in the range of 1-1000 ng mL(-1) (sulfamethoxazole, cefuroxime axetil), 5-1000 ng mL(-1) (tinidazole), 10-1000 ng mL(-1) (chloramphenicol), 2-1000 ng mL(-1) (levofloxacin oxytetracycline, doxycycline, tetracycline, and ciprofloxacin) and 1-400 ng mL(-1) (sulfadiazine) with a good precision. The LOD and LOQ of the method were at very low levels, below 1.67 and 5.57 ng mL(-1), respectively. The relative recoveries of the target analytes were in the range from 64.16% to 99.80% with relative standard deviations between 0.7 and 8.4%. The matrix effect of this method showed a great decrease compared with solid-phase extraction and a significant value of enrichment factor (EF) compared with dispersive liquid-liquid microextraction. The developed method was successfully applied to the extraction and analysis of antibiotics in different water samples with satisfactory results.

  5. Combined dispersive solid-phase extraction-dispersive liquid-liquid microextraction-derivatization for gas chromatography-mass spectrometric determination of aliphatic amines on atmospheric fine particles.

    PubMed

    Majedi, Seyed Mohammad; Lee, Hian Kee

    2017-02-24

    Short-chain aliphatic amines are ubiquitous in the atmospheric environment. They play an important role in the formation and growth of atmospheric particles. As such, there is a pressing need to monitor these particle-bound compounds present at trace quantities. The present work describes an efficient, one-step microextraction technique for the preconcentration and detection of trace levels of 10 aliphatic amines on fine particles (particulate matter of 2.5μm or less (PM2.5)) in the atmosphere. After extraction of amines from particles in acidified water samples, carbon-based sorbents (in dispersive solid-phase extraction mode), and vortex agitation were utilized for simultaneous derivatization-extraction and dispersive liquid-liquid microextraction. The approach significantly increased the recoveries and enrichment of the amine derivatives. This one-step, combined technique is proposed for the first time. Several influential factors including type and concentration of derivatization reagent (for gas chromatographic separation), type of buffer, sample pH, types and volumes of extraction and disperser solvents, type and amount of sorbent, vortex time and temperature, desorption solvent type and volume, and salt content were investigated and optimized. Under the optimum conditions, high enrichment factors (in the range of between 307 and 382) and good reproducibility (relative standard deviations, below 7.0%, n=5) were achieved. The linearity ranged from 0.1μg/L-100μg/L, and from 0.5μg/L-100μg/L, depending on the analytes. The limits of detection were between 0.02μg/L (corresponding to ∼0.01ng/m(3) in air) and 0.09μg/L (corresponding to ∼0.04ng/m(3) in air). The developed method was successfully applied to the analysis of PM2.5 samples collected by air sampling through polytetrafluoroethylene filters. The concentration levels of amines ranged from 1.04 to 4.16ng/m(3) in the air sampled.

  6. High-throughput salting-out-assisted liquid-liquid extraction for the simultaneous determination of atorvastatin, ortho-hydroxyatorvastatin, and para-hydroxyatorvastatin in human plasma using ultrafast liquid chromatography with tandem mass spectrometry.

    PubMed

    Yang, Yong; Xu, Qiufang; Zhou, Lei; Zhong, Dafang; Chen, Xiaoyan

    2015-03-01

    A high-throughput, specific, and rapid liquid chromatography with tandem mass spectrometry method was established and validated for the simultaneous determination of atorvastatin and its two major metabolites, ortho-hydroxyatorvastatin and para-hydroxyatorvastatin, in human plasma. A simple salting-out-assisted liquid-liquid extraction using acetonitrile and a mass-spectrometry-friendly salt, ammonium acetate, was employed to extract the analytes from human plasma. A recovery of more than 81% for all analytes was achieved in 1 min extraction time. Chromatographic separation was performed on a Kinetex XB C18 column utilizing a gradient elution starting with a 60% of water solution (1% formic acid), followed by increasing percentages of acetonitrile. Analytes were detected on a tandem mass spectrometer equipped with an electrospray ionization source that was operated in the positive mode, using the transitions of m/z 559.3 → m/z 440.2 for atorvastatin, and m/z 575.3 → m/z 440.2 for both ortho- and para-hydroxyatorvastatin. Deuterium-labeled compounds were used as the internal standards. The method was validated over the concentration ranges of 0.0200-15.0 ng/mL for atorvastatin and ortho-hydroxyatorvastatin, and 0.0100-2.00 ng/mL for para-hydroxyatorvastatin with acceptable accuracy and precision. It was then successfully applied in a bioequivalence study of atorvastatin.

  7. Nanomaterials at Liquid/Liquid Interfaces-A Review.

    PubMed

    Divya, V; Sangaranarayanan, M V

    2015-09-01

    The charge transfer processes occurring at the interface between two immiscible electrolyte solutions are of considerable importance in diverse fields of chemistry and biology. The introduction to nanoparticles and analysis of nanostructures in diverse branches of science and engineering are provided. The chemical and electrochemical techniques pertaining to the synthesis of metal nanoparticles, polymeric nanostructures and metal-polymer nanocomposites at liquid/liquid interfaces are surveyed. The unique features pertaining to the chemical synthesis of metal nanoparticles while employing diverse electrolytes and solvents are outlined. The advantages of various electrochemical synthetic protocols such as four-electrode assembly, thin film electrode, Scanning Electrochemical Microscopy and Solid/liquid/liquid interfaces for the study of nanoparticles at liquid/liquid interfaces are emphasized. The crucial role played by the liquid/liquid interfaces in altering the morphological patterns of metal nanoparticles, conducting polymers and metal-polymer nanocomposites is indicated. A few typical novel applications of these nanomaterials in fabrication of biosensors, electrochemical supercapacitors, and electrocatalysts have been outlined.

  8. Monodisperse droplet generation for microscale mass transfer studies

    NASA Astrophysics Data System (ADS)

    Roberts, Christine; Rao, Rekha; Grillet, Anne; Jove-Colon, Carlos; Brooks, Carlton; Nemer, Martin

    2011-11-01

    Understanding interfacial mass transport on a droplet scale is essential for modeling liquid-liquid extraction processes. A thin flow-focusing microfluidic channel is evaluated for generating monodisperse liquid droplets for microscale mass transport studies. Surface treatment of the microfluidic device allows creation of both oil in water and water in oil emulsions, facilitating a large parameter study of viscosity and flow rate ratios. The unusually thin channel height promotes a flow regime where no droplets form. Through confocal microscopy, this regime is shown to be highly influenced by the contact angle of the liquids with the channel. Drop sizes are found to scale with a modified capillary number. Liquid streamlines within the droplets are inferred by high speed imagery of microparticles dispersed in the droplet phase. Finally, species mass transfer to the droplet fluid is quantitatively measured using high speed imaging. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85.

  9. OPTIMIZED DETERMINATION OF TRACE JET FUEL VOLATILE ORGANIC COMPOUNDS IN HUMAN BLOOD USING IN-FIELD LIQUID-LIQUID EXTRACTION WITH SUBSEQUENT LABORATORY GAS CHROMATOGRAPHIC-MASS SPECTROMETRIC ANALYSIS AND ON-COLUMN LARGE VOLUME INJECTION

    EPA Science Inventory

    A practical and sensitive method to assess volatile organic compounds (VOCs) from JP-8 jet fuel in human whole blood was developed by modifying previously established liquid-liquid extraction procedures, optimizing extraction times, solvent volume, specific sample processing te...

  10. OPTIMIZED DETERMINATION OF TRACE JET FUEL VOLATILE ORGANIC COMPOUNDS IN HUMAN BLOOD USING IN-FIELD LIQUID-LIQUID EXTRACTION WITH SUBSEQUENT LABORATORY GAS CHROMATOGRAPHIC-MASS SPECTROMETRIC ANALYSIS AND ON-COLUMN LARGE VOLUME INJECTION

    EPA Science Inventory

    A practical and sensitive method to assess volatile organic compounds (VOCs) from JP-8 jet fuel in human whole blood was developed by modifying previously established liquid-liquid extraction procedures, optimizing extraction times, solvent volume, specific sample processing te...

  11. Accurate determination of 3-alkyl-2-methoxypyrazines in wines by gas chromatography quadrupole time-of-flight tandem mass spectrometry following solid-phase extraction and dispersive liquid-liquid microextraction.

    PubMed

    Fontana, Ariel; Rodríguez, Isaac; Cela, Rafael

    2017-09-15

    A new reliable method for the determination 3-alkyl-2-methoxypyrazines (MPs) in wine samples based on the sequential combination of solid-phase extraction (SPE), dispersive liquid-liquid microextraction (DLLME) and gas chromatography (GC) quadrupole time-of-flight accurate tandem mass spectrometry (QTOF-MS/MS) is presented. Primary extraction of target analytes was carried out by using a reversed-phase Oasis HLB (200mg) SPE cartridge combined with acetonitrile as elution solvent. Afterwards, the SPE extract was submitted to DLLME concentration using 0.06mL carbon tetrachloride (CCl4) as extractant. Under final working conditions, sample concentration factors above 379 times and limits of quantification (LOQs) between 0.3 and 2.1ngL(-1) were achieved. Moreover, the overall extraction efficiency of the method was unaffected by the particular characteristics of each wine; thus, accurate results (relative recoveries from 84 to 108% for samples spiked at concentrations from 5 to 25ngL(-1)) were obtained using matrix-matched standards, without using standard additions over every sample. Highly selective chromatographic records were achieved considering a mass window of 5mDa, centered in the quantification product ion corresponding to each compound. Twelve commercial wines, elaborated with grapes from different varieties and geographical origins, were processed with the optimized method. The 2-isobutyl-3-methoxypyrazine (IBMP) was determined at levels above the LOQs of the method in half of the samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Simultaneous Determination of Food-Related Biogenic Amines and Precursor Amino Acids Using in Situ Derivatization Ultrasound-Assisted Dispersive Liquid-Liquid Microextraction by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry.

    PubMed

    He, Yongrui; Zhao, Xian-En; Wang, Renjun; Wei, Na; Sun, Jing; Dang, Jun; Chen, Guang; Liu, Zhiqiang; Zhu, Shuyun; You, Jinmao

    2016-11-02

    A simple, rapid, sensitive, selective, and environmentally friendly method, based on in situ derivatization ultrasound-assisted dispersive liquid-liquid microextraction (in situ DUADLLME) coupled with ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) using multiple reaction monitoring (MRM) mode has been developed for the simultaneous determination of food-related biogenic amines and amino acids. A new mass-spectrometry-sensitive derivatization reagent 4'-carbonyl chloride rosamine (CCR) was designed, synthesized, and first reported. Parameters and conditions of in situ DUADLLME and UHPLC-MS/MS were optimized in detail. Under the optimized conditions, the in situ DUADLLME was completed speedily (within 1 min) with high derivatization efficiencies (≥98.5%). With the cleanup and concentration of microextraction step, good analytical performance was obtained for the analytes. The results showed that this method was accurate and practical for quantification of biogenic amines and amino acids in common food samples (red wine, beer, wine, cheese, sausage, and fish).

  13. High-throughput salting-out assisted liquid-liquid extraction with acetonitrile for the determination of anandamide in plasma of hemodialysis patients with liquid chromatography tandem mass spectrometry.

    PubMed

    Xiong, Xin; Zhang, Lei; Cheng, Litao; Mao, Wei

    2015-09-01

    Anandamide (AEA) is an endocannabinoid present in human plasma that is associated with several physiological functions and disease states. However, low AEA plasma levels pose challenges in terms of analytical characterization. Classical liquid-based lipid extraction and solid-phase extraction require complicated procedures and the drying down of relatively large volumes of solvents, making them unsuitable for high-throughput analysis. Here a high-throughput salting-out assisted liquid-liquid extraction (SALLE) method with acetonitrile and mass spectrometry compatible salts for liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis of AEA in human plasma has been developed and validated. The seamless interface of SALLE and LC-MS eliminated the drying-down step, only 100 μL of plasma is required and minimal volumes of organic solvent are used. Good reproducibility, accuracy and precision were demonstrated during the method validation. The method is linear up to 10 ng/mL with a lower limit of quantitation of 0.1 ng/mL for AEA, the accuracy for AEA was from 93.3 to 96.7% and the precision was <8.57%. This new methodology was successfully applied to analysis of clinical samples from maintenance hemodialysis patients. Copyright © 2015 John Wiley & Sons, Ltd.

  14. Dual ultrasonic-assisted dispersive liquid-liquid microextraction coupled with microwave-assisted derivatization for simultaneous determination of 20(S)-protopanaxadiol and 20(S)-protopanaxatriol by ultra high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhao, Xian-En; Lv, Tao; Zhu, Shuyun; Qu, Fei; Chen, Guang; He, Yongrui; Wei, Na; Li, Guoliang; Xia, Lian; Sun, Zhiwei; Zhang, Shijuan; You, Jinmao; Liu, Shu; Liu, Zhiqiang; Sun, Jing; Liu, Shuying

    2016-03-11

    This paper, for the first time, reported a speedy hyphenated technique of low toxic dual ultrasonic-assisted dispersive liquid-liquid microextraction (dual-UADLLME) coupled with microwave-assisted derivatization (MAD) for the simultaneous determination of 20(S)-protopanaxadiol (PPD) and 20(S)-protopanaxatriol (PPT). The developed method was based on ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) detection using multiple-reaction monitoring (MRM) mode. A mass spectrometry sensitizing reagent, 4'-carboxy-substituted rosamine (CSR) with high reaction activity and ionization efficiency was synthesized and firstly used as derivatization reagent. Parameters of dual-UADLLME, MAD and UHPLC-MS/MS conditions were all optimized in detail. Low toxic brominated solvents were used as extractant instead of traditional chlorinated solvents. Satisfactory linearity, recovery, repeatability, accuracy and precision, absence of matrix effect and extremely low limits of detection (LODs, 0.010 and 0.015ng/mL for PPD and PPT, respectively) were achieved. The main advantages were rapid, sensitive and environmentally friendly, and exhibited high selectivity, accuracy and good matrix effect results. The proposed method was successfully applied to pharmacokinetics of PPD and PPT in rat plasma.

  15. Mass transfer between binary stars

    NASA Technical Reports Server (NTRS)

    Modisette, J. L.; Kondo, Y.

    1980-01-01

    The transfer of mass from one component of a binary system to another by mass ejection is analyzed through a stellar wind mechanism, using a model which integrates the equations of motion, including the energy equation, with an initial static atmosphere and various temperature fluctuations imposed at the base of the star's corona. The model is applied to several situations and the energy flow is calculated along the line of centers between the two binary components, in the rotating frame of the system, thereby incorporating the centrifugal force. It is shown that relatively small disturbances in the lower chromosphere or photosphere can produce mass loss through a stellar wind mechanism, due to the amplification of the disturbance propagating into the thinner atmosphere. Since there are many possible sources of the disturbance, the model can be used to explain many mass ejection phenomena.

  16. Energy conversion at liquid/liquid interfaces: artificial photosynthetic systems

    NASA Technical Reports Server (NTRS)

    Volkov, A. G.; Gugeshashvili, M. I.; Deamer, D. W.

    1995-01-01

    This chapter focuses on multielectron reactions in organized assemblies of molecules at the liquid/liquid interface. We describe the thermodynamic and kinetic parameters of such reactions, including the structure of the reaction centers, charge movement along the electron transfer pathways, and the role of electric double layers in artificial photosynthesis. Some examples of artificial photosynthesis at the oil/water interface are considered, including water photooxidation to the molecular oxygen, oxygen photoreduction, photosynthesis of amphiphilic compounds and proton evolution by photochemical processes.

  17. Energy conversion at liquid/liquid interfaces: artificial photosynthetic systems

    NASA Technical Reports Server (NTRS)

    Volkov, A. G.; Gugeshashvili, M. I.; Deamer, D. W.

    1995-01-01

    This chapter focuses on multielectron reactions in organized assemblies of molecules at the liquid/liquid interface. We describe the thermodynamic and kinetic parameters of such reactions, including the structure of the reaction centers, charge movement along the electron transfer pathways, and the role of electric double layers in artificial photosynthesis. Some examples of artificial photosynthesis at the oil/water interface are considered, including water photooxidation to the molecular oxygen, oxygen photoreduction, photosynthesis of amphiphilic compounds and proton evolution by photochemical processes.

  18. Hydraulics and mass transfer efficiency of a commercial-scale membrane extractor

    SciTech Connect

    Seibert, A.F.; Py, X.; Mshewa, M.; Fair, J.R.

    1993-01-01

    In recent years there has been significant interest in utilizing microporous hollow fiber membranes for liquid-liquid extraction. The membrane extractor resembles the shell and tube heat exchanger with the tube section composed of 1,000-2,500 fibers/in{sup 2}. The diameter of each fiber is approximately 300 microns. In this process, the feed may be passed through the shell side, while the solvent is passed through the fiber side, or vice versa. Mass transfer occurs across the liquid-liquid interface formed in the pores of the fiber wall. The advantages of this technology are high throughput capacities, independence of density difference between the feed and solvent, and potentially high mass transfer areas. The mass transfer performance of an available commercial scale nonbaffled membrane extraction module was determined to be lower than expected from results obtained in smaller scale modules. Mass transfer studies of a commercial-scale membrane extraction module at the Separations Research Program have shown that a significant portion of the fibers are bypassed by the shell side fluid and consequently only a fraction of the total fiber surface area is utilized. A hydraulic study using a dye tracer technique verified this finding with an aqueous flow on the shell side. A model which incorporates mass transfer correlations reported by others has been developed and shown to have excellent agreement with the experimental data obtained. In this paper, the efficiency of the membrane extractor is compared with conventional spray, sieve tray, and packed columns; the effect of shell side bypassing is also presented.

  19. Multiresidue determination of pesticides in industrial and fresh orange juice by hollow fiber microporous membrane liquid-liquid extraction and detection by liquid chromatography-electrospray-tandem mass spectrometry.

    PubMed

    Bedendo, Gizelle Cristina; Jardim, Isabel Cristina Sales Fontes; Carasek, Eduardo

    2012-01-15

    A procedure involving hollow fiber microporous membrane liquid-liquid extraction (HF-MMLLE) and detection by liquid chromatography with tandem mass spectrometry was developed and applied. The extraction is based on liquid-liquid microextraction with a polypropylene porous membrane as a solid support for the solvent. On the membrane walls the solvent forms a renewable liquid membrane which improves the trueness of the method and promotes the sample clean-up. The applicability of this method was evaluated through the simultaneous extraction of 18 pesticides of different classes: polar organophosphates, carbamates, neonicotinoids, amides, pyrimidines, benzimidazoles and triazoles in industrial and fresh orange juice. The parameters affecting the extraction efficiency were optimized by multivariable designs. Under optimized conditions, analytes were concentrated onto 1.5 cm long microporous membranes placed directly into the sample containing 9mL of juice at pH 7.0, 4 g of ammonium sulfate and 400 μL of toluene:ethyl acetate (85:15, v/v). The best extraction conditions were achieved at 25°C with 35 min of extraction time. The analyte desorption was carried out using 50 μL of methanol:acetone (50:50, v/v) for 2 min in an ultrasonic bath. Limits of detection ranging between 0.003-0.33 mgL(-1), 0.003-0.35 mg L(-1) and 0.003-0.15 mgL(-1) were obtained for the carton orange juice, carton light orange juice and fresh orange juice samples, respectively. Good repeatability (lower than 7.6%) was obtained for all three sample types. The method was applied to five different juice samples containing soybean extract, orange pulp, nectar, light juice and fresh orange juice. The results suggest that the proposed method represents a very simple and low-cost alternative microextraction procedure rendering adequate limits of quantification for the determination of these pesticides in juice samples. Copyright © 2011 Elsevier B.V. All rights reserved.

  20. A novel method of ultrasound-assisted dispersive liquid-liquid microextraction coupled to liquid chromatography-mass spectrometry for the determination of trace organoarsenic compounds in edible oil.

    PubMed

    Wang, Wei-Xun; Yang, Tzung-Jie; Li, Zu-Guang; Jong, Ting-Ting; Lee, Maw-Rong

    2011-04-01

    A novel approach, ultrasound-assisted dispersive liquid-liquid microextraction combined with liquid chromatography-mass spectrometry (UA-DLLME with LC-MS) is demonstrated to be quite useful for the determination of trace amounts of organoarsenic compounds in edible oil. The organoarsenic compounds studied include dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and 3-nitro-4-hydroxyphenyl arsenic acid (Roxarsone). Orthogonal array experimental design (OAD) was utilized to investigate the parameter space of conditions for UA-DLLME. The optimum conditions were found to be 4 min of ultrasonic extraction using 1.25 mL of mixed solvent with 50 μL of buffer solution. Under these optimal conditions, the linear range was from 10 ng g(-1) to 500 ng g(-1) for DMA and Roxarsone, from 25 ng g(-1) to 500 ng g(-1) for MMA. Limits of detection of DMA, MMA and Roxarsone were 1.0 ng g(-1), 3.0 ng g(-1) and 5.8 ng g(-1), respectively. The precisions and recoveries also were investigated by spiking 3-level concentrations in edible oil. The recoveries obtained were over 89.9% with relative standard deviation (RSD) of 9.6%. The new approach was utilized to successfully detect trace amounts of organoarsenic compounds in various edible oil samples.

  1. Simultaneous liquid-liquid extraction and dispersive solid-phase extraction as a sample preparation method to determine acidic contaminants in river water by gas chromatography/mass spectrometry.

    PubMed

    Jiménez, Juan J

    2013-11-15

    A sample preparation procedure that combines a liquid-liquid extraction (LLE) with a dispersive solid-phase extraction (DSPE) has been devised to determine residues of four phenoxyacid herbicides, two aminopolycarboxylic acids and five acidic anti-inflammatory drugs in small volumes of river water samples. Two aliquots of acetone (3 and 0.5 mL) were used to extract the analytes from a 10 mL water sample at pH 2 containing 5 mg of octadecylsilane (ODS) sorbent and NaCl at a 5.5 M concentration. Acetone was isolated by the salting-out effect, collected, evaporated and the extract was treated with BF3/methanol to obtain the methyl esters of the analytes and determine them by GC with mass spectrometric detection. Recoveries were comprised between 82% and 114% with relative standard deviations about 5-15% (n=5) within a concentration range about 0.03-44 µg L(-1). The amount of ODS added to sample resulted to be a significant factor in the recovery for most of the analytes as deduced from an experimental design; the sample pH was not a so critical factor. A robustness study of the proposed sample preparation was carried out as defined by Youden and Steiner and an estimation of the uncertainties of the measured concentrations was made following the EURACHEM/CITAC guidelines, too. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. High-throughput method for macrolides and lincosamides antibiotics residues analysis in milk and muscle using a simple liquid-liquid extraction technique and liquid chromatography-electrospray-tandem mass spectrometry analysis (LC-MS/MS).

    PubMed

    Jank, Louise; Martins, Magda Targa; Arsand, Juliana Bazzan; Campos Motta, Tanara Magalhães; Hoff, Rodrigo Barcellos; Barreto, Fabiano; Pizzolato, Tânia Mara

    2015-11-01

    A fast and simple method for residue analysis of the antibiotics classes of macrolides (erythromycin, azithromycin, tylosin, tilmicosin and spiramycin) and lincosamides (lincomycin and clindamycin) was developed and validated for cattle, swine and chicken muscle and for bovine milk. Sample preparation consists in a liquid-liquid extraction (LLE) with acetonitrile, followed by liquid chromatography-electrospray-tandem mass spectrometry analysis (LC-ESI-MS/MS), without the need of any additional clean-up steps. Chromatographic separation was achieved using a C18 column and a mobile phase composed by acidified acetonitrile and water. The method was fully validated according the criteria of the Commission Decision 2002/657/EC. Validation parameters such as limit of detection, limit of quantification, linearity, accuracy, repeatability, specificity, reproducibility, decision limit (CCα) and detection capability (CCβ) were evaluated. All calculated values met the established criteria. Reproducibility values, expressed as coefficient of variation, were all lower than 19.1%. Recoveries range from 60% to 107%. Limits of detection were from 5 to 25 µg kg(-1).The present method is able to be applied in routine analysis, with adequate time of analysis, low cost and a simple sample preparation protocol.

  3. Liquid-liquid extraction/headspace/gas chromatographic/mass spectrometric determination of benzene, toluene, ethylbenzene, (o-, m- and p-)xylene and styrene in olive oil using surfactant-coated carbon nanotubes as extractant.

    PubMed

    Carrillo-Carrión, Carolina; Lucena, Rafael; Cárdenas, Soledad; Valcárcel, Miguel

    2007-11-09

    BTEX-S compounds are widely distributed in the environment and can be present in different foodstuffs, including olive oil. Taking into account the risks of the exposure to these compounds, analytical methods for their determination in different matrices are mandatory. In this paper, the use of surfactant-coated multiwalled carbon nanotubes as additive in liquid-liquid extraction is applied for the determination of single-ring aromatic compounds in olive oil samples. After sample treatment, the aqueous extracts are subsequently analyzed by headspace/gas chromatography/mass spectrometry allowing the determination of BTEX-S within ca. 15 min. Each stage of the proposed LLE/HS/GC/MS configuration involves a selectivity enhancement avoiding the interference of other compounds of the sample matrix. Limits of detection were in the range 0.25 ng mL(-1) (obtained for ethylbenzene) and 0.43 ng mL(-1) (for benzene). The repeatability of the proposed method expressed as RSD varied between 1.9% (styrene) and 3.3% (benzene) (n=11).

  4. In situ aqueous derivatization and determination of non-steroidal anti-inflammatory drugs by salting-out-assisted liquid-liquid extraction and gas chromatography-mass spectrometry.

    PubMed

    Noche, Gloria Grueiro; Laespada, María Esther Fernández; Pavón, José Luis Pérez; Cordero, Bernardo Moreno; Lorenzo, Soledad Muniategui

    2011-09-16

    A new analytical method for the determination of trace levels of five non-steroidal anti-inflammatory drugs (NSAIDs: clofibric acid, ibuprofen, naproxen, diclofenac and ketoprofen) in water samples is described. The analytical procedure involves in situ aqueous derivatization with N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) and salting-out liquid-liquid extraction (SALLE), followed by gas chromatography-programmed temperature vaporizer-mass spectrometry (GC-PTV-MS). The influence of several parameters on the efficiency of the derivatization (stirring time, reaction time, reagent concentration and pH), and the extraction (solvent, volume, salts and stirring time) and injection steps (liner, injection volume, liner temperature, injection time, venting time and venting flow) was investigated. The detection limits of the method in water varied from 0.042 μg/L for ibuprofen to 1.2 μg/L for ketoprofen. The relative standard deviations (RSD) values were found to be relatively low (<10% for all compounds). The methodology developed was applied to the determination of NSAIDs in several environmental matrices including tap, river, sea and influent and effluent waste water samples. The results obtained show the presence of ibuprofen and naproxen in the influent waste water sample.

  5. A fast method for bisphenol A and six analogues (S, F, Z, P, AF, AP) determination in urine samples based on dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry.

    PubMed

    Rocha, Bruno Alves; da Costa, Bruno Ruiz Brandão; de Albuquerque, Nayara Cristina Perez; de Oliveira, Anderson Rodrigo Moraes; Souza, Juliana Maria Oliveira; Al-Tameemi, Maha; Campiglia, Andres Dobal; Barbosa, Fernando

    2016-07-01

    In this study, a novel method combining dispersive liquid-liquid microextraction (DLLME) and fast liquid chromatography coupled to mass spectrometry (LC-MS/MS) was developed and validated for the extraction and determination of bisphenol A (BPA) and six bisphenol analogues, namely bisphenol S (BPS), bisphenol F (BPF), bisphenol P (BPP), bisphenol Z (BPZ), bisphenol AP (BPAP) and bisphenol AF (BPAF) in human urine samples. Type and volume of extraction and disperser solvents, pH sample, ionic strength, and agitation were evaluated. The matrix-matched calibration curves of all analytes were linear with correlation coefficients higher than 0.99 in the range level of 0.5-20.0ngmL(-1). The relative standard deviation (RSD), precision, at three concentrations (1.0, 8.0 and 15.0ngmL(-1)) was lower than 15% with accuracy ranging from 90 to 112%. The biomonitoring capability of the new method was confirmed with the analysis of 50 human urine samples randomly collected from Brazilians. BPA was detected in 92% of the analyzed samples at concentrations ranging

  6. Salting-out assisted liquid-liquid extraction coupled to ultra-high performance liquid chromatography-tandem mass spectrometry for the determination of tetracycline residues in infant foods.

    PubMed

    Moreno-González, David; García-Campaña, Ana M

    2017-04-15

    The use of salting-out assisted liquid-liquid extraction (SALLE) combined with ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) has been evaluated for the determination of tetracyclines in infant foods based on meat and vegetables or in milk. To obtain satisfactory extraction efficiencies for the studied analytes, several parameters affecting the SALLE procedure were optimized. Analytical performances of the method were satisfactory, obtaining limits of quantification lower than 0.48μgkg(-1) in all cases. The precision, expressed as relative standard deviation (%, RSD) was below 11.3%. The extraction efficiency for fortified samples ranged from 89.2 to 96.8%, with RSDs lower than 7.3%. Matrix effect was evaluated for all samples studied, being lower than |21|% in all cases. In relation to the low solvent consumption, the proposed methodology could be considered rapid, cheap and environmentally friendly. Its applicability has been successfully tested in a wide range of infant foods.

  7. Trace determination of organophosphate esters in white wine, red wine, and beer samples using dispersive liquid-liquid microextraction combined with ultra-high-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Pang, Long; Yang, Huiqiang; Yang, Peijie; Zhang, Hongzhong; Zhao, Jihong

    2017-08-15

    In this study, dispersive liquid-liquid microextraction coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry was developed for the analysis of five representative organophosphate esters (OPEs) in wine samples. Under optimized conditions, the proposed method resulted in good linearity (R(2)>0.9933) over the range of 0.1-100μgL(-1), with limits of detection (LODs, S/N =3) and quantification (LOQs, S/N =10) in the ranges of 0.48-18.8ngL(-1) and 1.58-62.5ngL(-1), respectively. Inter- and intra-assay precisions of RSD% ranged from 3.21% to 6.13% and from 1.69% to 7.63%, respectively. The spiked recoveries of target OPEs from white wine, red wine, and beer samples were in the ranges of 80-122%, 76-120%, and 76-110%, respectively, at two different concentration levels. The total concentrations of five OPEs found in white wine, red wine, and beer samples were in the ranges of 0.29-0.85μgL(-1), 1.00-3.05μgL(-1), and 0.86-1.47μgL(-1), respectively.

  8. Ultrasonic-assisted extraction and dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry as an efficient and sensitive method for determining of acrylamide in potato chips samples.

    PubMed

    Zokaei, Maryam; Abedi, Abdol-Samad; Kamankesh, Marzieh; Shojaee-Aliababadi, Saeedeh; Mohammadi, Abdorreza

    2017-11-01

    In this research, for the first time, we successfully developed ultrasonic-assisted extraction and dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry as a new, fast and highly sensitive method for determining of acrylamide in potato chips samples. Xanthydrol was used as a derivatization reagent and parameters affecting in the derivatization and microextraction steps were studied and optimized. Under optimum conditions, the calibration curves showed high levels of linearity (R(2)>0.9993) for acrylamide in the range of 2-500ngmL(-1). The relative standard deviation (RSD) for the seven analyses was 6.8%. The limit of detection (LOD) and limit of quantification (LOQ) were 0.6ngg(-1) and 2ngg(-1), respectively. The UAE-DLLME-GC-MS method demonstrated high sensitivity, good linearity, recovery, and enrichment factor. The performance of the new proposed method was evaluated for the determination of acrylamide in various types of chips samples and satisfactory results were obtained. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Trace determination of antibacterial pharmaceuticals in fishes by microwave-assisted extraction and solid-phase purification combined with dispersive liquid-liquid microextraction followed by ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Huang, Peiting; Zhao, Pan; Dai, Xinpeng; Hou, Xiaohong; Zhao, Longshan; Liang, Ning

    2016-02-01

    A novel pretreatment method involving microwave-assisted extraction and solid-phase purification combined with dispersive liquid-liquid microextraction (MAE-SPP-DLLME) followed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was established for the simultaneous determination of six antibacterial pharmaceuticals including metronidazole, tinidazole, chloramphenicol, thiamphenicol, malachite green and crystal violet. The conditions of MAE were optimized using an orthogonal design and the optimal conditions were found to be 8mL for acetonitrile, 50°C for 5min. Then, neutral alumina column was employed in the solid-phase purification. Finally, the critical parameters affecting DLLME, including selection of extraction and dispersive solvent, adjustment of pH, salt concentration, extraction time, were investigated by single factor study. Under optimum conditions, good linearities (r>0.9991) and satisfied recoveries (Recoveries>87.0%, relative standard deviation (RSD)<6.3%) were observed for all of the target analytes. The limits of detection and quantification were 4.54-101.3pgkg(-1) and 18.02-349.1pgkg(-1), respectively. Intra-day and inter-day RSDs were all lower than 3.6%. An obvious reduction in matrix effect was observed by this method compared with microwave assisted extraction followed by purification. The established method was sensitive, rapid, accurate and employable to simultaneously determine target analytes in farmed fish, river fish and marine fish.

  10. Rapid analysis of six phthalate esters in wine by ultrasound-vortex-assisted dispersive liquid-liquid micro-extraction coupled with gas chromatography-flame ionization detector or gas chromatography-ion trap mass spectrometry.

    PubMed

    Cinelli, Giuseppe; Avino, Pasquale; Notardonato, Ivan; Centola, Angela; Russo, Mario Vincenzo

    2013-03-26

    An Ultrasound-Vortex-Assisted Dispersive Liquid-Liquid Micro-Extraction (USVADLLME) procedure coupled with Gas Chromatography-Flame Ionization Detector (GC-FID) or Gas Chromatography-Ion Trap Mass Spectrometry (GC-IT/MS) is proposed for rapid analysis of six phthalate esters in hydroalcoholic beverages (alcohol by volume, alc vol(-1), ≤40%). Under optimal conditions, the enrichment factor of the six analytes ranges from 220- to 300-fold and the recovery from 85% to 100.5%. The limit of detection (LOD) and limit of quantification (LOQ) are ≥0.022 μg L(-1) and ≥0.075 μg L(-1), respectively. Intra-day and inter-day precisions expressed as relative standard deviation (RSD), are ≤8.2% and ≤7.0%, respectively. The whole proposed methodology has demonstrated to be simple, reproducible and sensible for the determination of trace phthalate esters in red and white wine samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Combination of accelerated solvent extraction and vortex-assisted liquid-liquid microextraction for the determination of dimethyl fumarate in textiles and leathers by gas chromatography-mass spectrometry.

    PubMed

    Lu, Yang; Zhu, Yan

    2014-02-01

    A simple and environmentally friendly sample preparation procedure coupled with gas chromatography-mass spectrometry was developed to assay dimethyl fumarate in textiles and leathers. The sample preparation procedure involved an accelerated solvent extraction (ASE) using water as the extract solvent, followed by the extraction and concentration of dimethyl fumarate from the aqueous solution using vortex-assisted liquid-liquid microextraction (VALLME). The parameters affecting the ASE and VALLME were optimized to achieve the maximum extraction efficiency, and the performance of the developed method was evaluated. Good linearity was observed over the range assayed (0.01-1mg/kg) with a regression coefficient of 0.998. The limit of detection and enrichment factor for the VALLME step were 0.001 mg/kg and 53, respectively. The intra- and inter-day precision were below 8.9%, and the recovery was approximately 84-103%. The as-developed method was successfully applied to textiles and leather samples.

  12. [Ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction for the determination of eight drugs in biological samples by gas chromatography-triple quadrupole mass spectrometry].

    PubMed

    Meng, Liang; Zhu, Binling; Zheng, Kefang; Zhang, Wenwen; Meng, Pinjia

    2015-03-01

    A novel microextraction technique based on ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction (UA-LDS-DLLME) has been developed for the determination of multiple drugs of abuse in biological samples by gas chromatography-triple quadrupole mass spectrometry (GC-QQQ-MS). A total of 100 µL of toluene as extraction solvent was dropped into the sample solution. Then the mixture was sonicated drastically in an ultrasonic bath for 3 min with occasional manual shaking to form a cloudy suspension. After centrifugation at 10,000 r/min for 3 min, the upper layer of low-density extractant was withdrawn and injected into the GC-QQQ-MS for analysis. The parameters affecting extraction efficiency have been investigated and optimized. Under the optimum conditions, good linearities were observed for all analytes with the correlation coefficients ranging from 0. 998 4 to 0. 999 4. The recoveries of 79.3%-100.3% with RSDs < 5.7% were obtained. The LODs (S/N = 3) were in the range from 0.05 to 0.40 µg/L. UA-LDS-DLLME technique has the advantages of less extraction time, suitable for batches of sample pretreatment simultaneously, and higher extraction efficiency. It was successfully applied to the analysis of amphetamines in real human urine samples.

  13. Application of dispersive liquid-liquid microextraction and gas chromatography with mass spectrometry for the determination of oxygenated volatile organic compounds in effluents from the production of petroleum bitumen.

    PubMed

    Boczkaj, Grzegorz; Makoś, Patrycja; Przyjazny, Andrzej

    2016-07-01

    We present a new procedure for the determination of oxygenated volatile organic compounds in samples of postoxidative effluents from the production of petroleum bitumens using dispersive liquid-liquid microextraction and gas chromatography with mass spectrometry. The eight extraction parameters were optimized for 43 oxygenated volatile organic compounds. The detection limits obtained ranged from 0.07 to 0.82 μg/mL for most of the analytes, the precision was good (relative standard deviation below 2.91% at the 5 μg/mL level and 4.75% at the limit of quantification), the recoveries for the majority of compounds varied from 70.6 to 118.9%, and the linear range was wide, which demonstrates the usefulness of the procedure. The developed procedure was used for the determination of oxygenated volatile organic compounds in samples of raw postoxidative effluents and in effluents after chemical treatment. In total, 23 compounds at concentration levels from 0.37 to 32.95 μg/mL were identified in real samples. The same samples were also analyzed in the SCAN mode, which resulted in four more phenol derivatives being identified and tentatively determined. The studies demonstrated the need for monitoring volatile organic compounds content in effluents following various treatments due to the formation of secondary oxygenated volatile organic compounds.

  14. Automated liquid-liquid extraction based on 96-well plate format in conjunction with ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) for the quantitation of methoxsalen in human plasma.

    PubMed

    Yadav, Manish; Contractor, Pritesh; Upadhyay, Vivek; Gupta, Ajay; Guttikar, Swati; Singhal, Puran; Goswami, Sailendra; Shrivastav, Pranav S

    2008-09-01

    A sensitive, specific and high throughput bioanalytical method using automated sample processing via 96-well plate liquid-liquid extraction and ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) has been developed for the determination of methoxsalen in human plasma. Plasma samples with ketoconazole as internal standard (IS) were prepared by employing 0.2 mL human plasma in ethyl acetate:dichloromethane (80:20, v/v). The chromatographic separation was achieved on a Waters Acquity UPLC BEH C18 column using isocratic mobile phase, consisting of 10 mM ammonium formate and acetonitrile (60:40, v/v), at a flow rate of 0.5 mL/min. The linear dynamic range was established over the concentration range 1.1-213.1 ng/mL for methoxsalen. The method was rugged and rapid with a total run time of 1.5 min. It was successfully applied to a pivotal bioequivalence study in 12 healthy human subjects after oral administration of 10 mg extended release methoxsalen formulation under fasting condition.

  15. Multi-residue method for determination of 58 pesticides, pharmaceuticals and personal care products in water using solvent demulsification dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry.

    PubMed

    Caldas, Sergiane Souza; Rombaldi, Caroline; Arias, Jean Lucas de Oliveira; Marube, Liziane Cardoso; Primel, Ednei Gilberto

    2016-01-01

    A rapid and efficient sample pretreatment using solvent-based de-emulsification dispersive liquid-liquid microextraction (SD-DLLME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was studied for the extraction of 58 pharmaceuticals and personal care products (PPCPs) and pesticides from water samples. Type and volume of extraction and disperser solvents, pH, salt addition, amount of salt and type of demulsification solvent were evaluated. Limits of quantification (LOQ) in the range from 0.0125 to 1.25 µg L(-1) were reached, and linearity was in the range from the LOQ of each compound to 25 μg L(-1). Recoveries ranged from 60% to 120% for 84% of the compounds, with relative standard deviations lower than 29%. The proposed method demonstrated, for the first time, that sample preparation by SD-DLLME with determination by LC-MS/MS can be successfully used for the simultaneous extraction of 32 pesticides and 26 PPCPs from water samples. The entire procedure, including the extraction of 58 organic compounds from the aqueous sample solution and the breaking up of the emulsion after extraction with water, rather than with an organic solvent, was environmentally friendly. In addition, this technique was less expensive and faster than traditional techniques. Finally, the analytical method under study was successfully applied to the analysis of all 58 pesticides and PPCPs in surface water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. LIQUID-LIQUID EXTRACTION COLUMNS

    DOEpatents

    Thornton, J.D.

    1957-12-31

    This patent relates to liquid-liquid extraction columns having a means for pulsing the liquid in the column to give it an oscillatory up and down movement, and consists of a packed column, an inlet pipe for the dispersed liquid phase and an outlet pipe for the continuous liquid phase located in the direct communication with the liquid in the lower part of said column, an inlet pipe for the continuous liquid phase and an outlet pipe for the dispersed liquid phase located in direct communication with the liquid in the upper part of said column, a tube having one end communicating with liquid in the lower part of said column and having its upper end located above the level of said outlet pipe for the dispersed phase, and a piston and cylinder connected to the upper end of said tube for applying a pulsating pneumatic pressure to the surface of the liquid in said tube so that said surface rises and falls in said tube.

  17. RapidFire Mass Spectrometry with Enhanced Throughput as an Alternative to Liquid-Liquid Salt Assisted Extraction and LC/MS Analysis for Sulfonamides in Honey.

    PubMed

    Veach, Brian T; Mudalige, Thilak K; Rye, Peter

    2017-03-21

    The use of veterinary drugs in honey bees for the prevention of infectious disease is ever increasing due to the spread of colony collapse disorder around the world. The United States Food and Drug Administration is concerned about the presence of these drugs residues in honey as they often lead to health concerns or potential antibiotic resistance. Currently there is a need for a rapid screening method for the detection of veterinary drugs in honey. Herein is a method that utilizes automated solid-phase extraction that is directly coupled to a mass spectrometer for the quantitative screening of 12 different regulated sulfonamides in honey. Identification of the residues was performed using tandem mass spectrometry (MS/MS) with a triple quadrupole mass spectrometer. The acquisition method developed for this analysis can extract with the automated solid-phase extraction system and analyze a single sample on the mass spectrometer in approximately 20 s, with minimal sample preparation. A target testing limit of 10 ng/g in honey for the sulfonamides was used based upon action limits set for other food commodities regulated by the United States Food and Drug Administration. A complete method validation procedure was conducted to evaluate the effectiveness of this quantitative screening method.

  18. PHREEQC. Geochemical Speciation Mass Transfer

    SciTech Connect

    Parkhurst, D.L.

    1995-01-01

    PHREEQC is designed to model geochemical reactions. Based on an ion association aqueous model, PHREEQC can calculate pH, redox potential, and mass transfer as a function of reaction progress. It can be used to describe geochemical processes for both far-field and near-field performance assessment and to evaluate data acquisition needs and test data. It can also calculate the composition of solutions in equilibrium with multiple phases. The data base, including elements, aqueous species, and mineral phases, is independent of the program and is completely user-definable. PHREEQC requires thermodynamic data for each solid, gaseous, or dissolved chemical species being modeled. The two data bases, PREPHR and DEQPAK7, supplied with PHREEQC are for testing purposes only and should not be applied to real problems without first being carefully examined. The conceptual model embodied in PHREEQC is the ion-association model of Pearson and Noronha. In this model a set of mass action equations are established for each ion pair (and controlling solid phases when making mass transfer calculations) along with a set of mass balance equations for each element considered. These sets of equations are coupled using activity coefficient values for each aqueous species and solved using a continued fraction approach for the mass balances combined with a modified Newton-Raphson technique for all other equations. The activity coefficient expressions in PHREEQC include the extended Debye-Huckel, WATEQ Debye-Huckel, and Davies equations from the original United States Geological Survey version of the program. The auxiliary preprocessor program PHTL, which is derived from EQTL, converts EQ3/6 thermodynamic data to PHREEQC format so that the two programs can be compared. PHREEQC can be used to determine solubility limits on the radionuclides present in the waste form. These solubility constraints may be input to the WAPPA leach model.

  19. Comparative evaluation of liquid-liquid extraction, solid-phase extraction and solid-phase microextraction for the gas chromatography-mass spectrometry determination of multiclass priority organic contaminants in wastewater.

    PubMed

    Robles-Molina, José; Gilbert-López, Bienvenida; García-Reyes, Juan F; Molina-Díaz, Antonio

    2013-12-15

    The European Water Framework Directive (WFD) 2000/60/EC establishes guidelines to control the pollution of surface water by sorting out a list of priority substances that involves a significant risk to or via the aquatic systems. In this article, the analytical performance of three different sample preparation methodologies for the GC-MS/MS determination of multiclass organic contaminants-including priority comprounds from the WFD-in wastewater samples using gas chromatography-mass spectrometry was evaluated. The methodologies tested were: (a) liquid-liquid extraction (LLE) with n-hexane; (b) solid-phase extraction (SPE) with C18 cartridges and elution with ethyl acetate:dichloromethane (1:1 (v/v)), and (c) headspace solid-phase microextraction (HS-SPME) using two different fibers: polyacrylate and polydimethylsiloxane/carboxen/divinilbenzene. Identification and confirmation of the selected 57 compounds included in the study (comprising polycyclic aromatic hydrocarbons (PAHs), pesticides and other contaminants) were accomplished using gas chromatography tandem mass spectrometry (GC-MS/MS) with a triple quadrupole instrument operated in the multiple reaction monitoring (MRM) mode. Three MS/MS transitions were selected for unambiguous confirmation of the target chemicals. The different advantages and pitfalls of each method were discussed. In the case of both LLE and SPE procedures, the method was validated at two different concentration levels (15 and 150 ng L(-1)) obtaining recovery rates in the range 70-120% for most of the target compounds. In terms of analyte coverage, results with HS-SPME were not satisfactory, since 14 of the compounds tested were not properly recovered and the overall performance was worse than the other two methods tested. LLE, SPE and HS-SPME (using polyacrylate fiber) procedures also showed good linearity and precision. Using any of the three methodologies tested, limits of quantitation obtained for most of the detected compounds were in

  20. Quantitative analysis of simvastatin and its beta-hydroxy acid in human plasma using automated liquid-liquid extraction based on 96-well plate format and liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhang, Nanyan; Yang, Amy; Rogers, John Douglas; Zhao, Jamie J

    2004-01-27

    An assay based on automated liquid-liquid extraction (LLE) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) has been developed and validated for the quantitative analysis of simvastatin (SV) and its beta-hydroxy acid (SVA) in human plasma. A Packard MultiProbe II workstation was used to convert human plasma samples collected following administration of simvastatin and quality control (QC) samples from individual tubes into 96-well plate format. The workstation was also used to prepare calibration standards and spike internal standards. A Tomtec Quadra 96-channel liquid handling workstation was used to perform LLE based on 96-well plates including adding solvents, separating organic from aqueous layer and reconstitution. SV and SVA were separated through a Kromasil C18 column (50 mm x 2 mm i.d., 5 microm) and detected by tandem mass spectrometry with a TurboIonspray interface. Stable isotope-labeled SV and SVA, 13CD(3)-SV and 13 CD(3)-SVA, were used as the internal standards for SV and SVA, respectively. The automated procedures reduced the overall analytical time (96 samples) to 1/3 of that of manual LLE. Most importantly, an analyst spent only a fraction of time on the 96-well LLE. A limit of quantitation of 50 pg/ml was achieved for both SV and SVA. The interconversion between SV and SVA during the 96-well LLE was found to be negligible. The assay showed very good reproducibility, with intra- and inter-assay precision (%R.S.D.) of less than 7.5%, and accuracy of 98.7-102.3% of nominal values for both analytes. By using this method, sample throughput should be enhanced at least three-fold compared to that of the manual procedure.

  1. Micro liquid-liquid extraction combined with large-volume injection gas chromatography-mass spectrometry for the determination of haloacetaldehydes in treated water.

    PubMed

    Serrano, María; Silva, Manuel; Gallego, Mercedes

    2011-11-18

    Haloacetaldehydes (HAs) are becoming the most widespread disinfection by-products (DBPs) found in drinking water, besides trihalomethanes and haloacetic acids, generated by the interaction of chemical disinfectants with organic matter naturally present in water. Because of their high potential toxicity, HAs have currently received a singular attention, especially trichloroacetaldehyde (chloral hydrate, CH), the most common and abundant compound found in treated water. The aims of this study are focused on the miniaturisation of EPA Method 551.1, including some innovations such as the use of ethyl acetate as the extracting solvent, the enhancement of HAs stability in aqueous solutions by adjusting the pH ~3.2 and the use of a large-volume sample injection (30 μL) coupled to programmed temperature vaporizer-gas chromatography-mass spectrometry to improve both sensitivity and selectivity. In optimised experimental conditions, the limits of detection for the 7 HAs studied ranged from 6 to 20 ng/L. Swimming pools have recently been recognized as an important source of exposure to DBPs and as a result, in this research for the first time, HAs have been determined in this type of water. Two HAs have been found in the analysed water: CH at concentrations between 1.2-38 and 53-340 μg/L and dichloroacetaldehyde between 0.07-4.0 and 1.8-23 μg/L in tap and swimming pool waters, respectively.

  2. Extraction of hydroxyaromatic compounds in river water by liquid-liquid-liquid microextraction with automated movement of the acceptor and the donor phase.

    PubMed

    Melwanki, Mahaveer B; Huang, Shang-Da

    2006-08-01

    Liquid-liquid-liquid microextraction with automated movement of the acceptor and the donor phase technique is described for the extraction of six hydroxyaromatic compounds in river water using a disposable and ready to use hollow fiber. Separation and quantitative analyses were performed using LC with UV detection at 254 nm. Analytes were extracted from the acidified sample solution (donor phase) into the organic solvent impregnated in the pores of the hollow fiber and then back extracted into the alkaline solution (acceptor phase) inside the lumen of the hollow fiber. The fiber was held by a conventional 10 microL LC syringe. The acceptor phase was sandwitched between the plunger and a small volume of the organic solvent (microcap). The acceptor solution was repeatedly moved in and out of the hollow fiber using a syringe pump. This movement provides a fresh acceptor phase to come in contact with the organic phase and thus enhancing extraction kinetics thereby leading to the improvement in enrichment of the analytes. The microcap separates the acceptor phase and the donor phase in addition to being partially responsible for mass transfer of the analytes from the donor solution to the acceptor solution. Under stirring, a fresh donor phase will enter through the open end of the fiber that will also contribute to the mass transfer. Various parameters affecting the extraction efficiency viz type of organic solvent, extraction time, stirring speed, effect of sodium chloride, and concentration of donor and acceptor phases were studied. RSD (3.9-5.6%), correlation coefficient (0.995-0.997), detection limit (2.0-51.2 ng/mL), enrichment factor (339-630), relative recovery (93.2-97.9%), and absolute recovery (33.9-63.0%) have also been investigated. The developed method was applied for the analysis of river water.

  3. Extraction of pesticides, dioxin-like PCBs and PAHs in water based commodities using liquid-liquid microextraction and analysis by gas chromatography-mass spectrometry.

    PubMed

    Dasgupta, Soma; Banerjee, Kaushik; Utture, Sagar; Kusari, Parijat; Wagh, Sameer; Dhumal, Kondiba; Kolekar, Sanjay; Adsule, Pandurang G

    2011-09-23

    Water based samples such as flavored drinks, juices and drinking water may contain contaminants at ultra trace level belonging to different chemical classes. A novel, simple, low-cost and fast method was developed and validated for trace residue extraction of pesticides, dioxin-like PCBs and PAHs from water and water based samples followed by analysis through gas chromatography (GC) coupled with time-of-flight mass spectrometry (ToFMS). The extraction solvent type, volume; sample volume and other extraction conditions were optimized. This was achieved by extracting 10 mL sample with 250 μL chloroform by vortexing (1 min, standing time of 2 min) followed by centrifugation (6000 rpm, 5 min). The bottom organic layer (200 μL) was pipetted out, evaporated to near dryness and reconstituted in 20 μL of ethyl acetate+cyclohexane (1:9) mixture resulting in an enrichment factor of 400. The recoveries of all compounds were within 76-120% (±10%) with the method detection limit (MDL) ranging from 1 to 250 ng/L depending on the analyte response. The MDLs were 400 times lower than the instrument quantification limits that ranged from 0.4 to 100 ng/mL. The method was further validated in water based drinks (e.g. apple, lemon, pineapple, orange, grape and pomegranate juice). For the juices with suspended pulp, the extraction was carried out with 400 μL chloroform. The extract was analyzed by GC-ToFMS at both 1D and GC×GC modes to chromatographically separate closely eluting interfering compounds the effect of which could not be minimized otherwise. The resulting peak table was filtered to identify a range of compounds belonging to specific classes viz. polycyclic aromatic hydrocarbons, chlorinated, brominated, and nitro compounds. User developed scripts were employed on the basis of identification of the molecular ion and isotope clusters or other spectral characteristics. The method performed satisfactorily in analyzing both incurred as well as market samples. Copyright

  4. [Simultaneous determination of multi-organotin compounds in seawater by liquid-liquid extraction-high performance liquid chromatography-inductively coupled plasma mass spectrometry].

    PubMed

    Yu, Zhen-Hua; Jing, Miao; Wang, Xiao-Ru; Chen, Deng-Yun; Huang, Yan-Liang

    2009-10-01

    The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds (trimethyltin, dibutyltin, tributyltin, diphenyltin and triphenyltin) in seawater samples. Agilent TC-C18 column was used for the separation, the mobile phase of HPLC was CH3CN : H2O : CH3COOH = 65 : 23 : 12 (phi3), 0.05% TEA, and pH value was adjusted to 3.0 by diluent ammonia. The flow rate was 0.6 mL x min(-1). Five mixed organotin compounds in a mix standard solution from 100 to 0.5 microg x L(-1) were applied for the method assessment. The experimental results indicate that the correlation coefficient of calibration curves (R2) for each organotin compound was over 0.998 and the detection limits of the five organotin compounds were lower than 3 ng x L(-1). Different mixed organic solvents including dichloromethane or toluene were used for extraction of organotin and the extraction condition of organotin from seawater was optimized. The 100 mL seawater acidized by hydrochloric acid was extracted by 10 mL carbon dichloride (CH2 Cl2) with 2% tropolone for 10 min twice. Extracted organic solvents were mixed and blown to one drop by nitrogen with the rate of 1.7 mL x min(-1), then 1 mL acetonitrile was added to the drop for redissolving the organotin compounds. Finally, the mixed redissolution was filtered by 0.22 microm organic filter membrane before analysis. It was found that the only organotin compound in seawater was triphenyltin (TPHT) and the content was 53.2 ng x L(-1). The recoveries test from the standard addition for diphenyltin (DPHT), dibutyltin (DBT), tributyltin (TBT) and triphenyltin (TPHT) were over 80%. However, the recovery for trimethyltin (TMT) was relatively low and the value was 50%. The reason might be attributed to the decomposition or adsorption of those compounds during the extraction procedure. Further study on this subject is in

  5. Quantification of free and total bisphenol A and bisphenol B in human urine by dispersive liquid-liquid microextraction (DLLME) and heart-cutting multidimensional gas chromatography-mass spectrometry (MD-GC/MS).

    PubMed

    Cunha, S C; Fernandes, J O

    2010-11-15

    A novel method combining dispersive liquid-liquid microextraction (DLLME) and heart-cutting multidimensional gas chromatography coupled to mass spectrometry was developed for the determination of free and total bisphenol A (BPA) and bisphenol B (BPB) in human urine samples. The DLLME procedure combines extraction, derivatization and concentration of the analytes into one step. Several important variables influencing the extraction efficiency and selectivity such as nature and volume of extractive and dispersive solvents as well as the amount of acetylating reagent were investigated. The temperature and time to hydrolyze BPA and BPB conjugates with a β-glucuronidase and sulfatase enzyme preparation were also studied. Under the optimized conditions good efficiency extraction (71-93%) and acceptable total DLLME yields (56-77%) were obtained for both analytes. Matrix-matched calibration curves were linear with correlation coefficients higher than 0.996 in the range level 0.1-5 μg/l, and the relative standard deviations (%RSD) were lower than 20% (n=6). The limits of detection were 0.03 and 0.05 μg/l for BPA and BPB, respectively. The applicability of the proposed method for determining urinary free and total BPA and BPB was assessed by analyzing the human urine of a group of 20 volunteers. Free BPA was detected in 45% of the sample whereas total BPA was detected in 85% of the samples at concentrations ranging between 0.39 and 4.99 μg/l. BPB was detected in conjugated form in two samples.

  6. Determination of bisphenol A and bisphenol B in canned seafood combining QuEChERS extraction with dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Cunha, S C; Cunha, C; Ferreira, A R; Fernandes, J O

    2012-11-01

    A new simple and reliable method combining an acetonitrile partitioning extractive procedure followed by dispersive solid-phase cleanup (QuEChERS) with dispersive liquid-liquid microextraction (DLLME) and further gas chromatography mass spectrometry analysis was developed for the simultaneous determination of bisphenol A (BPA) and bisphenol B (BPB) in canned seafood samples. Besides the great enrichment factor provided, the final DLLME extractive step was designed in order to allow the simultaneous acetylation of the compounds required for their gas chromatographic analysis. Tetrachloroethylene was used as extractive solvent, while the acetonitrile extract obtained from QuEChERS was used as dispersive solvent, and anhydride acetic as derivatizing reagent. The main factors influencing QuEChERS and DLLME efficiency including nature of QuEChERS dispersive-SPE sorbents, amount of DLLME extractive and dispersive solvents and nature and amount of derivatizing reagent were evaluated. DLLME procedure provides an effective enrichment of the extract, allowing the required sensitivity even using a single quadropole MS as detector. The optimized method showed to be accurate (>68 % recovery), reproducible (<21 % relative standard deviation) and sensitive for the target analytes (method detection limits of 0.2 μg/kg for BPA and 0.4 μg/kg for BPB). The screening of several canned seafood samples commercialized in Portugal (total = 47) revealed the presence of BPA in more than 83 % of the samples with levels ranging from 1.0 to 99.9 μg/kg, while BPB was found in only one sample at a level of 21.8 μg/kg.

  7. Quantification of β-carotene, retinol, retinyl acetate and retinyl palmitate in enriched fruit juices using dispersive liquid-liquid microextraction coupled to liquid chromatography with fluorescence detection and atmospheric pressure chemical ionization-mass spectrometry.

    PubMed

    Viñas, Pilar; Bravo-Bravo, María; López-García, Ignacio; Hernández-Córdoba, Manuel

    2013-02-01

    A detailed optimization of dispersive liquid-liquid microextraction (DLLME) was carried out for developing liquid chromatographic (HPLC) techniques, using both fluorescence and atmospheric pressure chemical ionization mass spectrometric (APCI-MS) detection, for the simultaneous analysis of preforms of vitamin A: retinol (R), retinyl acetate (RA), retinyl palmitate (RP) and β-carotene (β-C). The HPLC analyses were carried out using a mobile phase composed of methanol and water, with gradient elution. The APCI-MS and fluorescence spectra permitted the correct identification of compounds in the analyzed samples. Parameters affecting DLLME were optimized using 2 mL of methanol (disperser solvent) containing 150 μL carbon tetrachloride (extraction solvent). The precision ranged from 6% to 8% (RSD) and the limits of detection were between 0.03 and 1.4 ng mL(-1), depending on the compound. The enrichment factor values were in the 21-44 range. Juice samples were analyzed without saponification and no matrix effect was found when using fluorescence detection, so calibration was possible with aqueous standards. However, a matrix effect appeared with APCI-MS, in which case it was necessary to apply matrix-matched calibration. There was great variability in the forms of vitamin A present in the juices, the most abundant ester being retinyl acetate (0.04 to 3.4 μg mL(-1)), followed by the amount of retinol (0.01 to 0.16 μg mL(-1)), while retinyl palmitate was not detected, except in the milk-containing juice, in which RP was the main form. The representative carotenoid β-carotene was present in the orange, peach, mango and multifruit juices in high amounts. The method was validated using two certified reference materials. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Determination of perfluorooctanoic acid and perfluorooctane sulfonate in cooking oil and pig adipose tissue using reversed-phase liquid-liquid extraction followed by high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Tang, Caiming; Tan, Jianhua; Wang, Chunwei; Peng, Xianzhi

    2014-05-09

    Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are two perfluorinated compounds (PFCs) ubiquitously present in the environment, which could pose potential adverse effects on human health. Contamination and presence of PFOA and PFOS should be eliminated or rigidly restricted in food stuffs such as cooking oils and lard (from pig adipose tissue). This work describes a rapid, simple, reliable and sensitive method for quantitative analysis of PFOA and PFOS in cooking oils and pig adipose tissue with liquid chromatography tandem mass spectrometry (LC-MS/MS). The pretreatment mainly included a one-step reversed-phase liquid-liquid extraction using the mixture of basified water/methanol as the aqueous system, and dichloromethane (DCM) as the non-polar system. PFOA and PFOS can be successfully separated from the two lipid-rich matrices, i.e., cooking oil and adipose tissue, and extracted into the aqueous system, and then directly analyzed with LC-MS/MS. This method was validated in terms of accuracy (both intra- and inter-batch), precision, recovery, linearity, sensitivity and applicability. The intra-batch accuracies for PFOA and PFOS in cooking oil samples were within 93.9-101.9% with relative standard deviation (RSD) no more than 10.9%, and the inter-batch accuracies were 91.2-96.2% with RSD not exceeding 10.0%. The intra-batch accuracies of the analytes in pig adipose tissue samples were 102.9-113.0% with RSD of 8.8-13.1%. And the quantification ranges of PFOA and PFOS were 0.01-25ng/mL. This method has been applied to the analysis of PFOA and PFOS in real samples collected from local markets in Guangzhou, China. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction for the determination of 4 designer benzodiazepines in urine samples by gas chromatography-triple quadrupole mass spectrometry.

    PubMed

    Meng, Liang; Zhu, Binling; Zheng, Kefang; Fu, Shanlin

    2017-05-15

    A novel microextraction technique based on ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction (UA-LDS-DLLME) had been applied for the determination of 4 designer benzodiazepines (phenazepam, diclazepam, flubromazepam and etizolam) in urine samples by gas chromatography- triple quadrupole mass spectrometry (GC-QQQ-MS). Ethyl acetate (168μL) was added into the urine samples after adjusting pH to 11.3. The samples were sonicated in an ultrasonic bath for 5.5min to form a cloudy suspension. After centrifugation at 10000rpm for 3min, the supernatant extractant was withdrawn and injected into the GC-QQQ-MS for analysis. Parameters affecting the extraction efficiency have been investigated and optimized by means of single factor experiment and response surface methodology (Box-Behnken design). Under the optimum extraction conditions, a recovery of 73.8-85.5% were obtained for all analytes. The analytical method was linear for all analytes in the range from 0.003 to 10μg/mL with the correlation coefficient ranging from 0.9978 to 0.9990. The LODs were estimated to be 1-3ng/mL. The accuracy (expressed as mean relative error MRE) was within ±5.8% and the precision (expressed as relative standard error RSD) was less than 5.9%. UA-LDS-DLLME technique has the advantages of shorter extraction time and is suitable for simultaneous pretreatment of samples in batches. The combination of UA-LDS-DLLME with GC-QQQ-MS offers an alternative analytical approach for the sensitive detection of these designer benzodiazepines in urine matrix for clinical and medico-legal purposes. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Comparison of turbulent-flow chromatography with automated solid-phase extraction in 96-well plates and liquid-liquid extraction used as plasma sample preparation techniques for liquid chromatography-tandem mass spectrometry.

    PubMed

    Zimmer, D; Pickard, V; Czembor, W; Müller, C

    1999-08-27

    Turbulent flow chromatography (TFC) combined with the high selectivity and sensitivity of tandem mass spectrometry (MS-MS) is a new technique for the fast direct analysis of drugs from crude plasma. TFC in the 96-well plate format reduces significantly the time required for sample clean-up in the laboratory. For example, for 100 samples the workload for a technician is reduced from about 8 h by a manual liquid-liquid extraction (LLE) assay to about 1 h in the case of TFC. Sample clean-up and analysis are performed on-line on the same column. Similar chromatographic performance and validation results were achieved using HTLC Turbo-C18 columns (Cohesive Technologies) and Oasis HLB extraction columns (Waters). One 96-well plate with 96 plasma samples is analyzed within 5.25 h, corresponding to 3.3 min per sample. Compared to this LLE and analysis of 96 samples takes about 16 h. Two structurally different and highly protein bound compounds, drug A and drug B, were analyzed under identical TFC conditions and the assays were fully validated for the application to toxicokinetics studies (compliant with Good Laboratory Practices-GLP). The limit of quantitation was 1.00 microg/l and the linear working range covered three orders of magnitude for both drugs. In the case of drug A the quality of analysis by TFC was similar to the reference LLE assay and slightly better than automated solid-phase extraction in 96-well plates. The accuracy was -3.1 to 6.7% and the precision was 3.1 to 6.8% in the case of drug A determined for dog plasma by TFC-MS-MS. For drug B the accuracy was -3.7 to 3.5% and the precision was 1.6 to 5.4% for rat plasma, which is even slightly better than what was achieved with the validated protein precipitation assay.

  11. Comparison of hollow fiber liquid-phase microextraction and ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction for the determination of drugs of abuse in biological samples by gas chromatography-mass spectrometry.

    PubMed

    Meng, Liang; Zhang, Wenwen; Meng, Pinjia; Zhu, Binling; Zheng, Kefang

    2015-05-01

    Two microextraction techniques based on hollow fiber liquid-phase microextraction (HF-LPME) and ultrasound-assisted low-density solvent dispersive liquid-liquid microextraction (UA-LDS-DLLME) had been applied for the determination of drugs of abuse (methamphetamine, amphetamine, 3,4-methylenedioxymethamphetamine, 3,4-methylenedioxyamphetamine, methcathinone, ketamine, meperidine, and methadone) in urine and blood samples by gas chromatography-mass spectrometry. Parameters affecting extraction efficiency have been investigated and optimized for both methods. Under the optimum conditions, linearities were observed for all analytes in the range 0.0030-10 μg/ml with the correlation coefficient (R) ranging from 0.9985 to 0.9995 for HF-LPME and in the range 0.0030-10 μg/ml with the R ranging from 0.9985 to 0.9994 for DLLME. The recovery of 79.3-98.6% with RSDs of 1.2-4.5% was obtained for HF-LPME, and the recovery of 79.3-103.4% with RSDs of 2.4-5.7% was obtained for DLLME. The LODs (S/N=3) were estimated to be in the range from 0.5 to 5 ng/ml and 0.5 to 4 ng/ml, respectively. Compared with HF-LPME, the UA-LDS-DLLME technique had the advantages of less extraction time, suitability for batches of sample pretreatment simultaneously, and higher extraction efficiency, while HF-LPME has excellent sample clean-up effect, and is a robust and suitable technique for various sample matrices with better repeatability. Both methods were successfully applied to the analysis of drugs of abuse in real human blood sample. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Ultrasound-assisted leaching-dispersive solid-phase extraction followed by liquid-liquid microextraction for the determination of polybrominated diphenyl ethers in sediment samples by gas chromatography-tandem mass spectrometry.

    PubMed

    Fontana, Ariel R; Lana, Nerina B; Martinez, Luis D; Altamirano, Jorgelina C

    2010-06-30

    Ultrasound-assisted leaching-dispersive solid-phase extraction followed by dispersive liquid-liquid microextraction (USAL-DSPE-DLLME) technique has been developed as a new analytical approach for extracting, cleaning up and preconcentrating polybrominated diphenyl ethers (PBDEs) from sediment samples prior gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis. In the first place, PBDEs were leached from sediment samples by using acetone. This extract was cleaned-up by DSPE using activated silica gel as sorbent material. After clean-up, PBDEs were preconcentrated by using DLLME technique. Thus, 1 mL acetone extract (disperser solvent) and 60 microL carbon tetrachloride (extraction solvent) were added to 5 mL ultrapure water and a DLLME technique was applied. Several variables that govern the proposed technique were studied and optimized. Under optimum conditions, the method detection limits (MDLs) of PBDEs calculated as three times the signal-to-noise ratio (S/N) were within the range 0.02-0.06 ng g(-1). The relative standard deviations (RSDs) for five replicates were <9.8%. The calibration graphs were linear within the concentration range of 0.07-1000 ng g(-1) for BDE-47, 0.09-1000 ng g(-1) for BDE-100, 0.10-1000 ng g(-1) for BDE-99 and 0.19-1000 ng g(-1) for BDE-153 and the coefficients of estimation were > or =0.9991. Validation of the methodology was carried out by standard addition method at two concentration levels (0.25 and 1 ng g(-1)) and by comparing with a reference Soxhlet technique. Recovery values were > or =80%, which showed a satisfactory robustness of the analytical methodology for determination of low PBDEs concentration in sediment samples.

  13. Miniscale Liquid-Liquid Extraction Coupled with Full Evaporation Dynamic Headspace Extraction for the Gas Chromatography/Mass Spectrometric Analysis of Polycyclic Aromatic Hydrocarbons with 4000-to-14 000-fold Enrichment.

    PubMed

    Liew, Christina Shu Min; Li, Xiao; Lee, Hian Kee

    2016-09-20

    A new sample preparation approach of combining a miniscale version of liquid-liquid extraction (LLE), termed miniscale-LLE (msLLE), with automated full evaporation dynamic headspace extraction (FEDHS) was developed. Its applicability was demonstrated in the extraction of several polycyclic aromatic hydrocarbons (PAHs) (acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene) from aqueous samples. In the first step, msLLE was conducted with 1.75 mL of n-hexane, and all of the extract was vaporized through a Tenax TA sorbent tube via a nitrogen gas flow, in the FEDHS step. Due to the stronger π-π interaction between the Tenax TA polymer and PAHs, only the latter, and not n-hexane, was adsorbed by the sorbent. This selectivity by the Tenax TA polymer allowed an effective concentration of PAHs while eliminating n-hexane by the FEDHS process. After that, thermal desorption was applied to the PAHs to channel them into a gas chromatography/mass spectrometric (GC/MS) system for analysis. Experimental parameters affecting msLLE (solvent volume and mixing duration) and FEDHS (temperature and duration) were optimized. The obtained results achieved low limits of detection (1.85-3.63 ng/L) with good linearity (r(2) > 0.9989) and high enrichment factors ranging from 4200 to 14 100. The optimized settings were applied to the analysis of canal water sampled from an industrial area and tap water, and this methodology was compared to stir-bar sorptive extraction (SBSE). This innovative combined extraction-concentration approach proved to be fast, effective, and efficient in determining low concentrations of PAHs in aqueous samples.

  14. New reversed phase dispersive liquid-liquid microextraction method for the determination of phenolic compounds in virgin olive oil by rapid resolution liquid chromathography with ultraviolet-visible and mass spectrometry detection.

    PubMed

    Godoy-Caballero, M P; Acedo-Valenzuela, M I; Galeano-Díaz, T

    2013-10-25

    The determination of phenolic compounds in virgin olive oil using a new reversed phase dispersive liquid-liquid microextraction (RP-DLLME) procedure coupled with rapid resolution liquid chromatography-diode array and mass spectrometry detection (RRLC-DAD-MS) have been performed. A rapid resolution Zorbax Eclipse XDB-C18 column (4.6 mm × 50 mm, 1.8 μm particle size) has been employed and eighteen phenolic compounds belonging to different families have been identified and quantified spending a total time of 26 and 13 min with UV-visible and MS detection, respectively. Response surface methodology has been applied by means of a central composite design for the optimization of the variables affecting the extraction procedure searching for the best recovery. The validation of the methods was performed through the establishment of the external standard calibration curves and the analytical figures of merit. Limits of detection ranging from 10 to 400 ng mL(-1) and 1 to 200 ng mL(-1) were achieved using UV-visible and MS detection, respectively. The extraction of phenolic compounds from virgin olive oil was performed in a simple and rapid way by RP-DLLME with ethanol:water 60:40 (v/v) as extracting solvent and 1,4-dioxane as disperser solvent. The quantification of the phenolic compounds in virgin olive oils from different olive varieties was carried out by means of the standard addition method and, finally the procedure for the sample treatment was validated using the well established solid phase extraction procedure with Diol cartridges. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Improved gas chromatography-negative ion chemical ionization tandem mass spectrometric method for determination of 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid in hair using mechanical pulverization and bead-assisted liquid-liquid extraction.

    PubMed

    Kim, Jin Young; Cheong, Jae Chul; Lee, Jae Il; In, Moon Kyo

    2011-03-20

    A gas chromatography-negative ion chemical ionization tandem mass spectrometric (GC-NCI-MS/MS) method was developed and validated for the determination of 11-nor-Δ(9)-tetrahydrocannabinol-9-carboxylic acid (THC-COOH) in human hair. After decontamination, hair samples were weighed (25mg), mechanically pulverized with a bead mill, and incubated in 0.7 mL of 1.0M sodium hydroxide at 95 °C for 30 min. Bead-assisted liquid-liquid extraction was performed with n-hexane:ethyl acetate (9:1, v/v), a method developed in our laboratory. The extract was evaporated to dryness, derivatized with pentafluoropropanol and pentafluoropropionic anhydride, and analyzed by GC-MS/MS in the negative ion chemical ionization mode using methane as the reagent gas. The linear ranges were 0.05-10.0 pg/mg for THC-COOH with the coefficient of determination (r(2) = 0.9976). The intra-day and inter-day precisions were within 1.7 and 13.8%, respectively. The intra-day and inter-day accuracies were -4.8 to 10.0% and -3.9 to 3.8%, respectively. The limit of detection and quantification were 0.015 and 0.05 pg/mg, respectively. The recoveries were in the range of 79.4-87.1%. The results indicate that the proposed method is simple, rapid, accurate, and precise for determination of THC-COOH in hair. The method identified THC-COOH in hair specimens from suspected marijuana abusers.

  16. Dispersive liquid-liquid microextraction followed by microwave-assisted silylation and gas chromatography-mass spectrometry analysis for simultaneous trace quantification of bisphenol A and 13 ultraviolet filters in wastewaters.

    PubMed

    Cunha, S C; Pena, A; Fernandes, J O

    2015-10-02

    A novel multi-residue gas chromatography-mass spectrometry (GC-MS) method was validated for the simultaneous determination of trace levels (ng/L) of 13 UV-filters and bisphenol A (BPA) in wastewater samples. It was based on dispersive liquid-liquid microextraction (DLMME) followed by rapid microwave-assisted silylation of the analytes. Several parameters of both extraction and derivatization steps such as type of extractive and dispersive solvents, solvent volumes, pH, salt addition, time and power of microwave were evaluated to achieve the highest yield and to attain the lowest detection limits. Optimized DLLME consisted in the formation of a cloudy solution promoted by the fast addition to the sample (10mL) of a mixture of tetrachloroethylene (50μL, extraction solvent) in acetone (1mL, dispersive solvent). The sedimented phase obtained was evaporated and further silylated under the irradiation of 600W microwave for 5min, being the derivatization yields similar to those obtained after a conventional heating process for 30min at 75°C. Limits of detection and quantification of the method using real samples were 2ng/L and 10ng/L, respectively. Mean extraction efficiency of 82% for three concentrations were achieved, supporting the accuracy of the method. Intra-day and inter-day repeatability of measurements (expressed as relative standard deviation) were lower than 22%. The method was successfully applied to the determination of UV-filters and BPA in samples collected from 15 wastewater treatment plants (WWTPs) in Portugal. Eight analytes were detected, among which 2-hydroxy-4-methoxybenzophenone, 2-ethylhexyl-4-(dimethylamino)benzoate, octocrylene, and BPA were consistently found in the three seasons of collection.

  17. Molecularly imprinted polymer coupled with dispersive liquid-liquid microextraction and injector port silylation: a novel approach for the determination of 3-phenoxybenzoic acid in complex biological samples using gas chromatography-tandem mass spectrometry.

    PubMed

    Mudiam, Mohana Krishna Reddy; Chauhan, Abhishek; Jain, Rajeev; Dhuriya, Yogesh Kumar; Saxena, Prem Narain; Khanna, Vinay Kumar

    2014-01-15

    A novel analytical approach based on molecularly imprinted solid phase extraction (MISPE) coupled with dispersive liquid-liquid microextraction (DLLME), and injector port silylation (IPS) has been developed for the selective preconcentration, derivatization and analysis of 3-phenoxybenzoic acid (3-PBA) using gas chromatography-tandem mass spectrometry (GC-MS/MS) in complex biological samples such as rat blood and liver. Factors affecting the synthesis of MIP were evaluated and the best monomer and cross-linker were selected based on binding affinity studies. Various parameters of MISPE, DLLME and IPS were optimized for the selective preconcentration and derivatization of 3-PBA. The developed method offers a good linearity over the calibration range of 0.02-2.5ngmg(-1) and 7.5-2000ngmL(-1) for liver and blood respectively. Under optimized conditions, the recovery of 3-PBA in liver and blood samples were found to be in the range of 83-91%. The detection limit was found to be 0.0045ngmg(-1) and 1.82ngmL(-1) in liver and blood respectively. SRM transition of 271→227 and 271→197 has been selected as quantifier and qualifier transition for 3-PBA derivative. Intra and inter-day precision for five replicates in a day and for five, successive days was found to be less than 8%. The method developed was successfully applied to real samples, i.e. rat blood and tissue for quantitative evaluation of 3-PBA. The analytical approach developed is rapid, economic, simple, eco-friendly and possess immense utility for the analysis of analytes with polar functional groups in complex biological samples by GC-MS/MS.

  18. Multiclass method for the determination of pharmaceuticals and personal care products in compost from sewage sludge using ultrasound and salt-assisted liquid-liquid extraction followed by ultrahigh performance liquid chromatography-tandem mass spectrometry analysis.

    PubMed

    Luque-Muñoz, A; Vílchez, J L; Zafra-Gómez, A

    2017-07-21

    An analytical method for the analysis of 16 pharmaceuticals and personal care products in compost from sewage sludge is successfully validated. Ultrasound assisted extraction with a mixture of acetonitrile:ethyl acetate (1:1, v/v) containing 10% (v/v) of acetic acid was carried out. Two cycles of extraction of 10min were applied. A clean-up of the extracts using salt-assisted liquid-liquid extraction (SALLE) was also included. Experimental design was used for the optimization of the main parameters involved in the extraction and cleaned-up steps. The chromatographic separation was carried out by ultrahigh performance liquid chromatography using a mobile phase gradient mixture of a 13mM buffer ammonium formate solution (pH 9.25) (solvent A) and methanol (solvent B). An ACQUITY UPLC(®) BEH C18 column (1.7μm; 2.1×50mm) column was used. Analytes were separated in less than 11min. The compounds were detected and quantified using single reaction monitoring electrospray tandem mass spectrometry. The limits of detection calculated ranged from 0.5 to 4ngg(-1)d.w., and the limits of quantification from 2 to 13ngg(-1)d.w. Recoveries from 93% to 111%, with relative standar deviations lower than 11% in all cases, were obtained. The method was applied to natural compost samples. High concentrations of some analytes were found. Ketoprofen (510ngg(-1)d.w.), methylparaben (240ngg(-1)d.w.), diclofenac (175ngg(-1)d.w.) and flufenamic acid (128ngg(-1)d.w.) were the most abundant. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Hollow fiber-based liquid-liquid-liquid micro-extraction with osmosis: I. Theoretical simulation and verification.

    PubMed

    Wu, Qian; Wu, Dapeng; Geng, Xuhui; Shen, Zheng; Guan, Yafeng

    2012-07-27

    Osmosis in hollow fiber-based liquid-liquid-liquid micro-extraction (HF-LLLME) was validated and utilized to improve enrichment factor of extraction in this study. When donor phase (sample solution) with higher ion strength than acceptor phase (extraction phase) was used, osmosis was established from acceptor phase, through organic membrane to donor phase. The mass flux expression of analytes across the organic membrane was established based on the convective-diffusive kinetic model, and the kinetic process for HF-LLLME with osmosis was simulated. Simulation results indicated that osmosis from acceptor phase to donor phase can increase enrichment factor of HF-LLLME, accelerate extraction process, and even result in the distribution ratio of analytes between donor and acceptor phase exceeding their partition coefficient. This phenomenon was verified by the experimental data of extraction with six organic acids and four organic bases as the model analytes. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Qualitative detection of diuretics and acidic metabolites of other doping agents in human urine by high-performance liquid chromatography-tandem mass spectrometry: comparison between liquid-liquid extraction and direct injection.

    PubMed

    Deventer, K; Pozo, O J; Van Eenoo, P; Delbeke, F T

    2009-07-31

    Direct injection of urine has gained interest in the field of analytical toxicology, including doping control analysis. However, implementation of a direct urinalysis method for the LC-MS/MS detection of 34 diuretics and 9 other doping agents yielded several analytical problems, which were not observed using a traditional liquid-liquid extraction. Therefore a comparative study was made between liquid-liquid extraction and direct injection. Comparison of validation results showed that the liquid-liquid extraction at pH 7 allows to analyze samples without major drawbacks regarding matrix effects. Hence, good sensitivity was observed and detection limits ranged between 1 and 250 ng/mL for all compounds. In the direct injection approach shifted retention times were observed for several acidic and basic compounds due to unwanted matrix effects. This shift was reduced by a 25-fold dilution of the urine samples. Besides the improved retention time stability the diluted samples also exhibited lower ion suppression than the undiluted ones. After 25-fold dilution, detection limits ranged between 10 and 250 ng/mL for all compounds. Since these detection limits are at or below the minimum required performance level, imposed by the World Anti-Doping Agency, the method could be applied to routine anti-doping analysis. Samples, previously declared positive, were reanalysed using both the liquid-liquid extraction and direct injection. With both techniques all 26 samples were found to be positive, showing the applicability of direct injection for the analysis of diuretics.

  1. Hollow fiber apparatus and use thereof for fluids separations and heat and mass transfers

    SciTech Connect

    Bikson, Benjamin; Etter, Stephen; Ching, Nathaniel

    2014-06-10

    A hollow fiber device includes a hollow fiber bundle, comprising a plurality of hollow fibers, a first tubesheet and a second tubesheet encapsulating respective distal ends of the hollow fiber bundle. The tubesheets have boreholes in fluid communication with bores of the hollow fibers. In at least one of the tubesheets, the boreholes are formed radially. The hollow fiber device can be utilized in heat exchange, in gas/gas, liquid/liquid and gas/liquid heat transfer, in combined heat and mass transfer and in fluid separation assemblies and processes. The design disclosed herein is light weight and compact and is particularly advantageous when the pressure of a first fluid introduced into the bores of hollow fibers is higher than the pressure on the shell side of the device.

  2. The balanced-force volume tracking algorithm and global embedded interface formulation for droplet dynamics with mass transfer

    SciTech Connect

    Francois, Marianne M; Carlson, Neil N

    2010-01-01

    Understanding the complex interaction of droplet dynamics with mass transfer and chemical reactions is of fundamental importance in liquid-liquid extraction. High-fidelity numerical simulation of droplet dynamics with interfacial mass transfer is particularly challenging because the position of the interface between the fluids and the interface physics need to be predicted as part of the solution of the flow equations. In addition, the discontinuity in fluid density, viscosity and species concentration at the interface present additional numerical challenges. In this work, we extend our balanced-force volume-tracking algorithm for modeling surface tension force (Francois et al., 2006) and we propose a global embedded interface formulation to model the interfacial conditions of an interface in thermodynamic equilibrium. To validate our formulation, we perform simulations of pure diffusion problems in one- and two-dimensions. Then we present two and three-dimensional simulations of a single droplet dynamics rising by buoyancy with mass transfer.

  3. Hollow fiber-based liquid-liquid-liquid micro-extraction with osmosis: II. Application to quantification of endogenous gibberellins in rice plant.

    PubMed

    Wu, Qian; Wu, Dapeng; Duan, Chunfeng; Shen, Zheng; Guan, Yafeng

    2012-11-23

    The phenomenon and benefits of osmosis in hollow fiber-based liquid-liquid-liquid micro-extraction (HF-LLLME) were theoretically discussed in part I of this study. In this work, HF-LLLME with osmosis was coupled with high performance liquid chromatography-triple quadrupole mass spectrometry (HPLC-triple quadrupole MS/MS) to analyze eight gibberellins (gibberellin A(1), gibberellin A(3), gibberellin A(4), gibberellin A(7), gibberellin A(8), gibberellin A(9), gibberellin A(19) and gibberellin A(20)) in rice plant samples. According to the theory of HF-LLLME with osmosis, single factor experiments, orthogonal design experiments and mass transfer simulation of extraction process were carried out to select the optimal conditions. Cyclohexanol - n-octanol (1:3, v/v) was selected as organic membrane. Donor phase of 12 mL was adjusted to pH 2 and 20% NaCl (w/v) was added. Acceptor phase with an initial volume of 20 μL was the solution of 0.12 mol L(-1) Na(2)CO(3)-NaHCO(3) buffer (pH 9). Temperature was chosen to be 30 °C and extraction time was selected to be 90 min. Under optimized conditions, this method provided good linearity (r, 0.99552-0.99991) and low limits of detection (0.0016-0.061 ng mL(-1)). Finally, this method was applied to the analysis of endogenous gibberellins from plant extract which was obtained with traditional solvent extraction of rice plant tissues, and the relative recoveries were from 62% to 166%. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Dynamical mass transfer in cataclysmic binaries

    NASA Technical Reports Server (NTRS)

    Melia, Fulvio; Lamb, D. Q.

    1987-01-01

    When a binary comes into contact and mass transfer begins, orbital angular momentum is stored in the accretion disk until the disk couples tidally to the binary system. Taam and McDermott (1987) have suggested that this leads to unstable dynamical mass transfer in many cataclysmic variables in which mass transfer would otherwise be stable, and that it explains the gap between 2 and 3 h in the orbital period distribution of these systems. Here the consequences of this hypothesis for the evolution of cataclysmic binaries are explored. It is found that systems coming into contact longward of the period gap undergo one or more episodes of dynamical mass transfer.

  5. Solid-phase extraction combined with dispersive liquid-liquid microextraction and chiral liquid chromatography-tandem mass spectrometry for the simultaneous enantioselective determination of representative proton-pump inhibitors in water samples.

    PubMed

    Zhao, Pengfei; Deng, Miaoduo; Huang, Peiting; Yu, Jia; Guo, Xingjie; Zhao, Longshan

    2016-09-01

    This report describes, for the first time, the simultaneous enantioselective determination of proton-pump inhibitors (PPIs-omeprazole, lansoprazole, pantoprazole, and rabeprazole) in environmental water matrices based on solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME) and chiral liquid chromatography-tandem mass spectrometry. The optimized results of SPE-DLLME were obtained with PEP-2 column using methanol-acetonitrile (1/1, v/v) as elution solvent, dichloroethane, and acetonitrile as extractant and disperser solvent, respectively. The separation and determination were performed using reversed-phase chromatography on a cellulose chiral stationary phase, a Chiralpak IC (250 mm × 4.6 mm, 5 μm) column, under isocratic conditions at 0.6 mL min(-1) flow rate. The analytes were detected in multiple reaction monitoring (MRM) mode by triple quadrupole mass spectrometry. Isotopically labeled internal standards were used to compensate matrix interferences. The method provided enrichment factors of around 500. Under optimal conditions, the mean recoveries for all eight enantiomers from the water samples were 89.3-107.3 % with 0.9-10.3 % intra-day RSD and 2.3-8.1 % inter-day RSD at 20 and 100 ng L(-1) levels. Correlation coefficients (r (2)) ≥ 0.999 were achieved for all enantiomers within the range of 2-500 μg L(-1). The method detection and quantification limits were at very low levels, within the range of 0.67-2.29 ng L(-1) and 2.54-8.68 ng L(-1), respectively. This method was successfully applied to the determination of the concentrations and enantiomeric fractions of the targeted analytes in wastewater and river water, making it applicable to the assessment of the enantiomeric fate of PPIs in the environment. Graphical Abstract Simultaneous enantioselective determination of representative proton-pump inhibitors in water samples.

  6. Mathematical modelling of Liquid -Liquid extraction in the slug flow regime in a microchannel

    NASA Astrophysics Data System (ADS)

    Ramji, Sundari; Bhagavatula, Dinesh; Rakesh, Arjun; Pushpavanam, S.

    2016-11-01

    Mixing in the slug flow regime in microchannels is enhanced by the presence of internal circulations induced by shear due to wall. This helps improve mass transfer in this flow regime. We exploit the low Re characteristic of the flow and seek a numerical solution to understand the structure of the vortex patterns formed in the two phases in the slug flow regime. We study liquid-liquid extraction in the system to determine the improvement in mass transfer. The system was analyzed for two cases when there is (i) no film surrounding the slug (ii) a thin film surrounding the slug. The 2D governing equations for fluid flow are solved using two approaches: a) a stream function formulation based on finite differences b) primitive variable formulation with the Chebyshev collocation method. The effect of viscosity ratio, slug length and film thickness on the vortex structure were studied. While secondary vortices were induced in the less viscous phase in the case where the thin film is absent, they are always generated in the slug irrespective of the viscosity ratio in the case where the film is present. The species balance equation was then solved numerically using two approaches: a) an Alternating Direction Explicit method and b) the Locally One Dimensional splitting technique. The effect of varying Peclet number from 0 to 104 on the solute transfer from the slug to the continuous phase was studied. The extraction performance is analyzed in terms of extraction efficiency and mass transfer coefficient.

  7. Simultaneous determination of 12 pharmaceuticals in water samples by ultrasound-assisted dispersive liquid-liquid microextraction coupled with ultra-high performance liquid chromatography with tandem mass spectrometry.

    PubMed

    Guan, Jin; Zhang, Chi; Wang, Yang; Guo, Yiguang; Huang, Peiting; Zhao, Longshan

    2016-11-01

    A new analytical method was developed for simultaneous determination of 12 pharmaceuticals using ultrasound-assisted dispersive liquid-liquid microextraction (DLLME) followed by ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC-MS/MS). Six nonsteroidal anti-inflammatory drugs (NSAIDs, ketoprofen, mefenamic acid, tolfenamic acid, naproxen, sulindac, and piroxicam) and six antibiotics (tinidazole, cefuroxime axetil, ciprofloxacin, sulfamethoxazole, sulfadiazine, and chloramphenicol) were extracted by ultrasound-assisted DLLME using dichloromethane (800 μL) and methanol/acetonitrile (1:1, v/v, 1200 μL) as the extraction and dispersive solvents, respectively. The factors affecting the extraction efficiency, such as the type and volume of extraction and dispersive solvent, vortex and ultrasonic time, sample pH, and ionic strength, were optimized. The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution by using a small volume of dispersive solvent, which increased the extraction efficiency and reduced the equilibrium time. Under the optimal conditions, the calibration curves showed good linearity in the range of 0.04-20 ng mL(-1) (ciprofloxacin and sulfadiazine), 0.2-100 ng mL(-1) (ketoprofen, tinidazole, cefuroxime axetil, naproxen, sulfamethoxazole, and sulindac), and 1-200 ng mL(-1) (mefenamic acid, tolfenamic acid, piroxicam, and chloramphenicol). The LODs and LOQs of the method were in the range of 0.006-0.091 and 0.018-0.281 ng mL(-1), respectively. The relative recoveries of the target analytes were in the range from 76.77 to 99.97 % with RSDs between 1.6 and 8.8 %. The developed method was successfully applied to the extraction and analysis of 12 pharmaceuticals in five kinds of water samples (drinking water, running water, river water, influent and effluent wastewater) with satisfactory results. Graphical Abstract Twelve pharmaceuticals in water samples analyted by UHPLC

  8. Multiclass method for the determination of quinolones and β-lactams, in raw cow milk using dispersive liquid-liquid microextraction and ultra high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Junza, Alexandra; Dorival-García, Noemí; Zafra-Gómez, Alberto; Barrón, Dolores; Ballesteros, Oscar; Barbosa, José; Navalón, Alberto

    2014-08-22

    An analytical method based on a sample treatment by dispersive liquid-liquid microextraction (DLLME) followed by ultra high performance liquid chromatography-tandem mass spectrometry analysis (UHPLC-MS/MS) for the determination of 17 quinolones and 14 β-lactams (penicillins and cephalosporins) in raw cow milk, was validated according to the European Commission guidelines as cited in the Decision 2002/657/EC. The extraction efficiency of the DLLME depends on several parameters such as the nature and volumes of extractant and dispersive solvents, pH, concentration of salt, shaking time and time of centrifugation. These variables were accurately optimized using multivariate optimization strategies. A Plackett-Burman design to select the most influential parameters and a Doehlert design to obtain the optimum conditions have been applied. Two different pH values were used for the extraction of compounds (pH 3 for acidic quinolones and β-lactams and pH 8 for amphoteric quinolones). The method was validated using matrix-matched standard calibration followed by a recovery assay with spiked samples. The limits of quantification found ranged from 0.3 ng g(-1) for amoxicillin to 6.6 ng g(-1) for ciprofloxacin, and the precision was lower than 15% in all cases as is required by the European Regulation. The decision limits (CCα) ranged between 4.1 and 104.8 ng g(-1), while detection capabilities (CCβ) from 4.2 to 109.7 ng g(-1). These values were very close to the corresponding maximum residue limits (MLRs) for the studied antibiotics. Recoveries between 72 and 110% were also obtained. Finally, in order to evaluate the applicability of the method, 28 raw cow milk samples were analysed and it was observed that 28% of the samples were positive. However, only 11% were considered non-compliant with the current EU legislation (Commission Regulation 37/2010), due to some milk samples corresponded to treated cows with these antibiotics.

  9. In situ derivatization-ultrasound-assisted dispersive liquid-liquid microextraction for the determination of neurotransmitters in Parkinson's rat brain microdialysates by ultra high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    He, Yongrui; Zhao, Xian-En; Zhu, Shuyun; Wei, Na; Sun, Jing; Zhou, Yubi; Liu, Shu; Liu, Zhiqiang; Chen, Guang; Suo, Yourui; You, Jinmao

    2016-08-05

    Simultaneous monitoring of several neurotransmitters (NTs) linked to Parkinson's disease (PD) has important scientific significance for PD related pathology, pharmacology and drug screening. A new simple, fast and sensitive analytical method, based on in situ derivatization-ultrasound-assisted dispersive liquid-liquid microextraction (in situ DUADLLME) in a single step, has been proposed for the quantitative determination of catecholamines and their biosynthesis precursors and metabolites in rat brain microdialysates. The method involved the rapid injection of the mixture of low toxic bromobenzene (extractant) and acetonitrile (dispersant), which containing commercial Lissamine rhodamine B sulfonyl chloride (LRSC) as derivatization reagent, into the aqueous phase of sample and buffer, and the following in situ DUADLLME procedure. After centrifugation, 50μL of the sedimented phase (bromobenzene) was directly injected for ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) detection in multiple reaction monitoring (MRM) mode. This interesting combination brought the advantages of speediness, simpleness, low matrix effects and high sensitivity in an effective way. Parameters of in situ DUADLLME and UHPLC-MS/MS conditions were all optimized in detail. The optimum conditions of in situ DUADLLME were found to be 30μL of microdialysates, 150μL of acetonitrile containing LRSC, 50μL of bromobenzene and 800μL of NaHCO3-Na2CO3 buffer (pH 10.5) for 3.0min at 37°C. Under the optimized conditions, good linearity was observed with LODs (S/N>3) and LOQs (S/N>10) of LRSC derivatized-NTs in the range of 0.002-0.004 and 0.007-0.015 nmol/L, respectively. It also brought good precision (3.2-12.8%, peak area CVs%), accuracy (94.2-108.6%), recovery (94.5-105.5%) and stability (3.8-8.1%, peak area CVs%) results. Moreover, LRSC derivatization significantly improved chromatographic resolution and MS detection sensitivity of NTs when compared with the

  10. Simultaneous determination of bisphenol A and bisphenol B in beverages and powdered infant formula by dispersive liquid-liquid micro-extraction and heart-cutting multidimensional gas chromatography-mass spectrometry.

    PubMed

    Cunha, S C; Almeida, C; Mendes, E; Fernandes, J O

    2011-04-01

    The purpose of this study was to establish a reliable, cost-effective, fast and simple method to quantify simultaneously both bisphenol A (BPA) and bisphenol B (BPB) in liquid food matrixes such as canned beverages (soft drinks and beers) and powdered infant formula using dispersive liquid-liquid micro-extraction (DLLME) with in-situ derivatisation coupled with heart-cutting gas chromatography-mass spectrometry (GC-MS). For the optimisation of the DLLME procedure different amounts of various extractive and dispersive solvents as well as different amounts of the derivative reagent were compared for their effects on extraction efficiency and yields. The optimised procedure consisted of the injection of a mixture containing tetrachloroethylene (extractant), acetonitrile (dispersant) and acetic anhydride (derivatising reagent) directly into an aliquot of beverage samples or into an aqueous extract of powdered milk samples obtained after a pretreatment of the samples. Given the compatibility of the solvents used, and the low volumes involved, the procedure was easily associated with GC-MS end-point determination, which was accomplished by means of an accurate GC dual column (heart-cutting) technique. Careful optimisation of heart-cutting GC-MS conditions, namely pressure of front and auxiliary inlets, have resulted in a good analytical performance. The linearity of the matrix-matched calibration curves was acceptable, with coefficients of determination (r2) always higher than 0.99. Average recoveries of the BPA and BPB spiked at two concentration levels into beverages and powdered infant formula ranged from 68% to 114% and the relative standard deviation (RSD) was <15%. The limits of detection (LOD) in canned beverages were 5.0 and 2.0 ng l(-1) for BPA and BPB, respectively, whereas LOD in powdered infant formula were 60.0 and 30.0 ng l(-1), respectively. The limits of quantification (LOQ) in canned beverages were 10.0 and 7.0 ng l-1 for BPA and BPB, respectively

  11. Mass transfer in corrugated membranes

    NASA Astrophysics Data System (ADS)

    Gronda, Ann Mclaughry

    Research on the chemical and physical structure of membranes has failed to overcome the inverse relationship between selectivity and permeability. While this permeability is partially responsible for the rate of separation, the geometry of the membrane contributes significantly to this rate. In this work, we focused on the system geometry by examining the effect of corrugations on the rate of membrane separations. We developed a theory to describe mass transport in corrugations and to predict the effectiveness of corrugated membranes. To verify this theory, membranes with millimeter-sized corrugations were made. Pervaporation experiments with highly permeable and less permeable solutes showed excellent agreement with the theory. Based on the membrane geometry and permeability, the effectiveness factor and the flux enhancement can be quantified by a modified Thiele analysis. We used this theory to examine the effect of small corrugations on the mass transfer of both liquids and gases across membranes, including the effects of free convection, membrane supports, and Knudsen diffusion. In systems with a liquid feed, corrugations are promising only for very impermeable solutes. In gases, corrugations are more effective, especially when supported by a porous structure. We attempted to make smaller corrugations in two ways. The more promising method is phase-inversion of diblock copolymers. These diblocks were dissolved in a solvent, made into a thin film, and immersed in a liquid that was a nonsolvent for the majority block and a solvent for the minority block. In this way, we attempted to draw the minority block to the surface of an undulating structure created by the phase inversion. Ideally, the minority block would be selective and the majority block would be highly permeable or porous. Scanning electron microscopy showed promising structures made from polystyrene-polyisoprene and polyacrylonitrile-polyethylene oxide. The other, less promising, attempt at making

  12. A Simple Experiment for Mass Transfer.

    ERIC Educational Resources Information Center

    Rodriguez, Jesus M.; Henriquez, Vicente; Macias-Machin, Agustin

    1998-01-01

    Presents an experiment in which students use laboratory data to calculate the interphase mass transfer coefficient for a fluid passed over a sphere and obtain correlations for solid-gas mass transfer. Students develop a realistic mathematical model to describe the sublimation process. (DDR)

  13. How We Make Mass Transfer Seem Difficult.

    ERIC Educational Resources Information Center

    Cussler, E. L.

    1984-01-01

    Indicates that teaching of mass transfer can be improved by: (1) using a single, simple definition of mass transfer coefficients; (2) altering use of analogies; and (3) repeatedly stressing differences between mathematical models used for chemical reactions and the actual chemistry of these reactions. Examples for undergraduate/graduate courses…

  14. How We Make Mass Transfer Seem Difficult.

    ERIC Educational Resources Information Center

    Cussler, E. L.

    1984-01-01

    Indicates that teaching of mass transfer can be improved by: (1) using a single, simple definition of mass transfer coefficients; (2) altering use of analogies; and (3) repeatedly stressing differences between mathematical models used for chemical reactions and the actual chemistry of these reactions. Examples for undergraduate/graduate courses…

  15. A Simple Experiment for Mass Transfer.

    ERIC Educational Resources Information Center

    Rodriguez, Jesus M.; Henriquez, Vicente; Macias-Machin, Agustin

    1998-01-01

    Presents an experiment in which students use laboratory data to calculate the interphase mass transfer coefficient for a fluid passed over a sphere and obtain correlations for solid-gas mass transfer. Students develop a realistic mathematical model to describe the sublimation process. (DDR)

  16. Liquid-liquid-liquid microextraction with automated movement of the acceptor and the donor phase for the extraction of phenoxyacetic acids prior to liquid chromatography detection.

    PubMed

    Chen, Chung-Chiang; Melwanki, Mahaveer B; Huang, Shang-Da

    2006-02-03

    A simple liquid-liquid-liquid microextraction with automated movement of the acceptor and the donor phase (LLLME/AMADP) technique is described for the quantitative determination of five phenoxyacetic acids in water using a disposable and ready to use hollow fiber. The target compounds were extracted from the acidified sample solution (donor phase) into the organic solvent residing in the pores of the hollow fiber and then back extracted into the alkaline solution (acceptor phase) inside the lumen of the hollow fiber. The fiber was held by a conventional 10-microl syringe. The acceptor phase was sandwiched between the plunger and a small volume of the organic solvent (microcap). The acceptor solution was repeatedly moved in and out of the hollow fiber assisted by a programmable syringe pump. This repeated movement provides a fresh acceptor phase to come in-contact with the organic phase and thus enhancing extraction kinetics leading to high enrichment of the analytes. The microcap separates the aqueous acceptor phase and the donor phase in addition of being partially responsible for mass transfer of the analytes from donor solution (moving in and out of the hollow fiber from the open end of the fiber) to the acceptor solution. Separation and quantitative analyses were then performed using liquid chromatography (LC) with ultraviolet (UV) detection at 280 nm. Various parameters affecting the extraction efficiency viz. type of organic solvent used for immobilization in the pores of the hollow fiber, extraction time, stirring speed, effect of sodium chloride, and concentration of donor and acceptor phases were studied. Repeatability (RSD, 3.2-7.4%), correlation coefficient (0.996-0.999), detection limit (0.2-2.8 ng ml(-1)) and enrichment factors (129-240) were also investigated. Relative recovery (87-101%) and absolute recoveries (4.6-13%) have also been calculated. The developed method was applied for the analysis of river water.

  17. Mass Transfer Cooling Near The Stagnation Point

    NASA Technical Reports Server (NTRS)

    Roberts, Leonard

    1959-01-01

    A simplified analysis is made of mass transfer cooling, that is, injection of a foreign gas, near the stagnation point for two-dimensional and axisymmetric bodies. The reduction in heat transfer is given in terms of the properties of the coolant gas and it is shown that the heat transfer may be reduced considerably by the introduction of a gas having appropriate thermal and diffusive properties. The mechanism by which heat transfer is reduced is discussed.

  18. Binary stars: Mass transfer and chemical composition

    NASA Technical Reports Server (NTRS)

    Lambert, D. L.

    1982-01-01

    It is noted that mass exchange (and mass loss) within a binary system should produce observable changes in the surface chemical composition of both the mass losing and mass gaining stars as a stellar interior exposed to nucleosyntheses is uncovered. Three topics relating mass exchange and/or mass loss to nucleosynthesis are sketched: the chemical composition of Algol systems; the accretion disk of a cataclysmic variable fed by mass from a dwarf secondary star; and the hypothesis that classical Ba II giants result from mass transfer from a more evolved companion now present as a white dwarf.

  19. Dynamics of liquid-liquid displacement.

    PubMed

    Fetzer, Renate; Ramiasa, Melanie; Ralston, John

    2009-07-21

    Capillary driven liquid-liquid displacement in a system with two immiscible liquids of comparable viscosity was investigated by means of optical high speed video microscopy. For the first time, the impact of substrate wettability on contact line dynamics in liquid-liquid systems was studied. On all substrates, qualitatively different dynamics, in two distinct velocity regimes, were found. Hydrodynamic models apply to the fast stage of initial spreading, while nonhydrodynamic dissipation dominates contact line motion in a final stage at low speed, where the molecular kinetic theory (MKT) successfully captured the dynamics. The MKT model parameter values showed no systematic dependence on substrate wettability. This unexpected result is interpreted in terms of local contact line pinning.

  20. REDISTRIBUTOR FOR LIQUID-LIQUID EXTRACTION COLUMNS

    DOEpatents

    Bradley, J.G.

    1957-10-29

    An improved baffle plate construction to intimately mix immiscible liquid solvents for solvent extraction processes in a liquid-liquid pulse column is described. To prevent the light and heavy liquids from forming separate continuous homogeneous vertical channels through sections of the column, a baffle having radially placed rectangular louvers with deflection plates opening upon alternate sides of the baffle is placed in the column, normal to the axis. This improvement substantially completely reduces strippiig losses due to poor mixing.

  1. Ozone mass transfer and kinetics experiments

    SciTech Connect

    Bollyky, L.J.; Beary, M.M.

    1981-12-01

    Experiments were conducted at the Hanford Site to determine the most efficient pH and temperature levels for the destruction of complexants in Hanford high-level defense waste. These complexants enhance migration of radionuclides in the soil and inhibit the growth of crystals in the evaporator-crystallizer. Ozone mass transfer and kinetics tests have been outlined for the determination of critical mass transfer and kinetics parameters of the ozone-complexant reaction.

  2. Development, Fabrication, and Testing of a Liquid/Liquid Microchannel Heat Exchanger for Constellation Spacecrafts

    NASA Technical Reports Server (NTRS)

    Hawkins-Reynolds, Ebony; Le,Hung; Stephans, Ryan A.

    2009-01-01

    Minimizing mass and volume is critically important for space hardware. Microchannel technology can be used to decrease both of these parameters for heat exchangers. Working in concert with NASA, Pacific Northwest National Laboratories (PNNL) has developed a microchannel liquid/liquid heat exchanger that has resulted in significant mass and volume savings. The microchannel heat exchanger delivers these improvements without sacrificing thermal and pressure drop performance. A conventional heat exchanger has been tested and the performance of it recorded to compare it to the microchannel heat exchanger that PNNL has fabricated. The microchannel heat exchanger was designed to meet all of the requirements of the baseline heat exchanger, while reducing the heat exchanger mass and volume. The baseline heat exchanger was designed to have an transfer approximately 3.1 kW for a specific set of inlet conditions. The baseline heat exchanger mass was 2.7 kg while the microchannel mass was only 2.0 kg. More impressive, however, was the volumetric savings associated with the microchannel heat exchanger. The microchannel heat exchanger was an order of magnitude smaller than the baseline heat exchanger (2180cm3 vs. 311 cm3). This paper will describe the test apparatus designed to complete performance tests for both heat exchangers. Also described in this paper will be the performance specifications for the microchannel heat exchanger and how they compare to the baseline heat exchanger.

  3. Development, Fabrication, and Testing of a Liquid/Liquid Microchannel Heat Exchanger for Constellation Spacecrafts

    NASA Technical Reports Server (NTRS)

    Hawkins-Reynolds, Ebony; Le,Hung; Stephans, Ryan A.

    2009-01-01

    Minimizing mass and volume is critically important for space hardware. Microchannel technology can be used to decrease both of these parameters for heat exchangers. Working in concert with NASA, Pacific Northwest National Laboratories (PNNL) has developed a microchannel liquid/liquid heat exchanger that has resulted in significant mass and volume savings. The microchannel heat exchanger delivers these improvements without sacrificing thermal and pressure drop performance. A conventional heat exchanger has been tested and the performance of it recorded to compare it to the microchannel heat exchanger that PNNL has fabricated. The microchannel heat exchanger was designed to meet all of the requirements of the baseline heat exchanger, while reducing the heat exchanger mass and volume. The baseline heat exchanger was designed to have an transfer approximately 3.1 kW for a specific set of inlet conditions. The baseline heat exchanger mass was 2.7 kg while the microchannel mass was only 2.0 kg. More impressive, however, was the volumetric savings associated with the microchannel heat exchanger. The microchannel heat exchanger was an order of magnitude smaller than the baseline heat exchanger (2180cm3 vs. 311 cm3). This paper will describe the test apparatus designed to complete performance tests for both heat exchangers. Also described in this paper will be the performance specifications for the microchannel heat exchanger and how they compare to the baseline heat exchanger.

  4. Mass transfer cycles in cataclysmic variables

    NASA Technical Reports Server (NTRS)

    King, A. R.; Frank, J.; Kolb, U.; Ritter, H.

    1995-01-01

    It is well known that in cataclysmic variables the mass transfer rate must fluctuate about the evolutionary mean on timescales too long to be directly observable. We show that limit-cycle behavior can occur if the radius change of the secondary star is sensitive to the instantaneous mass transfer rate. The only reasonable way in which such a dependence can arise is through irradiation of this star by the accreting component. The system oscillates between high states, in which irradiation causes slow expansion of the secondary and drives an elevated transfer rate, and low states, in which this star contracts.

  5. Experimental investigation of liquid-liquid system drop size distribution in Taylor-Couette flow and its application in the CFD simulation

    NASA Astrophysics Data System (ADS)

    Farzad, Reza; Puttinger, Stefan; Pirker, Stefan; Schneiderbauer, Simon

    2016-11-01

    Liquid-liquid systems are widely used in the several industries such as food, pharmaceutical, cosmetic, chemical and petroleum. Drop size distribution (DSD) plays a key role as it strongly affects the overall mass and heat transfer in the liquid-liquid systems. To understand the underlying mechanisms single drop breakup experiments have been done by several researchers in the Taylor-Couette flow; however, most of those studies concentrate on the laminar flow regime and therefore, there is no sufficient amount of data in the case of in turbulent flows. The well-defined pattern of the Taylor-Couette flow enables the possibility to investigate DSD as a function of the local fluid dynamic properties, such as shear rate, which is in contrast to more complex devices such as stirred tank reactors. This paper deals with the experimental investigation of liquid-liquid DSD in Taylor-Couette flow. From high speed camera images we found a simple correlation for the Sauter mean diameter as a function of the local shear employing image processing. It is shown that this correlation holds for different oil-in-water emulsions. Finally, this empirical correlation for the DSD is used as an input data for a CFD simulation to compute the local breakup of individual droplets in a stirred tank reactor.

  6. Experimental investigation of liquid-liquid system drop size distribution in Taylor-Couette flow and its application in the CFD simulation

    NASA Astrophysics Data System (ADS)

    Farzad, Reza; Puttinger, Stefan; Pirker, Stefan; Schneiderbauer, Simon

    Liquid-liquid systems are widely used in the several industries such as food, pharmaceutical, cosmetic, chemical and petroleum. Drop size distribution (DSD) plays a key role as it strongly affects the overall mass and heat transfer in the liquid-liquid systems. To understand the underlying mechanisms single drop breakup experiments have been done by several researchers in the Taylor-Couette flow; however, most of those studies concentrate on the laminar flow regime and therefore, there is no sufficient amount of data in the case of in turbulent flows. The well-defined pattern of the Taylor-Couette flow enables the possibility to investigate DSD as a function of the local fluid dynamic properties, such as shear rate, which is in contrast to more complex devices such as stirred tank reactors. This paper deals with the experimental investigation of liquid-liquid DSD in Taylor-Couette flow. From high speed camera images we found a simple correlation for the Sauter mean diameter as a function of the local shear employing image processing. It is shown that this correlation holds for different oil-in-water emulsions. Finally, this empirical correlation for the DSD is used as an input data for a CFD simulation to compute the local breakup of individual droplets in a stirred tank reactor.

  7. Mass Transfer Enhancement in Moving Biofilm Structures

    PubMed Central

    Taherzadeh, Danial; Picioreanu, Cristian; Horn, Harald

    2012-01-01

    Biofilms are layers of microbial cells growing on an interface and they can form highly complex structures adapted to a wide variety of environmental conditions. Biofilm streamers have a small immobile base attached to the support and a flexible tail elongated in the flow direction, which can vibrate in fast flows. Herein we report numerical results for the role of the periodical movement of biofilm streamers on the nutrient uptake and in general on the solute mass transfer enhancement due to flow-induced oscillations. We developed what to our knowledge is a novel two-dimensional fluid-structure interaction model coupled to unsteady solute mass transport and solved the model using the finite element method with a moving mesh. Results demonstrate that the oscillatory movement of the biofilm tail significantly increases the substrate uptake. The mass transfer coefficient is the highest in regions close to the streamer tip. The reason for substrate transfer enhancement is the increase in speed of tip movement relative to the surrounding liquid, thereby reducing the thickness of the mass transfer boundary layer. In addition, we show that the relative mass transfer enhancement in unsteady conditions compared with the rigid static structure is larger at higher flow velocities, and this relative increase favors a more flexible structure. PMID:22500748

  8. Evaluation of the combination of a dispersive liquid-liquid microextraction method with micellar electrokinetic chromatography coupled to mass spectrometry for the determination of estrogenic compounds in milk and yogurt.

    PubMed

    D'Orazio, Giovanni; Asensio-Ramos, María; Hernández-Borges, Javier; Rodríguez-Delgado, Miguel Ángel; Fanali, Salvatore

    2015-02-01

    In this work, the suitability of a methodology based on dispersive liquid-liquid microextraction (DLLME) has been evaluated for the extraction of four endoestrogens (estriol, 17α-estradiol, 17β-estradiol, and estrone), an exoestrogen (17α-etynylestradiol), and a mycotoxin (zearalenone), together with some of their major metabolites (2-methoxyestradiol, α-zearalanol, β-zearalanol, α-zearalenol, and β-zearalenol) from different types of milk (whole and skimmed cow milk and semiskimmed goat milk) and whole natural yogurt. The methodology includes a previous protein precipitation with acidified ACN and a defatting step with n-hexane. Separation of the analytes, determination, and quantification were developed by MEKC coupled to ESI-MS using a BGE containing an aqueous solution of ammonium perfluorooctanoate as MS friendly surfactant. Calibration, precision, and accuracy studies of the described DLLME-MEKC-MS/MS method were evaluated obtaining a good linearity and LODs in the low micrograms per liter range.

  9. Liquid/liquid/solid contact angles

    NASA Astrophysics Data System (ADS)

    Borocco, Marine; Pellet, Charlotte; Authelin, Jean-René; Clanet, Christophe; Quéré, David; Compagnie des Interfaces Team

    2016-11-01

    Many studies have investigated solid/liquid/air interfaces and their corresponding wetting properties. We discuss what happens in less-studied liquid/liquid/solid systems, and focus on questions of dynamical wetting in a tube, having in mind applications in detergency. We use a capillary tube filled with water and containing a slug of silicone oil (or vice-versa), and present a series of experiments to determine static and dynamic wetting properties corresponding to this situation. We also discuss interfacial aging of such systems.

  10. Propagation of a liquid-liquid explosion

    SciTech Connect

    Harlow, F.H.; Ruppel, H.M.

    1981-08-01

    Direct contact between two liquids, one cold and the other hot, may be precluded by the presence of a vapor film. Bridging of this film by one or both fluids results in rapid local boiling, which may initiate a propagating liquid-liquid explosion. A mechanism is discussed for the propagation that involves implosion of the film, rapid mixing of the fluids, heat exchange to warm the cold fluid above the temperature for spontaneous nucleation, and the explosive generation of vapor, which in turn continues to sustain the film implosion. Plausibility for the model is demonstrated by means of numerical studies by high-speed computer.

  11. Reactions and Polymerizations at the Liquid-Liquid Interface.

    PubMed

    Piradashvili, Keti; Alexandrino, Evandro M; Wurm, Frederik R; Landfester, Katharina

    2016-02-24

    Reactions and polymerizations at the interface of two immiscible liquids are reviewed. The confinement of two reactants at the interface to form a new product can be advantageous in terms of improved reaction kinetics, higher yields, and selectivity. The presence of the liquid-liquid interface can accelerate the reaction, or a phase-transfer catalyst is employed to draw the reaction in one phase of choice. Furthermore, the use of immiscible systems, e.g., in emulsions, offers an easy means of efficient product separation and heat dissipation. A general overview on low molecular weight organic chemistry is given, and the applications of heterophase polymerization, occurring at or in proximity of the interface, (mostly) in emulsions are presented. This strategy can be used for the efficient production of nano- and microcarriers for various applications.

  12. Fundamental Drop Dynamics and Mass Transfer Experiments to Support Solvent Extraction Modeling Efforts

    SciTech Connect

    Kristi Christensen; Veronica Rutledge; Troy Garn

    2011-09-01

    In support of the Nuclear Energy Advanced Modeling Simulation Safeguards and Separations (NEAMS SafeSep) program, the Idaho National Laboratory (INL) worked in collaboration with Los Alamos National Laboratory (LANL) to further a modeling effort designed to predict mass transfer behavior for selected metal species between individual dispersed drops and a continuous phase in a two phase liquid-liquid extraction (LLE) system. The purpose of the model is to understand the fundamental processes of mass transfer that occur at the drop interface. This fundamental understanding can be extended to support modeling of larger LLE equipment such as mixer settlers, pulse columns, and centrifugal contactors. The work performed at the INL involved gathering the necessary experimental data to support the modeling effort. A custom experimental apparatus was designed and built for performing drop contact experiments to measure mass transfer coefficients as a function of contact time. A high speed digital camera was used in conjunction with the apparatus to measure size, shape, and velocity of the drops. In addition to drop data, the physical properties of the experimental fluids were measured to be used as input data for the model. Physical properties measurements included density, viscosity, surface tension and interfacial tension. Additionally, self diffusion coefficients for the selected metal species in each experimental solution were measured, and the distribution coefficient for the metal partitioning between phases was determined. At the completion of this work, the INL has determined the mass transfer coefficient and a velocity profile for drops rising by buoyancy through a continuous medium under a specific set of experimental conditions. Additionally, a complete set of experimentally determined fluid properties has been obtained. All data will be provided to LANL to support the modeling effort.

  13. An Entrance Region Mass Transfer Experiment.

    ERIC Educational Resources Information Center

    Youngquist, G. R.

    1979-01-01

    This paper describes an experiment designed to reveal the consequences of the development of a concentration boundary layer. The rate of a mass transfer limited electrochemical reaction is measured and used to obtain the dependence of average Sherwood number on Reynolds number and entrance length. (Author/BB)

  14. An Entrance Region Mass Transfer Experiment.

    ERIC Educational Resources Information Center

    Youngquist, G. R.

    1979-01-01

    This paper describes an experiment designed to reveal the consequences of the development of a concentration boundary layer. The rate of a mass transfer limited electrochemical reaction is measured and used to obtain the dependence of average Sherwood number on Reynolds number and entrance length. (Author/BB)

  15. Sensitive and precise monitoring of phosphatidylethanol in human blood as a biomarker for alcohol intake by ultrasound-assisted dispersive liquid-liquid microextraction combined with liquid chromatography tandem mass spectrometry.

    PubMed

    Wang, Siming; Yang, Ruiyue; Ji, Fusui; Li, Hongxia; Dong, Jun; Chen, Wenxiang

    2017-05-01

    Phosphatidylethanol (PEth) is a special phospholipid that is only formed in the presence of ethanol, and therefore, serves as a promising biomarker for alcohol intake. In this study, a simple, rapid and precise method based on LC-MS/MS combined with ultrasound-assisted dispersive liquid-liquid microextraction was developed and validated for the measurements of PEth (16:0/18:1, 16:0/18:2, 16:0/16:0, and 18:1/18:1) in human blood. The influences of several variables for sample extraction and MS detection were carefully investigated. The extraction efficiencies for all the four PEth species were markedly increased compared with the traditional extractions. A limit of detection below 0.56ngmL(-1) was obtained. This high sensitivity makes it possible to monitor various alcohol consumption levels in light to heavy drinkers. Good linearity was obtained for all the analytes without interference from the sample matrix. The imprecisions of the intra-run and total assays were lower than 3.1% and 6.5%, respectively, with an average recovery of 99.87%. In addition, the utility of the method was evaluated in an alcohol intake status study. The results indicate that the developed protocol is simple, precise, and sensitive, and can be easily adapted for objective and reliable assessments of alcohol intake in clinical research.

  16. A Rapid Method for the Quantitative Determination of 34 Pesticides in Nonalcoholic Carbonated Beverages Using Liquid-Liquid Extraction Coupled to Dispersive Solid-Phase Cleanup Followed by Gas Chromatography with Tandem Mass Spectrometry.

    PubMed

    Rai, Satyajeet; Gullapalli, Madhuri Devi; Srivastava, Anshuman; Shaik, Hussain; Siddiqui, Mohammed Haris; Mudiam, Mohana Krishna Reddy

    2017-05-01

    An economical, rapid, and sensitive multiresidue method using liquid-liquid extraction (LLE) coupled with dispersive SPE (dSPE) cleanup was developed for the quantitative determination of 34 multiclass multiresidue (MCMR) pesticides (14 organochlorines, eight organophosphates, 10 synthetic pyrethroids, and two herbicides) in nonalcoholic carbonated beverages (cola, orange, lemon-lime, and citra) using GC with tandem MS. The procedure mainly involved LLE by dichloromethane and dSPE cleanup in the presence of magnesium sulfate, primary secondary amine, and C18. The RSD of the developed method was found to be less than 14%. The LOD and LOQ values for all the analyzed pesticides were found in the ranges of 0.001-0.027 μg/L and 0.004-0.088 μg/L, respectively. The LOQ levels of the pesticides analyzed were found to be well below the recommended limit by the European Union (0.1 μg/L in water). The mean recoveries of pesticides in different nonalcoholic carbonated beverages (cola, orange, lemon-lime, and citra) were found to be in the range of 79-111%, with RSDs less than 11%. The validation data prove that the method can be acceptable to regulatory agencies for the routine analysis of MCMR pesticides in nonalcoholic carbonated beverages.

  17. Simultaneous derivatization and extraction of chlorophenols in water samples with up-and-down shaker-assisted dispersive liquid-liquid microextraction coupled with gas chromatography/mass spectrometric detection.

    PubMed

    Wang, Ke-Deng; Chen, Pai-Shan; Huang, Shang-Da

    2014-03-01

    A new up-and-down shaker-assisted dispersive liquid-liquid microextraction (UDSA-DLLME) for extraction and derivatization of five chlorophenols (4-chlorophenol, 4-chloro-2-methylphenol, 2,4-dichlorophenol, 2,4,6-trichloro-phenol, and pentachlorophenol) has been developed. The method requires minimal solvent usage. The relatively polar, water-soluble, and low-toxicity solvent 1-heptanol (12 μL) was selected as the extraction solvent and acetic anhydride (50 μL) as the derivatization reagent. With the use of an up-and-down shaker, the emulsification of aqueous samples was formed homogeneously and quickly. The derivatization and extraction of chlorophenols were completed simultaneously in 1 min. The common requirement of disperser solvent in DLLME could be avoided. After optimization, the linear range covered over two orders of magnitude, and the coefficient of determination (r (2)) was greater than 0.9981. The detection limit was from 0.05 to 0.2 μg L(-1), and the relative standard deviation was from 4.6 to 10.8 %. Real samples of river water and lake water had relative recoveries from 90.3 to 117.3 %. Other emulsification methods such as vortex-assisted, ultrasound-assisted, and manual shaking-enhanced ultrasound-assisted methods were also compared with the proposed UDSA-DLLME. The results revealed that UDSA-DLLME performed with higher extraction efficiency and precision compared with the other methods.

  18. Monitoring leachables from single-use bioreactor bags for mammalian cell culture by dispersive liquid-liquid microextraction followed by ultra high performance liquid chromatography quadrupole time of flight mass spectrometry.

    PubMed

    Dorival-García, N; Bones, J

    2017-08-25

    A method for the identification of leachables in chemically defined media for CHO cell culture using dispersive liquid-liquid microextraction (DLLME) and UHPLC-MS is described. A Box-Behnken design of experiments (DoE) approach was applied to obtain the optimum extraction conditions of the target analytes. Performance of DLLME as extraction technique was studied by comparison of two commercial chemically defined media for CHO cell culture. General extraction conditions for any group of leachables, regardless of their specific chemical functionalities can be applied and similar optimum conditions were obtained with the two media. Extraction efficiency and matrix effects were determined. The method was validated using matrix-matched standard calibration followed by recovery assays with spiked samples. Finally, cell culture media was incubated in 7 single use bioreactors (SUBs) from different vendors and analysed. TBPP was not detected in any of the samples, whereas DtBP and TBPP-ox were found in all samples, with bDtBPP detected in six SUBs. This method can be used for early identification of non-satisfactory SUB films for cultivation of CHO cell lines for biopharmaceutical production. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. A validated liquid chromatographic method for the determination of polycyclic aromatic hydrocarbons in honey after homogeneous liquid-liquid extraction using hydrophilic acetonitrile and sodium chloride as mass separating agent.

    PubMed

    Koltsakidou, Anastasia; Zacharis, Constantinos K; Fytianos, Konstantinos

    2015-01-16

    In the present report, a simple and cost-effective method for the determination of twelve US EPA priority polycyclic aromatic hydrocarbons (PAHs) in honey samples after salting-assisted liquid-liquid extraction and UHPLC with fluorescence detection is proposed. The sample treatment is based on the usage of hydrophilic acetonitrile as extraction solvent and its phase separation under high salinity conditions. Due to the high sugar content of the samples the phase separation is promoted effortlessly. Several parameters affecting the extraction efficiency and method sensitivity including the concentration of the honey samples, the type and volume of the extraction solvent, the type and quantity of the inorganic salt, extraction time and centrifugation time was systematically investigated. The method was validated in-house according to the Commission Decision 2002/657/EC guidelines. The limit of detection (LOD) of the method lay between 0.02 and 0.04ngmL(-1) (corresponding to 0.08 and 0.16ngg(-1)) which are close to the quality criteria established by European Regulation (EC) 836/2011 concerning the PAHs in foodstuffs. The mean analytical bias (expressed as relative recoveries) in all spiking levels was acceptable being in the range of 54-118% while the relative standard deviation (RSD) was lower than 19%. The proposed method has been satisfactorily applied for the analysis of the selected PAHs residues in various honey samples obtained from Greek region.

  20. Sensitive determination of trace urinary 3-hydroxybenzo[a]pyrene using ionic liquids-based dispersive liquid-liquid microextraction followed by chemical derivatization and high performance liquid chromatography-high resolution tandem mass spectrometry.

    PubMed

    Hu, Huan; Liu, Baizhan; Yang, Jun; Lin, Zuomin; Gan, Wuer

    2016-08-01

    3-Hydroxybenzo[a]pyrene (3-OHBaP) is widely used as a biomarker for assessing carcinogenic benzo[a]pyrene exposure risks. However, monitoring urinary 3-OHBaP suffers from an insufficient sensitivity due to the pg/mL level in urine excretion. In this study, a sensitive method for determination trace urinary 3-OHBaP was developed, involving enzymatic hydrolysis of the glucuronide and sulfate conjugates, ionic liquids dispersive liquid-liquid microextraction (IL-DLLME) enrichment, derivatization with dansyl chloride and HPLC-HRMS/MS analysis in the positive ion mode. Using IL-DLLME makes the enrichment of trace 3-OHBaP very simple, time-saving, efficiency and environmentally-friendly. To enhanced HPLC-HRMS/MS response, an MS-friendly dansyl group was introduced to increase the ionization and fragmentation efficiency. The optimal IL-DLLME extraction parameters and derivatization reaction conditions were investigated. Good linearity was obtained over a concentration range of 0.6-50.0pg/mL with correlation coefficients (r(2)) of 0.9918. The limit of detection (LOD) and limit of quantification (LOQ) values were 0.2pg/mL and 0.58pg/mL, respectively. The recoveries were 92.0±4.2% with the intra-day and inter-day RSD values ranged from 2.2% to 3.8% and from 3.3% to 6.8%, respectively. The proposed IL-DLLME-Dansylation-HPLC-HRMS/MS method was successfully applied to determine urinary 3-OHBaP of non-occupational exposed smokers and nonsmokers.

  1. Fast analysis of phthalates in freeze-dried baby foods by ultrasound-vortex-assisted liquid-liquid microextraction coupled with gas chromatography-ion trap/mass spectrometry.

    PubMed

    Russo, Mario Vincenzo; Avino, Pasquale; Notardonato, Ivan

    2016-11-25

    This paper is focused on the determination of phthalates (PAEs), compounds "plausibly" endocrine disruptors, in baby food products by means of a method based on ultrasound-vortex-assisted liquid-liquid microextraction coupled with GC-IT/MS (UVALLME-GC-IT/MS). Particularly, the whole procedure allows the determination of six phthalates such as DMP, DEP, DBP, iBcEP, BBP and DEHP. After dissolution of 0.1g product sample and addition of anthracene as Internal Standard, 250μL of n-heptane are used as extraction solvent. The solution, held for 5min on the vortex mixer and for 6min in an ultrasonic bath at 100W for favoring the solvent dispersion and consequently the analyte extraction, is centrifuged at 4000rpm for 30min. About 100μL of heptane are recovered and 1μL is injected into the GC-IT/MS. All the analytical parameters investigated are deeply discussed: under the best conditions, the percentage recoveries range between 96.2 and 109.2% with an RSD ≤10.5% whereas the Limit of Detections (LODs) and the Limit of Quantifications (LOQs) are below 11 and 20ngg(-1), respectively, for all the PAEs except for iBcEP (23 and 43ngg(-1), respectively). The linear dynamic range of this procedure is between 10 and 5000ngg(-1) with R(2) ≥0.92. The method has been applied to real commercial freeze-dried samples (chicken and turkey meats) available on the Italian pharmaceutical market: three PAEs were preliminary identified, i.e. DEP (14ngg(-1)), DBP (11ngg(-1)) and DEHP (64ngg(-1)).

  2. Ultra-preconcentration and determination of selected pharmaceutical and personal care products in different water matrices by solid-phase extraction combined with dispersive liquid-liquid microextraction prior to ultra high pressure liquid chromatography tandem mass spectrometry analysis.

    PubMed

    Celano, Rita; Piccinelli, Anna Lisa; Campone, Luca; Rastrelli, Luca

    2014-08-15

    Pharmaceutical and personal care products (PPCPs) are one of the most important classes of emerging contaminants. The potential of ecological and environmental impacts associated with PPCPs are of particular concern because they continually penetrate the aquatic environment. This work describes a novel ultra-preconcentration technique for the rapid and highly sensitive analysis of selected PPCPs in environmental water matrices at ppt levels. Selected PPCPs were rapidly extracted and concentrated from large volumes of aqueous solutions (500 and 250mL) by solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME) and then analyzed using UHPLC-MS/MS. Experimental parameters were carefully investigated and optimized to achieve the best SPE-DLLME efficiency and higher enrichment factors. The best results were obtained using the ternary mixture acetonitrile/methanol/dichloromethane 3:3:4, v/v/v, both as SPE eluent and DLLME extractant/dispersive mixture. DLLME aqueous solution (5% NaCl, 10mgL(-1) TBAB) was also modified to improve the extraction efficiency of more hydrophilic PPCPs. Under the optimal conditions, an exhaustive extraction for most of the investigated analytes (recoveries >70%), with a precision (RSD <10%) and very high enrichment factors were attained for different aqueous matrices (drinking, sea, river and wastewater). Method detection and quantification limits were at very low ppt levels and below 1 and 3ngL(-1), respectively, for 15 of selected PPCPs. The proposed analytical procedure offers numerous advantages such as the simplicity of operation, rapidity, a high enrichment factor and sensitivity. So it is suitable for monitoring and studies of occurrence of PPCPs in different environmental compartments.

  3. Ultrasound-assisted dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry in negative chemical ionization mode for the determination of polybrominated diphenyl ethers in water.

    PubMed

    Zhang, Qian; Liang, Tao; Guan, Lili

    2013-04-01

    A simple and economical method for the determination of eight polybrominated diphenyl ethers (BDE-28, 47, 99, 100,153,154,183, and 209) in water was developed. This method involves the use of ultrasound-assisted dispersive liquid-liquid microextraction combined with GC-MS in negative chemical ionization mode. Various parameters affecting the extraction efficiency, including the type and volume of extraction and dispersive solvents, salt concentration, extraction time, and ultrasonic time, were investigated. A volume of 1.0 mL of acetone (dispersive solvent) containing 10 μL tetrachloroethylene (extraction solvent) was injected into 5.0 mL of water samples and then emulsified by ultrasound for 2.0 min to produce the cloudy solution. Under the optimal condition, the enrichment factors for the eight PBDEs were varied from 845- to 1050-folds. Good linearity was observed in the range of 1.0-200 ng L(-1) for BDE-28, 47, 99, and 100; 5.0-200 ng L(-1) for BDE-153, 154, and 183; and 5.0-500 ng L(-1) for BDE-209. The RSD values were in the range of 2.5-8.4% (n = 5) and the LODs ranged from 0.40 to 2.15 ng L(-1) (S/N = 3). The developed method was applied for the determination of eight BPDEs in the river and lake water samples, and the mean recoveries at spiking levels of 5.0 and 50.0 ng L(-1) were in the range of 70.6-105.1%.

  4. 43 CFR 3106.4-3 - Mass transfers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 43 Public Lands: Interior 2 2014-10-01 2014-10-01 false Mass transfers. 3106.4-3 Section 3106.4-3... or Otherwise § 3106.4-3 Mass transfers. (a) A mass transfer may be utilized in lieu of the provisions... large number of Federal leases to the same transferee. (b) Three originally executed copies of the mass...

  5. 43 CFR 3106.4-3 - Mass transfers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 43 Public Lands: Interior 2 2011-10-01 2011-10-01 false Mass transfers. 3106.4-3 Section 3106.4-3... or Otherwise § 3106.4-3 Mass transfers. (a) A mass transfer may be utilized in lieu of the provisions... large number of Federal leases to the same transferee. (b) Three originally executed copies of the mass...

  6. 43 CFR 3106.4-3 - Mass transfers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 43 Public Lands: Interior 2 2013-10-01 2013-10-01 false Mass transfers. 3106.4-3 Section 3106.4-3... or Otherwise § 3106.4-3 Mass transfers. (a) A mass transfer may be utilized in lieu of the provisions... large number of Federal leases to the same transferee. (b) Three originally executed copies of the mass...

  7. 43 CFR 3106.4-3 - Mass transfers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 43 Public Lands: Interior 2 2012-10-01 2012-10-01 false Mass transfers. 3106.4-3 Section 3106.4-3... or Otherwise § 3106.4-3 Mass transfers. (a) A mass transfer may be utilized in lieu of the provisions... large number of Federal leases to the same transferee. (b) Three originally executed copies of the mass...

  8. Assembly of metal nanoparticle-carbon nanotube composite materials at the liquid/liquid interface.

    PubMed

    Lee, Kang Yeol; Kim, Minjung; Hahn, Joeoong; Suh, Jung Sang; Lee, Inhyung; Kim, Kwan; Han, Sang Woo

    2006-02-14

    Carbon nanotubes (CNTs)-mediated self-assembly of metal (Au and Ag) nanoparticles at the liquid/liquid interface in the form of a stable nanocomposite film is reported. The metallic luster results from the electronic coupling of nanoparticles, suggesting the formation of closely packed nanoparticle thin films. The interfacial film could be transferred to mica substrates and carbon-coated transmission electron microscopy (TEM) grids. The transferred films were very stable for a prolonged time. The samples were characterized by UV-vis spectroscopy, scanning electron microscopy (SEM), TEM, and X-ray photoelectron spectroscopy (XPS). SEM and TEM results show that the films formed at the liquid/liquid interface are indeed composite materials consisting of CNTs and nanoparticles. XPS measurements further indicate the presence of the interaction between nanoparticles and CNTs.

  9. Mass transfer and transport in salt repositories

    SciTech Connect

    Pigford, T.H.; Chambre, P.L.; Lee, W.W.L.

    1989-02-01

    Salt is a unique rock isolation of nuclear waste because it is dry'' and nearly impermeable. In this paper we summarize some mass-transfer and transport analyses of salt repositories. First we analyses brine migration. Heating by high-level waste can cause brine in grain boundaries to move due to pressure-gradients. We analyze brine migration treating salt as a thermoelastic solid and found that brine migration is transient and localized. We use previously developed techniques to estimate release rates from waste packages by diffusion. Interbeds exist in salt and may be conduits for radionuclide migration. We analyze steady-state migration due to brine flow in the interbed, as a function of the Peclet number. Then we analyze transient mass transfer, both into the interbed and directly to salt, due only to diffusion. Finally we compare mass transfer rates of a waste cylinder in granite facing a fracture and in salt facing an interbed. In all cases, numerical illustrations of the analytic solution are given. 10 refs., 4 figs., 3 tabs.

  10. Proton Transfer Reaction Ion Trap Mass Spectrometer

    SciTech Connect

    Prazeller, Peter; Palmer, Peter T.; Boscaini, Elena; Jobson, B Tom T.; Alexander, M. Lizabeth

    2003-06-11

    Proton transfer reaction mass spectrometry is a relatively new field that has attracted a great deal of interest in the last few years. This technique uses H₃Oþ as a chemical ionization (CI) reagent to measure volatile organic compounds (VOCs) in the parts per billion by volume (ppbv) to parts per trillion by volume (pptv) range. Mass spectra acquired with a proton transfer reaction mass spectrometer (PTR-MS) are simple because proton transfer chemical ionization is ‘soft’ and results in little or no fragmentation. Unfortunately, peak identification can still be difficult due to isobaric interferences. A possible solution to this problem is to couple the PTR drift tube to an ion trap mass spectrometer (ITMS). The use of an ITMS is appealing because of its ability to perform MS/MS and possibly distinguish between isomers and other isobars. Additionally, the ITMS duty cycle is much higher than that of a linear quadrupole so faster data acquisition rates are possible that will allow for detection of multiple compounds. Here we present the first results from a proton transfer reaction ion trap mass spectrometer (PTR-ITMS). The aim of this study was to investigate ion injection and storage efficiency of a simple prototype instrument in order to estimate possible detection limits of a second-generation instrument. Using this prototype a detection limit of 100 ppbv was demonstrated. Modifications are suggested that will enable further reduction in detection limits to the low-ppbv to high-pptv range. Furthermore, the applicability of MS/MS in differentiating between isobaric species was determined. MS/MS spectra of the isobaric compounds methyl vinyl ketone (MVK) and methacrolein (MACR) are presented and show fragments of different mass making differentiation possible, even when a mixture of both species is present in the same sample. However, MS/MS spectra of acetone and propanal produce fragments with the same molecular masses but with different intensity ratios

  11. Beyond dispersive liquid-liquid microextraction.

    PubMed

    Leong, Mei-I; Fuh, Ming-Ren; Huang, Shang-Da

    2014-03-28

    Dispersive liquid-liquid microextraction (DLLME) and other dispersion liquid-phase microextraction (LPME) methods have been developed since the first DLLME method was reported in 2006. DLLME is simple, rapid, and affords high enrichment factor, this is due to the large contact surface area of the extraction solvent. DLLME is a method suitable for the extraction in many different water samples, but it requires using chlorinated solvents. In recent years, interest in DLLME or dispersion LPME has been focused on the use of low-toxicity solvents and more conveniently practical procedures. This review examines some of the most interesting developments in the past few years. In the first section, DLLME methods are separated in two categories: DLLME with low-density extraction solvent and DLLME with high-density extraction solvent. Besides these methods, many novel special devices for collecting low-density extraction solvent are also mentioned. In addition, various dispersion techniques with LPME, including manual shaking, air-assisted LPME (aspirating and injecting the extraction mixture by syringe), ultrasound-assisted emulsification, vortex-assisted emulsification, surfactant-assisted emulsification, and microwave-assisted emulsification are described. Besides the above methods, combinations of DLLME with other extraction techniques (solid-phase extraction, stir bar sorptive extraction, molecularly imprinted matrix solid-phase dispersion and supercritical fluid extraction) are introduced. The combination of nanotechnique with DLLME is also introduced. Furthermore, this review illustrates the application of DLLME or dispersion LPME methods to separate and preconcentrate various organic analytes, inorganic analytes, and samples.

  12. Switchable water: microfluidic investigation of liquid-liquid phase separation mediated by carbon dioxide.

    PubMed

    Lestari, Gabriella; Abolhasani, Milad; Bennett, Darla; Chase, Preston; Günther, Axel; Kumacheva, Eugenia

    2014-08-27

    Increase in the ionic strength of water that is mediated by the reaction of carbon dioxide (CO2) with nitrogenous bases is a promising approach toward phase separation in mixtures of water with organic solvents and potentially water purification. Conventional macroscale studies of this complicated process are challenging, due to its occurrence via several consecutive and concurrent steps, mass transfer limitation, and lack of control over gas-liquid interfaces. We report a new microfluidic strategy for fundamental studies of liquid-liquid phase separation mediated by CO2 as well as screening of the efficiency of nitrogenous agents. A single set of microfluidic experiments provided qualitative and quantitative information on the kinetics and completeness of water-tetrahydrofuran phase separation, the minimum amount of CO2 required to complete phase separation, the total CO2 uptake, and the rate of CO2 consumption by the liquid mixture. The efficiency of tertiary diamines with different lengths of alkyl chain was examined in a time- and labor-efficient manner and characterized with the proposed efficiency parameter. A wealth of information obtained using the MF methodology can facilitate the development of new additives for switchable solvents in green chemistry applications.

  13. Proton Transfer Reaction Ion Trap Mass Spectrometer

    SciTech Connect

    Prazeller, Peter; Palmer, Peter T.; Boscaini, Elena; Jobson, B Tom; Alexander, M. Lizabeth

    2003-07-07

    Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a relatively new field that has attracted a great deal of interest in the last several years. This technique uses H3O+ as a chemical ionization (CI) agent for measuring volatile organic compounds (VOCs) in the parts per billion by volume (ppbv) - parts per trillion by volume (pptv) range. PTR-MS mass spectra are simple because the ionization method of proton transfer is “soft”, resulting in little or no fragmentation. Unfortunately, the simplicity of the mass spectra can cause problems in peak identification due to isobaric interferences. A possible solution to this problem is to couple the PTR drift tube to an ion trap mass spectrometer (ITMS). ITMS is appealing because of the ability to perform MS/MS and possibly distinguish between isomers and other isobars. Additionally, the ITMS duty cycle is much higher than that of a linear quadrupole so faster data acquisition rates can be realized for detection of multiple compounds. We present here the first results from a Proton Transfer Reaction Ion Trap Mass Spectrometer (PTR-ITMS). The aim of this study was to investigate ion injection and storage efficiency of a simple prototype interface in order to estimate possible detection limits of a second generation instrument. Using this prototype a detection limit of 100 ppbv was demonstrated for the PTR-ITMS. Modifications are suggested that will enable further reduction in detection limits to the low ppbv to pptv range. Furthermore the applicability of MS/MS to differentiate between isobaric species was determined. MS/MS spectra of the isobaric compounds methyl vinyl ketone (MVK) and methacrolein (MACR) are presented and show fragments of different mass making a differentiation possible even when a mixture of both species is present in the same sample. MS/MS spectra of acetone and propanal produce fragments with the same molecular weight but different ratios, allowing quantitative distinction only if one species

  14. Development, Fabrication, and Testing of a Liquid/Liquid Microchannel Heat Exchanger for Constellation Spacecrafts

    NASA Technical Reports Server (NTRS)

    Hawkins-Reynolds, Ebony; Le, Hung; Stephan, Ryan

    2010-01-01

    Microchannel technology can be incorporated into heat exchanger designs to decrease the mass and volume of space hardware. The National Aeronautics and Space Administration at the Johnson Space Center (NASA JSC) partnered with Pacific Northwest National Laboratories (PNNL) to develop a liquid/liquid microchannel heat exchanger that has significant mass and volume savings without sacrificing thermal and pressure drop performance. PNNL designed the microchannel heat exchanger to the same performance design requirements of a conventional plate and fin liquid/liquid heat exchanger; 3 kW duty with inlet temperatures of 26 C and 4 C. Both heat exchangers were tested using the same test parameters on a test apparatus and performance data compared.

  15. [Solvent demulsification-dispersive liquid-liquid microextraction based on solidification of floating organic drop coupled with gas chromatography-mass spectrometry for simultaneous determination of organochlorine pesticides in aqueous samples].

    PubMed

    Wang, Yu; Zhu, Chenghua; Zou, Xiaoli; Huang, Lizhi; Yan, Dong

    2013-11-01

    A novel method for simultaneous determination of eight organochlorine pesticides in solidification of floating organic drop coupled with gas chromatography-mass spectrometry (GC-MS) was established. A mixture of extractant (n-hexadecane) and dispersive agent (acetone) at the ratio of 1/5 (v/v) was injected into aqueous sample to form an emulsion and an extraction process was accomplished. The demulsifier (750 microL acetone) was then injected to break up the emulsion. The two phases were separated quickly without centrifugation. After being solidified in an ice-bath, the upper layer (n-hexadecane) was transferred into an Eppendorf tube and analyzed by GC-MS after melted at room temperature. Factors affecting extraction efficiency such as the type and volume of extractant, dispersive agent and demulsifier, also ionic strength and pH value of extraction system were studied. Under the optimized conditions, the working curve of the proposed method provided a good linearity in the range of 0.025-2.00 microg/L (r = 0.999 5-0.999 9). The detection limits of the organochlorine pesticides calculated by Hubaux-Vos method were 0.012-0.024 microg/L and the relative standard deviations (RSDs) ranged from 3.15% to 4.53%. The enrichment factors (EF) were 96-101. When the method was applied to the determination of farmland water, the average spiked recoveries were 96.77%-102.93% with the relative standard deviations of 2.68%-4.86%. The proposed method is sensitive and fast. It also has the advantage of little organic solvent consumption so that it is friendly to environment and suitable for batch analysis of organochlorine pesticides in aqueous samples. Meanwhile, it provides technical and methodological support for achieving the automation of sample pretreatment.

  16. Liquid-liquid ion transport junctions based on paired gold electrodes in generator-collector mode.

    PubMed

    French, Robert W; Chan, Yohan; Bulman-Page, Philip C; Marken, Frank

    2009-10-01

    Simultaneous electrochemically driven double anion transfer across liquid-liquid interfaces is demonstrated at a gold-gold junction electrode. In the presence of two closely spaced electrodes (generator and collector), anion uptake into the organic phase (oxidation) and anion expulsion into the aqueous phase (reduction) can be combined to result in a generator-collector anion transport system across the liquid-liquid interface. In this report we are employing a paired gold junction grown by electro-deposition to ca. 5 microm gap size with the N,N-diethyl-N',N'-didodecyl-phenylene-diamine water immiscible redox liquid immobilized into the gap to demonstrate simultaneous perchlorate anion uptake and expulsion. The effects of redox liquid volume and scan rate on the magnitude of currents and two mechanistic pathways for ion transport are discussed in the context of micro-electrophoretic processes.

  17. Extensible automated dispersive liquid-liquid microextraction.

    PubMed

    Li, Songqing; Hu, Lu; Chen, Ketao; Gao, Haixiang

    2015-05-04

    In this study, a convenient and extensible automated ionic liquid-based in situ dispersive liquid-liquid microextraction (automated IL-based in situ DLLME) was developed. 1-Octyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]imide ([C8MIM]NTf2) is formed through the reaction between [C8MIM]Cl and lithium bis[(trifluoromethane)sulfonyl]imide (LiNTf2) to extract the analytes. Using a fully automatic SPE workstation, special SPE columns packed with nonwoven polypropylene (NWPP) fiber, and a modified operation program, the procedures of the IL-based in situ DLLME, including the collection of a water sample, injection of an ion exchange solvent, phase separation of the emulsified solution, elution of the retained extraction phase, and collection of the eluent into vials, can be performed automatically. The developed approach, coupled with high-performance liquid chromatography-diode array detection (HPLC-DAD), was successfully applied to the detection and concentration determination of benzoylurea (BU) insecticides in water samples. Parameters affecting the extraction performance were investigated and optimized. Under the optimized conditions, the proposed method achieved extraction recoveries of 80% to 89% for water samples. The limits of detection (LODs) of the method were in the range of 0.16-0.45 ng mL(-1). The intra-column and inter-column relative standard deviations (RSDs) were <8.6%. Good linearity (r>0.9986) was obtained over the calibration range from 2 to 500 ng mL(-1). The proposed method opens a new avenue for automated DLLME that not only greatly expands the range of viable extractants, especially functional ILs but also enhances its application for various detection methods. Furthermore, multiple samples can be processed simultaneously, which accelerates the sample preparation and allows the examination of a large number of samples.

  18. Single drop liquid-liquid-liquid microextraction of methamphetamine and amphetamine in urine.

    PubMed

    He, Yi; Kang, Youn-Jung

    2006-11-10

    Single drop liquid-liquid-liquid microextraction (LLLME) combined with high performance liquid chromatography (HPLC)-UV detection was investigated for the determination of a popular drug of abuse, methamphetamine (MAP), and its major metabolite, amphetamine (AP), in urine samples. The target compounds were extracted from NaOH modified sample solution to a thin layer of organic solvent membrane, and back-extracted to an acidic acceptor drop suspended on the tip of a 50-microL HPLC syringe in the aforementioned organic layer. This syringe was also used for direct injection after extraction. Factors affecting extraction efficiency were studied. At optimal conditions, the overall enrichment factor (EF) was 500-fold for AP and 730-fold for MAP, respectively. The method exhibited a wide linear range (1.0-1500 microg/L), low detection limit (0.5 microg/L), and good repeatability (RSD<5.0%) for both analytes. The feasibility of the method was demonstrated by the analysis of human urine samples.

  19. Single Fusion Events at Polarized Liquid-Liquid Interfaces.

    PubMed

    Laborda, Eduardo; Molina, Angela; Espín, Vanesa Fernández; Martínez-Ortiz, Francisco; García de la Torre, José; Compton, Richard G

    2017-01-16

    A new electrochemical framework for tracking individual soft particles in solution and monitoring their fusion with polarized liquid-liquid interfaces is reported. The physicochemical principle lies in the interfacial transfer of an ionic probe confined in the particles dispersed in solution and that is released upon their collision and fusion with the fluid interface. As a proof-of-concept, spike-like transients of a stochastic nature are reported in the current-time response of 1,2-dichloroethane(DCE)|water(W) submilli-interfaces after injection of DCE-in-W emulsions. The sign and potential dependence of the spikes reflect the charge and lipophilicity of the ionic load of the droplets. A comparison with dynamic light scattering measurements indicates that each spike is associated with the collision of a single sub-picoliter droplet. This opens a new framework for the study of single fusion events at the micro- and nanoscale and of ion transport across biomimetic soft interfaces.

  20. Interrupted Binary Mass Transfer in Star Clusters

    NASA Astrophysics Data System (ADS)

    Leigh, Nathan W. C.; Geller, Aaron M.; Toonen, Silvia

    2016-02-01

    Binary mass transfer (MT) is at the forefront of some of the most exciting puzzles of modern astrophysics, including SNe Ia, gamma-ray bursts, and the formation of most observed exotic stellar populations. Typically, the evolution is assumed to proceed in isolation, even in dense stellar environments such as star clusters. In this paper, we test the validity of this assumption via the analysis of a large grid of binary evolution models simulated with the SeBa code. For every binary, we calculate analytically the mean time until another single or binary star comes within the mean separation of the mass-transferring binary, and compare this timescale to the mean time for stable MT to occur. We then derive the probability for each respective binary to experience a direct dynamical interruption. The resulting probability distribution can be integrated to give an estimate for the fraction of binaries undergoing MT that are expected to be disrupted as a function of the host cluster properties. We find that for lower-mass clusters (≲ {10}4 {M}⊙ ), on the order of a few to a few tens of percent of binaries undergoing MT are expected to be interrupted by an interloping single, or more often binary, star, over the course of the cluster lifetime, whereas in more massive globular clusters we expect \\ll 1% to be interrupted. Furthermore, using numerical scattering experiments performed with the FEWBODY code, we show that the probability of interruption increases if perturbative fly-bys are considered as well, by a factor ˜2.

  1. Influence of high voltage electric fields applied across a horizontal liquid-liquid interface on the rate of metal extraction using a rotating diffusion cell

    SciTech Connect

    Kuipa, P.K.; Hughes, M.A.

    1999-09-01

    The effect of an applied electrical field across a plane liquid-liquid interface on the rate of metal extraction using hydroxyoximes and dialkylphosphoric acids as extractants is examined. The results indicate that applied electric fields have no marked influence on the observed rate of metal extraction when aliphatic hydrocarbons are employed as the diluents in the organic phase. Increases in mass transfer rates of up to 250% were observed when mixtures of octanol and an aliphatic hydrocarbon were employed as the diluent in the organic phase. The mechanism of transfer is thought to be a combination of movement of charges in the bulk of the nonconducting organic phase and electrohydrodynamic flows due to local variations in the effective interfacial tension as a result of the applied electric fields.

  2. Mass transfer mechanism in hydrophilic interaction chromatography.

    PubMed

    Gritti, Fabrice; Guiochon, Georges

    2013-08-09

    The mass transfer mechanism in HILIC was investigated in depth. The reduced heights equivalent to a theoretical plate (HETP) of five low molecular weigh compounds with retention factors of -0.05 (slight exclusion from the surface due to the presence of a water-rich layer in which naphthalene is insoluble) to 3.64 were measured at room temperature for a 4.6mm×100mm column packed with 3.5μm 140Å XBridge HILIC particles in a wide range of flow velocities. The mobile phase was a buffered acetonitrile-water mixture (92.5/7.5, v/v). Using a physically reliable model of effective diffusion in binary composite media (Torquato's model), the longitudinal diffusion and solid-liquid mass transfer resistance reduced HETP terms were measured. The reduced short-range eddy dispersion HETP was taken from the literature data. The long-range reduced HETP was directly measured from the subtraction of these HETP terms to the overall HETP measured from moment analysis. In contrast to RPLC, the plots of the reduced HETP versus the reduced velocity depend weakly on the retention factor, due to the constant, low intra-particle diffusivity observed in HILIC. So, the reduced longitudinal diffusion HETP is smaller and the reduced solid-liquid mass transfer resistance HETP is larger in HILIC than in RPLC. Whereas border effects can be concealed in RPLC for retained analytes due to fast radial equilibration across the column diameter, a residual long-range eddy dispersion term persists in 4.6mm I.D. HILIC columns, even at very slow flow rates. Experiments show that the minor differences in the long-range eddy dispersion term between analytes having different retention factors is directly correlated to the reciprocal of their bulk diffusion coefficient. The performance of HILIC columns packed with fine particles is then more sensitive to the inlet sample distribution and to the outlet sample collection than RPLC columns due to the relatively poor radial mixing controlled by lateral diffusion.

  3. Strategies for liquid-liquid extraction of oxide particles for applications in supercapacitor electrodes and thin films.

    PubMed

    Chen, Ri; Ata, Mustafa S; Zhao, Xinya; Clifford, Amanda; Puri, Ishwar; Zhitomirsky, Igor

    2017-08-01

    Bottom-up and top-down liquid-liquid extraction methods have been developed for the transfer of colloidal metal oxide particles, synthesized in an aqueous phase, to organic phases. In such methods the agglomeration of the particles during the drying stage was avoided. Hexadecylamine was used as an extractor for MnO2 particles in the bottom-up extraction to the 1-butanol phase and top-down extraction to the dichloromethane phase. The reduction of particle agglomeration facilitated the fabrication of MnO2-carbon nanotube composite electrodes for electrochemical supercapacitors with enhanced mixing of the individual components and active mass as high as 35mgcm(-2). Electrochemical testing results showed superior performance of the composite MnO2-carbon nanotube electrodes, prepared by the bottom-up strategy. The new strategies allowed the fabrication of advanced electrodes, which showed a capacitance of 5.48Fcm(-2) at a scan rate of 2mVs(-1), good capacitance retention at high scan rates and low resistance. In another conceptually new bottom-up strategy colloidal titania particles were modified during synthesis with 2,3,4-trihydroxybenzaldehyde, which allowed strong catecholate-type bonding to the Ti atoms on the particle surface. The Schiff base reaction with hexadecylamine at the liquid-liquid interface allowed for particle extraction. The extraction strategies developed in this investigation pave the way for agglomerate-free processing of advanced films, coatings and devices by colloidal methods. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Heat and mass transfer in flames

    NASA Technical Reports Server (NTRS)

    Faeth, G. M.

    1986-01-01

    Heat- and mass-transfer processes in turbulent diffusion flames are discussed, considering turbulent mixing and the structure of single-phase flames, drop processes in spray flames, and nonluminous and luminous flame radiation. Interactions between turbulence and other phenomena are emphasized, concentrating on past work of the author and his associates. The conserved-scalar formalism, along with the laminar-flamelet approximation, is shown to provide reasonable estimates of the structure of gas flames, with modest levels of empiricism. Extending this approach to spray flames has highlighted the importance of drop/turbulence interactions; e.g., turbulent dispersion of drops, modification of turbulence by drops, etc. Stochastic methods being developed to treat these phenomena are yielding encouraging results.

  5. Heat and mass transfer in flames

    NASA Technical Reports Server (NTRS)

    Faeth, G. M.

    1986-01-01

    Heat- and mass-transfer processes in turbulent diffusion flames are discussed, considering turbulent mixing and the structure of single-phase flames, drop processes in spray flames, and nonluminous and luminous flame radiation. Interactions between turbulence and other phenomena are emphasized, concentrating on past work of the author and his associates. The conserved-scalar formalism, along with the laminar-flamelet approximation, is shown to provide reasonable estimates of the structure of gas flames, with modest levels of empiricism. Extending this approach to spray flames has highlighted the importance of drop/turbulence interactions; e.g., turbulent dispersion of drops, modification of turbulence by drops, etc. Stochastic methods being developed to treat these phenomena are yielding encouraging results.

  6. Mass transfer in a geologic environment

    SciTech Connect

    Zavoshy, S.J.; Chambre, P.L.; Pigford, T.H.

    1984-11-01

    A new analytical solution is presented that predicts the rate of dissolution of species from a waste package surrounded by a wet porous medium. By equating the rate of diffusive mass transfer into the porous rock to the rate of liquid-surface chemical reaction, an analytical solution for the time-dependent dissolution rate and the time-dependent concentration of dissolved species at the waste surface is obtained. From these results it is shown that for most of the important species in a package of radioactive waste the surface liquid quickly reaches near-saturation concentrations and the dissolution rate can be predicted by the simpler theory that assumes saturation concentrations in the surface liquid. 26 refs., 3 figs., 1 tab.

  7. Drop oscillation and mass transfer in alternating electric fields

    SciTech Connect

    Carleson, T.E.; Yang, W.

    1991-05-30

    After the second annual progress report to DOE in July 1990, we continued the experimental work for another liquid system. The mathematical model was also improved to include secondary effects due to drop deformation and charge redistribution on the deformed drop surface. Originally, we planned to study a mass transfer process after the hydrodynamic modelling. Due to difficulty in measuring drop concentration during oscillations, we decided to study a heat transfer process instead. Using the analogy between the mass transfer and the heat transfer, we can easily extend the results for the heat transfer study to the mass transfer problem.

  8. A microfluidic study of liquid-liquid extraction mediated by carbon dioxide.

    PubMed

    Lestari, Gabriella; Salari, Alinaghi; Abolhasani, Milad; Kumacheva, Eugenia

    2016-07-05

    Liquid-liquid extraction is an important separation and purification method; however, it faces a challenge in reducing the energy consumption and the environmental impact of solvent (extractant) recovery. The reversible chemical reactions of switchable solvents (nitrogenous bases) with carbon dioxide (CO2) can be implemented in reactive liquid-liquid extraction to significantly reduce the cost and energy requirements of solvent recovery. The development of new effective switchable solvents reacting with CO2 and the optimization of extraction conditions rely on the ability to evaluate and screen the performance of switchable solvents in extraction processes. We report a microfluidic strategy for time- and labour-efficient studies of CO2-mediated solvent extraction. The platform utilizes a liquid segment containing an aqueous extractant droplet and a droplet of a solution of a switchable solvent in a non-polar liquid, with gaseous CO2 supplied to the segment from both sides. Following the reaction of the switchable solvent with CO2, the solvent becomes hydrophilic and transfers from the non-polar solvent to the aqueous droplet. By monitoring the time-dependent variation in droplet volumes, we determined the efficiency and extraction time for the CO2-mediated extraction of different nitrogenous bases in a broad experimental parameter space. The platform enables a significant reduction in the amount of switchable solvents used in these studies, provides accurate temporal characterization of the liquid-liquid extraction process, and offers the capability of high-throughput screening of switchable solvents.

  9. Liquid-liquid-liquid microextraction for sample preparation of biological fluids prior to capillary electrophoresis.

    PubMed

    Pedersen-Bjergaard, S; Rasmussen, K E

    1999-07-15

    Methamphetamine as a model compound was extracted from 2.5-mL aqueous samples adjusted to pH 13 (donor solution) through a thin phase of 1-octanol inside the pores of a polypropylene hollow fiber and finally into a 25-microL acidic acceptor solution inside the hollow fiber. Following this liquid-liquid-liquid microextraction (LLLME), the acceptor solutions were analyzed by capillary zone electrophoresis (CE). Extractions were performed in simple disposable devices each consisting of a conventional 4-mL sample vial, two needles for introduction and collection of the acceptor solution, and a 8-cm piece of a porous polypropylene hollow fiber. From 5 to 20 different samples were extracted in parallel for 45 min, providing a high sample capacity. Methamphetamine was preconcentrated by a factor of 75 from aqueous standard solutions, human urine, and human plasma utilizing 10(-1) M HCl as the acceptor phase and 10(-1) M NaOH in the donor solution. In addition to preconcentration, LLLME also served as a technique for sample cleanup since large molecules, acidic compounds, and neutral components were not extracted into the acceptor phase. Utilizing diphenhydramine hydrochloride as internal standard, repetitive extractions varied less than 5.2% RSD (n = 6), while the calibration curve for methamphetamine was linear within the range 20 ng/microL to 10 micrograms/mL (r = 0.9983). The detection limit of methamphetamine utilizing LLLME/CE was 5 ng/mL (S/N = 3) in both human urine and plasma.

  10. Development of a new sample preparation method based on liquid-liquid-liquid extraction combined with dispersive liquid-liquid microextraction and its application on unfiltered samples containing high content of solids.

    PubMed

    Farajzadeh, Mir Ali; Abbaspour, Maryam

    2017-11-01

    A new sample preparation method based on liquid-liquid-liquid extraction combined with dispersive liquid-liquid microextraction followed by gas chromatography-flame ionization detection has been reported for the extraction/preconcentration and determination of trace levels of twelve pesticide residues from different samples with high content of solids without filtration. This method consists of a three-phase system including an aqueous phase (sample solution), acetonitrile, and hexane. The extraction mechanism is based on different affinities of the substances from the sample matrices towards each of the involved phase, which provides a high selectivity to the process. In other words, interfering hydrophobic compounds are transferred into hexane and will not be present in the final extract. Furthermore, ionic and polar compounds are retained in the aqueous phase. Therefore, only semi-polar compounds such as the studied pesticides are extracted into acetonitrile. In this method, a homogeneous solution of the aqueous phase and acetonitrile (a water-soluble extraction solvent) forms two clearly separated phases in the presence of sodium sulfate (as a phase separation agent) and simultaneously the analytes are extracted into the fine droplets of the acetonitrile collected on the surface of the aqueous phase. To achieve high enrichment factors, the acetonitrile phase is mixed with 1,2-dibromoethane (as a preconcentration solvent) at µL-level to perform the following dispersive liquid-liquid microextraction procedure. Several parameters that can affect extraction efficiency including kind and volume of extraction solvent, type and concentration of phase separation agent, hexane volume, kind of preconcentration solvent, and ionic strength were studied and optimized. Under the optimal conditions, extraction recoveries were obtained in the range of 53-93% and the calibration curves were linear in wide ranges with correlation coefficients ≥ 0.9983. Intra- (n = 6) and

  11. Cu(II)-mediated atom transfer radical polymerization of methyl methacrylate via a strategy of thermo-regulated phase-separable catalysis in a liquid/liquid biphasic system: homogeneous catalysis, facile heterogeneous separation, and recycling.

    PubMed

    Pan, Jinlong; Zhang, Bingjie; Jiang, Xiaowu; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2014-09-01

    A strategy of thermo-regulated phase-separable catalysis (TPSC) is applied to the Cu(II)-mediated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in a p-xylene/PEG-200 biphasic system. Initiators for continuous activator regeneration ATRP (ICAR ATRP) are used to establish the TPSC-based ICAR ATRP system using water-soluble TPMA as a ligand, EBPA as an initiator, CuBr2 as a catalyst, and AIBN as a reducing agent. By heating to 70 °C, unlimited miscibility of both solvents is achieved and the polymerization can be carried out under homogeneous conditions; then on cooling to 25 °C, the mixture separates into two phases again. As a result, the catalyst complex remains in the PEG-200 phase while the obtained polymers stay in the p-xylene phase. The catalyst can therefore be removed from the resultant polymers by easily separating the two different layers and can be reused again. It is important that well-defined PMMA with a controlled molecular weight and narrow molecular weight distribution could be obtained using this TPSC-based ICAR ATRP system. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Liquid / liquid ion-transfer processes at the dioctylphosphoric acid (N,N-didodecyl-N',N'-diethylphenylenediamine) / water (electrolyte) interface at graphite and mesoporous TiO2 substrates.

    PubMed

    Stott, Susan J; McKenzie, Katy J; Mortimer, Roger J; Hayman, Colin M; Buckley, Benjamin R; Bulman Page, Philip C; Marken, Frank; Shul, Galyna; Opallo, Marcin

    2004-09-15

    Biphasic electrode systems are studied for the case of the oxidation of the water-insoluble liquid N,N-didodecyl-N',N'-diethylphenylenediamine (DDPD) neat and dissolved in bis(2-ethylhexyl) phosphate (HDOP) and immersed in aqueous electrolyte media. The oxidation process in the absence of HDOP is accompanied by transfer of the anion (perchlorate or phosphate) from the water into the organic phase. However, in the presence of HDOP, oxidation is accompanied by proton exchange instead. This electrochemically driven proton exchange process occurs over a wide pH range. Organic microdroplet deposits of DDPD in HDOP at basal plane pyrolytic graphite electrodes are studied by voltammetric techniques and compared in their behavior to organic microphase deposits in mesoporous TiO2 thin films. The mesoporous TiO2 thin film acts as a host for the organic liquid and provides an alternative biphasic electrode system compared to the random microdroplet/graphite system. Two types of mesoporous TiO2 thin-film electrodes, (i) a 300-400-nm film on ITO and (ii) a 300-400-nm film on ITO sputter-coated with a 20-nm porous gold layer, are investigated.

  13. Dispersive liquid-liquid microextraction based on solidification of floating organic droplet followed by high-performance liquid chromatography with ultraviolet detection and liquid chromatography-tandem mass spectrometry for the determination of triclosan and 2,4-dichlorophenol in water samples.

    PubMed

    Zheng, Cao; Zhao, Jing; Bao, Peng; Gao, Jin; He, Jin

    2011-06-24

    A novel, simple and efficient dispersive liquid-liquid microextraction based on solidification of floating organic droplet (DLLME-SFO) technique coupled with high-performance liquid chromatography with ultraviolet detection (HPLC-UV) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed for the determination of triclosan and its degradation product 2,4-dichlorophenol in real water samples. The extraction solvent used in this work is of low density, low volatility, low toxicity and proper melting point around room temperature. The extractant droplets can be collected easily by solidifying it at a lower temperature. Parameters that affect the extraction efficiency, including type and volume of extraction solvent and dispersive solvent, salt effect, pH and extraction time, were investigated and optimized in a 5 mL sample system by HPLC-UV. Under the optimum conditions (extraction solvent: 12 μL of 1-dodecanol; dispersive solvent: 300 of μL acetonitrile; sample pH: 6.0; extraction time: 1 min), the limits of detection (LODs) of the pretreatment method combined with LC-MS/MS were in the range of 0.002-0.02 μg L(-1) which are lower than or comparable with other reported approaches applied to the determination of the same compounds. Wide linearities, good precisions and satisfactory relative recoveries were also obtained. The proposed technique was successfully applied to determine triclosan and 2,4-dichlorophenol in real water samples.

  14. Methods and problems in heat and mass transfer

    NASA Astrophysics Data System (ADS)

    Kotliar, Iakov Mikhailovich; Sovershennyi, Viacheslav Dmitrievich; Strizhenov, Dmitrii Sergeevich

    The book focuses on the mathematical methods used in heat and mass transfer problems. The theory, statement, and solution of some problems of practical importance in heat and mass transfer are presented, and methods are proposed for solving algebraic, transcendental, and differential equations. Examples of exact solutions to heat and mass transfer equations are given. The discussion also covers some aspects of the development of a mathematical model of turbulent flows.

  15. Mass Transfer and Rheology of Fiber Suspensions

    NASA Astrophysics Data System (ADS)

    Wang, Jianghui

    Rheological and mass transfer properties of non-Brownian fiber suspensions are affected by fiber characteristics, fiber interactions, and processing conditions. In this thesis we develop several simulation methods to study the dynamics of single fibers in simple shear flow, as well as the rheology and mass transfer of fiber suspensions. Isolated, rigid, neutrally-buoyant, non-Brownian, slightly curved, nonchiral fibers in simple shear flow of an incompressible Newtonian fluid at low Reynolds number can drift steadily in the gradient direction without external forces or torques. The average drift velocity and direction depend on the fiber aspect ratio, curvature and initial orientation. The drift results from the coupling of rotational and translational dynamics, and the combined effects of flipping, scooping, and spinning motions of the fiber. Irreversible fiber collisions in the suspensions cause shear-induced diffusion. The shear-induced self-diffusivity of dilute suspensions of fibers increases with increasing concentration and increasing static friction between contacts. The diffusivities in both the gradient and vorticity directions are larger for suspensions of curved fibers than for suspensions of straight fibers. For suspensions of curved fibers, significant enhancements in the diffusivity in the gradient direction are attributed to fiber drift in the gradient direction. The shear-induced self-diffusivity of concentrated suspensions of fibers increases with increasing concentration before fiber networks or flocs are formed, after which the diffusivity decreases with increasing concentration. The diffusivity increases with increasing fiber equilibrium bending angle, effective stiffness, coefficient of static friction, and rate of collisions. The specific viscosity of fiber suspensions increases with increasing fiber curvature, friction coefficient between mechanical contacts, and solids concentration. The specific viscosity increases linearly with

  16. Analysis of flavor compounds by GC/MS after liquid-liquid extraction from fruit juices

    NASA Astrophysics Data System (ADS)

    Tuşa, F. D.; Moldovan, Z.; Schmutzer, G.; Magdaş, D. A.; Dehelean, A.; Vlassa, M.

    2012-02-01

    In this work we describe a rapid method for analysis of volatile profiles of several commercial fruit juices using GC/MS instrument after liquid-liquid extraction. Volatile flavor compounds have been identified based on mass spectrum obtained in EI mode. This method allows to analyses a wide range of flavor compounds (esters, aldehydes, alcohols, terpenoids) the procedure was rapid, simple and inexpensive. Moreover, by means of volatile compounds it could be possible to distinguish between juices of organic and conventional production and those with flavorings addition. More of 20 compounds were identified and quantified as relative chromatogram area taken on larges ion in mass spectrum.

  17. [Mass transfer of magnesium in hemodialysis].

    PubMed

    Calzavara, P; Da Porto, A; Vianello, A; Gatti, P L; Maresca, M C; Caenaro, G

    1990-01-01

    The rate of mass-transfer (MT) of magnesium during hemodialysis was studied in thirty-five patients with hypermagnesemia (Mg = 3.75 +/- 0.72 mg/dl) undergoing chronic hemodialysis. The aim of the study was to verify which is the best dialytical approach to remove the excess of magnesium. The concentration of Mg in the dialysate was of 1.82 mg/dl for all patients. MT was -0.51 +/- 0.36 g and no statistical difference was found between patients treated with cuprophan hollow fibers dialyzers, PAN and cuprophan plates. Mg MT is not correlated with dialysis duration (r = -0.23; p:ns), urea clearance (r = -0.08; p:ns), KT/V index (r = -0.03; p:ns), blood flow (r = -0.15; p:ns). In conclusion from our data, in agreement with other Authors, reduction of serum Mg levels is more convenient by obtained by a decrease in Mg concentration in the dialysate under 1.82 mg/dl, in order to increase the blood-dialysate concentration gradient.

  18. Mass Transfers during Serpentinization of Oceanic Peridotites

    NASA Astrophysics Data System (ADS)

    Andreani, M.; Godard, M.; Delacour, A.; Escartin, J.; Mevel, C.; Muñoz, M.

    2011-12-01

    Mantle peridotites represent at least 20% of (ultra-)slow spread oceanic lithosphere. They are serpentinized down to several km below seafloor, and the numerous ultramafic-hosted hydrothermal systems emphasize the importance of serpentinization as a mean of chemical exchange between the mantle and the ocean. Characterizing the chemical modifications of peridotites during oceanic serpentinization and associated reactions is thus determinant to estimate the chemical fluxes near the ridges axis and the resulting input budget in subduction zones. However, these chemical exchanges are still poorly constrained. They depend on the initial chemical budget of peridotites (melting), on fluid sources (seawater or hydrothermal fluids), on sinks of elements (mineralogy), and on the operating mass transfer mechanisms, all expected to vary from one site to another. In order to better constrain mechanisms, scale and timing of mass transfers during serpentinization of oceanic peridotites, we carried out a combined (micro)-structural, mineralogical and geochemical study of variably refertilized and serpentinized peridotites drilled at the MARK area (ODP Site 920, 23°N Mid-Atlantic Ridge). The petrostructural study indicates that serpentinization is accompanied by adundant veining of different generations, characteristic of different mechanisms of deformation and transfer during the progressive tectonic exhumation of peridotites. Two main serpentinization stages are distinguished and rough constraints on the depth at which they occurred are provided by regional seismic velocity data. A diffusion-dominated stage occurs below ~2 km in depth. It is followed by an advection-dominated stage at shallower levels. This model is completed by a geochemical investigation of serpentinites using bulk and punctual analyses of traces elements by LA-HR-ICPMS, and iron redox state by XANES at iron K-edge. Results indicate that most samples preserve the bulk peridotite primary trace element signature

  19. Electrochemically modulated liquid-liquid extraction of ionized drugs under physiological conditions.

    PubMed

    Collins, Courtney J; Berduque, Alfonso; Arrigan, Damien W M

    2008-11-01

    Electrochemically modulated liquid-liquid extraction (EMLLE) enables the selective extraction and separation of ions from mixtures by choice of an applied interfacial potential difference. The extraction of ionized drugs from artificial urine is reported in this paper. The artificial urine matrix was characterized by cyclic voltammetry at the interface between two immiscible electrolyte solutions (ITIES), showing that components of that aqueous phase truncate the available potential window at the ITIES. The transfer of three cationic drugs from aqueous artificial urine to the 1,2-dichloroethane organic electrolyte phase was examined. Both propranolol and timolol were found to transfer across the artificial urine-organic interface. However, sotalol transfer was not possible within the available potential window. Extraction of propranolol and timolol from artificial urine into an organogel phase, by electrochemically modulated liquid-liquid extraction, was examined. The application of potentials positive of the drugs' formal transfer potentials enabled the selective extraction of both propranolol and timolol, with a higher potential being required for timolol. This work demonstrates the practical utility of EMLLE for the selective extraction of target compounds from a complex sample matrix.

  20. Mass transfer in white dwarf-neutron star binaries

    NASA Astrophysics Data System (ADS)

    Bobrick, Alexey; Davies, Melvyn B.; Church, Ross P.

    2017-05-01

    We perform hydrodynamic simulations of mass transfer in binaries that contain a white dwarf and a neutron star (WD-NS binaries), and measure the specific angular momentum of material lost from the binary in disc winds. By incorporating our results within a long-term evolution model, we measure the long-term stability of mass transfer in these binaries. We find that only binaries containing helium white dwarfs (WDs) with masses less than a critical mass of MWD, crit = 0.2 M⊙ undergo stable mass transfer and evolve into ultracompact X-ray binaries. Systems with higher mass WDs experience unstable mass transfer, which leads to tidal disruption of the WD. Our low critical mass compared to the standard jet-only model of mass-loss arises from the efficient removal of angular momentum in the mechanical disc winds, which develop at highly super-Eddington mass-transfer rates. We find that the eccentricities expected for WD-NS binaries when they come into contact do not affect the loss of angular momentum, and can only affect the long-term evolution if they change on shorter time-scales than the mass-transfer rate. Our results are broadly consistent with the observed numbers of both ultracompact X-ray binaries and radio pulsars with WD companions. The observed calcium-rich gap transients are consistent with the merger rate of unstable systems with higher mass WDs.

  1. Vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction.

    PubMed

    Yang, Zhong-Hua; Lu, Yue-Le; Liu, Yu; Wu, Tong; Zhou, Zhi-Qiang; Liu, Dong-Hui

    2011-10-07

    A novel sample pre-treatment technique, based on vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction (VSLLME), followed by gas chromatography-flame photometric detection (GC-FPD) has been developed for the determination of seven organophosphorus pesticides (OPPs) in wine and honey samples. In the VSLLME method, the extraction solvent was dispersed into the aqueous samples by the assistance of vortex agitator. Meanwhile, the addition of a surfactant, which was used as an emulsifier, could enhance the speed of the mass-transfer from aqueous samples to the extraction solvent. The main parameters relevant to this method were investigated and the optimum conditions were established: 15 μL chlorobenzene was used as extraction solvent, 0.2 mmol L(-1) Triton X-114 was selected as the surfactant, the extraction time was fixed at 30s, 3% sodium chloride was added and the extraction process was performed under the room temperature. Under the optimum conditions, limits of detections (LODs) were varied between 0.01 and 0.05 μg L(-1). The relative standard deviation (RSD, n=6) ranged from 2.3% and 8.9%. The linearity was obtained by five points in the concentration range of 0.1-50.0 μg L(-1). Correlation coefficients (r) varied from 0.9969 to 0.9991. The enrichment factors (EFs) were in a range of 282-309. Finally, the proposed method has been successfully applied to the determination of target analytes in real samples. The recoveries of the target analytes in wine and honey samples were between 81.2% and 108.0%.

  2. An electrically driven gas-liquid-liquid contactor for bioreactor and other applications

    SciTech Connect

    Tsouris, C.; Borole, A.P.; Kaufman, E.N.; DePaoli, D.W.

    1999-05-01

    An electrically driven gas-liquid-liquid bioreactor is described here, in which an aqueous medium containing a biocatalyst is introduced as a discontinuous phase into an organic-continuous liquid phase containing a substrate to be converted by the biocatalyst. A gas discontinuous phase, which may be needed to provide oxygen or a gaseous substrate to the biocatalyst, is also introduced into the bioreactor. In contrast to previous work on electrically driven contactors, it was found that the electroconvection generated by the electric field between parallel-plate electrodes may be employed to increase the volume fraction of the discontinuous gas phase in the bioreactor, providing the means for enhanced mass transfer. The electrically driven bioreactor was utilized for oil desulfurization experiments with Rhodococcus sp. IGTS8 bacteria as the biocatalyst. The organic phase used in the experiments was hexadecane containing dibenzothiophene, a model sulfur compound, that is oxidatively desulfurized to 2-hydroxybiphenyl (2-HBP) by the bacteria in the presence of air or oxygen. The gas volume fraction was increased by 60% by the application of a pulsed electric field, thus providing a means for increased transport of oxygen needed for oxidative desulfurization. The velocity of droplets and bubbles was measured by a phase Doppler velocimeter. The average rising velocity of bubbles was decreased from 13 to less than 3 cm/s and the average horizontal velocity was increased from 0 to 5 cm/s as the field strength was increased from 0 to 4 kV/cm. Desulfurization rates ranged from 1.0 to 5.50 mg of 2-HBP/g of dry cells/h. The desulfurization rate with aeration was doubled under the electric field as compared to the zero-field desulfurization under the same conditions.

  3. Automated dynamic liquid-liquid-liquid microextraction followed by high-performance liquid chromatography-ultraviolet detection for the determination of phenoxy acid herbicides in environmental waters.

    PubMed

    Wu, Jingming; Ee, Kim Huey; Lee, Hian Kee

    2005-08-05

    Automated dynamic liquid-liquid-liquid microextraction (D-LLLME) controlled by a programmable syringe pump and combined with HPLC-UV was investigated for the extraction and determination of 5 phenoxy acid herbicides in aqueous samples. In the extraction procedure, the acceptor phase was repeatedly withdrawn into and discharged from the hollow fiber by the syringe pump. The repetitive movement of acceptor phase into and out of the hollow fiber channel facilitated the transfer of analytes into donor phase, from the organic phase held in the pore of the fiber. Parameters such as the organic solvent, concentrations of the donor and acceptor phases, plunger movement pattern, speed of agitation and ionic strength of donor phase were evaluated. Good linearity of analytes was achieved in the range of 0.5-500 ng/ml with coefficients of determination, r2 > 0.9994. Good repeatabilities of extraction performance were obtained with relative standard deviations lower than 7.5%. The method provided up-to 490-fold enrichment within 13 min. In addition, the limits of detection (LODs) ranged from 0.1 to 0.4 ng/mL (S/N = 3). D-LLLME was successfully applied for the analysis of phenoxy acid herbicides from real environmental water samples.

  4. Redox chemistry at liquid/liquid interfaces

    NASA Technical Reports Server (NTRS)

    Volkov, A. G.; Deamer, D. W.

    1997-01-01

    The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.

  5. Redox chemistry at liquid/liquid interfaces

    NASA Technical Reports Server (NTRS)

    Volkov, A. G.; Deamer, D. W.

    1997-01-01

    The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.

  6. Instability of mass transfer in a planet-star system

    NASA Astrophysics Data System (ADS)

    Jia, Shi; Spruit, H. C.

    2017-02-01

    We show that the angular momentum exchange mechanism governing the evolution of mass-transferring binary stars does not apply to Roche lobe filling planets, because most of the angular momentum of the mass-transferring stream is absorbed by the host star. Apart from a correction for the difference in specific angular momentum of the stream and the centre of mass of the planet, the orbit does not expand much on Roche lobe overflow. We explore the conditions for dynamically unstable Roche lobe overflow as a function of planetary mass and mass and radius (age) of host star and equation of state of planet. For a Sun-like host, gas giant planets in a range of mass and entropy can undergo dynamical mass transfer. Examples of the evolution of the mass transfer process are given. Dynamic mass transfer of rocky planets depends somewhat sensitively on equation of state used. Silicate planets in the range 1 < Mp < 10 M⊕ typically go through a phase of dynamical mass transfer before settling to slow overflow when their mass drops to less than 1 M⊕.

  7. A mass transfer model of bauxite formation

    SciTech Connect

    Soler, J.M.; Lasaga, A.C.

    1996-12-01

    The formation of bauxite due to weathering of a granitic protolith has been simulated by means of a one-dimensional flow and reaction model based on the mass transfer principle. The model couples mineral dissolution and precipitation reactions, speciation in solution, and advective solute transport in a porous medium. A very important aspect of the modeling study is the use of mineral reaction rates determined experimentally in the laboratory. The important effects of solution saturation state and pH have been incorporated into the kinetic rate laws governing the heterogeneous reactions. The values of these parameters have been obtained from the scientific literature to guarantee that realistic reaction rates are used in the simulations. Albite and quartz are the minerals that make up the parent rock in the model. Gibbsite, kaolinite, and a Na-mica (as a surrogate for smectite) are the secondary minerals that have been taken into account. Long-term simulations (>1 Ma) have been run, and the formation of a bauxitic profile, with an upper gibbsite-rich and a lower kaolinite-rich zone, is predicted. In early stages of the process (up to a few hundreds of thousands of years), both gibbsite and kaolinite precipitate directly from solution as a consequence of albite dissolution. In later stages, the bulk of gibbsite precipitation derives from the incongruent dissolution of kaolinite, while kaolinite precipitation is still caused by the dissolution of albite. This is also reflected by the formation of two reaction fronts in the profile. These results are compared with weathering sequences from the Los Pijiguaos bauxite deposit, Venezuela. The overlap between the gibbsite and kaolinite zones and the replacement of kaolinite by gibbsite are consistent with model calculations. 59 refs., 22 figs., 1 tab.

  8. Multiresidue determination of 11 new fungicides in grapes and wines by liquid-liquid extraction/clean-up and programmable temperature vaporization injection with analyte protectants/gas chromatography/ion trap mass spectrometry.

    PubMed

    González-Rodríguez, Rosa M; Cancho-Grande, Beatriz; Simal-Gándara, Jesús

    2009-08-07

    A gas chromatographic ion trap mass spectrometry (GC-ITMS) method was developed for the determination of 11 new generation fungicides (benalaxyl, benalaxyl-M, boscalid, cyazofamid, famoxadone, fenamidone, fluquinconazole, iprovalicarb, pyraclostrobin, trifloxystrobin and zoxamide) in grapes and wines. Samples were extracted with ethyl acetate:hexane (1:1, v/v) and cleaned-up with graphitized carbon black/primary secondary amine (GCB/PSA) solid-phase extraction (SPE) cartridges using acetonitrile:toluene (3:1, v/v) as eluent. The addition of analyte protectants (3-ethoxy-1,2-propanediol, d-sorbitol and l-gulonic acid gamma-lactone) in the final extracts allowed to avoid the matrix-induced response enhancement effect on quantitation process with absolute recoveries ca. 100%. Precision (expressed as relative standard deviation) was lower than 16% for all fungicides. Limits of detection and quantitation were lower than 0.01 mg/kg or mg/L, except for cyazofamid, much smaller in all cases than maximum residue levels (MRLs) established by European Union for grapes and by Switzerland and Italy for wines. The proposed method was applied to determine fungicide residues in three different white grapes for vinification produced in Ribeiro area in Galicia (NW Spain), as well as in their corresponding final wines.

  9. Fast and simple procedure for liquid-liquid extraction of 136 analytes from different drug classes for development of a liquid chromatographic-tandem mass spectrometric quantification method in human blood plasma.

    PubMed

    Remane, Daniela; Meyer, Markus R; Peters, Frank T; Wissenbach, Dirk K; Maurer, Hans H

    2010-07-01

    In clinical and forensic toxicology, different extraction procedures as well as analytical methods are used to monitor different drug classes of interest in biosamples. Multi-analyte procedures are preferable because they make the analytical strategy much simpler and cheaper and allow monitoring of analytes of different drug classes in one single body sample. For development of such a multi-analyte liquid chromatography-tandem mass spectrometry approach, a rapid and simple method for the extraction of 136 analytes from the following drug classes has been established: antidepressants, neuroleptics, benzodiazepines, beta-blockers, oral antidiabetics, and analytes relevant in the context of brain death diagnosis. Recovery, matrix effects, and process efficiency were tested at two concentrations using six different lots of blank plasma. The recovery results obtained using absolute peak areas were compared with those calculated using area ratios analyte/internal standard. The recoveries ranged from 8% to 84% for antidepressants, from 10% to 79% for neuroleptics, from 60% to 81% for benzodiazepines, from 1% to 71% for beta-blockers, from 10% to 73% for antidiabetics, and from 60% to 86% for analytes relevant in the context of brain death diagnosis. With the exception of 52 analytes at low concentration and 37 at high concentration, all compounds showed recoveries with acceptable variability with less than 15% and 20% coefficients of variation. Recovery results obtained by comparing peak area ratios were nearly the same, but 35 analytes at low concentration and 17 at high concentration lay above the acceptance criteria. Matrix effects with more than 25% were observed for 18 analytes. The results were acceptable for 119 analytes at high concentrations.

  10. Superoleophobic yet Superhydrophilic surfaces for Continuous Liquid-Liquid Separation

    DTIC Science & Technology

    2011-12-08

    F. Jensen, Integrated continuous microfluidic liquid-liquid extraction. Lab Chip 7, 256 (2007). 39. D. E. Angelescu, B. Mercier, D. Siess, R... silane coupling agents. Langmuir 12, 3529 (1996). 30. S. J. Hutton, J. M. Crowther, J. P. S. Badyal, Complexation of Fluorosurfactants to

  11. Performance of sonication and microfluidization for liquid-liquid emulsification.

    PubMed

    Maa, Y F; Hsu, C C

    1999-05-01

    The purpose of this research was to evaluate and compare liquid-liquid emulsions (water-in-oil and oil-in-water) prepared using sonication and microfluidization. Liquid-liquid emulsions were characterized on the basis of emulsion droplet size determined using a laser-based particle size analyzer. An ultrasonic-driven benchtop sonicator and an air-driven microfluidizer were used for emulsification. Sonication generated emulsions through ultrasound-driven mechanical vibrations, which caused cavitation. The force associated with implosion of vapor bubbles caused emulsion size reduction and the flow of the bubbles resulted in mixing. An increase in viscosity of the dispersion phase improved the sonicator's emulsification capability, but an increase in the viscosity of the dispersed phase decreased the sonicator's emulsification capability. Although sonication might be comparable to homogenization in terms of emulsification efficiency, homogenization was relatively more effective in emulsifying more viscous solutions. Microfluidization, which used a high pressure to force the fluid into microchannels of a special configuration and initiated emulsification via a combined mechanism of cavitation, shear, and impact, exhibited excellent emulsification efficiency. Of the three methodologies, sonication generated more heat and might be less suitable for emulsion systems involving heat-sensitive materials. Homogenization is in general a more effective liquid-liquid emulsification method. The results derived from this study can serve as a basis for the evaluation of large-scale liquid-liquid emulsification in the microencapsulation process.

  12. Polymer Crystallization at Curved Liquid/Liquid Interface

    NASA Astrophysics Data System (ADS)

    Wang, Wenda

    Liquid/liquid interface, either flat or curved, is a unique template for studying self-assembly of a variety of nanomaterials such as nanoparticles and nanorods. The resultant monolayer films can be ordered or disordered depending on the regularity of the nanomaterials. Integration of nanoparticles into two-dimensional structure leads to intriguing collective properties of the nanoparticles. Crystallization can also be guided by liquid/liquid interface. Due to the particular shape of the interface, crystallization can happen in a different manner comparing to the normal solution crystallization. In this dissertation, liquid/liquid interface is employed to guide the crystallization of polymers, mainly focusing on using curved liquid/liquid interface. Due to the unique shape of the interface and feasibility to control the curvature, polymer crystallization can take place in different manner and lead to the formation of curved or vesicular crystals. Curved liquid/liquid interface is typically created through o/w emulsions. With the presence of surfactant, the emulsions are controlled to be stable at least for the polymer crystallization periods. The difference to normal solution crystallization is: the nuclei will diffuse to the curved interface due to the Pickering effect and guide the crystallization along the curved liquid/liquid interface. If the supercooling can be controlled to be very small, crystal growth in the bulk droplets can be avoided. The advantages of this strategy are: 1) the formation process of vesicular type crystals can be monitored by controlling the polymer supply; 2) curved crystals, bowl-like structures and enclosed capsules can be easily obtained comparing to the self-assembly method for vesicle formation; 3) the obtained vesicles will be made of polymer crystals, which will possess the extraordinary mechanical properties. Based on the nucleation type, this dissertation is divided into two parts. The first part is focused on the self

  13. Efficient Heat and Mass Transfer Formulations for Oil Shale Retorting

    NASA Astrophysics Data System (ADS)

    Parker, J. C.; Zhang, F.

    2007-12-01

    A mathematical model for oil shale retorting is described that considers kerogen pyrolysis, oil coking, residual carbon gasification, carbonate mineral decomposition, water-gas shift, and phase equilibria reaction. Reaction rate temperature-dependence is described by Arrhenius kinetics. Fractured rock is modeled as a bi-continuum consisting of fracture porosity in which advective and dispersive gas and heat transport occur, and rock matrix in which diffusive mass transport and thermal conduction occur. Heat transfer between fracture and matrix regions is modeled either by a partial differential equation for spherical conduction or by a linear first-order heat transfer formulation. Mass transfer is modeled in an analogous manner or assuming local equilibrium. First-order mass and heat transfer coefficients are computed by a theoretical model from fundamental rock matrix properties. The governing equations are solved using a 3-D finite element formulation. Simulations of laboratory retort experiments and hypothetical problems indicated thermal disequilibrium to be the dominant factor controlling retort reactions. Simulation accuracy was unaffected by choice of mass transfer formulation. However, computational effort to explicitly simulate diffusive mass transfer in the rock matrix increased computational effort by more than an order of magnitude compared with first-order mass transfer or equilibrium analyses. A first-order heat transfer approximation of thermal conduction can be used without significant loss of accuracy if the block size and/or heating rate are not too large, as quantified by a proposed dimensionless heating rate.

  14. Mass transfer from bypassed zones during gas injection

    SciTech Connect

    Burger, J.E.; Mohanty, K.K.

    1995-12-31

    Gasflooding in oil reservoirs leads to bypassing of the oil due to gravitational, viscous and/or heterogeneity effects. The bypassed oil can be recovered by the flowing solvent by pressure-driven, gravity-driven, dispersion/diffusion-driven and capillarity-driven crossflow/mass transfer. It is difficult to represent all of these mechanisms explicitly in large-scale simulations. In this work, we have studied the effect of the orientation of the bypassed region and the enrichment of the solvent on the mass transfer. Laboratory-scale mass transfer and coreflood experiments were conducted. Numerical simulation was used to identify the role of the different mechanisms. Results indicate that the mass transfer is the least for the vertical orientation, intermediate for the inverted orientation and the highest for the horizontal orientation. The mass transfer increases with enrichment for all orientations. Liquid phase diffusion controls vertical orientation mass transfer for the fluids studied. Phase behavior determines the liquid phase saturation. Capillary pumping does not contribute to the mass transfer of oil because the interfacial tension decreases towards the flowing region. Gravity-driven flow contributes the most to the mass transfer in the horizontal and the inverted orientations. The gravity-driven flow, however, is impeded by the capillarity whose magnitude decreases with solvent enrichment. Oil recovery in the horizontal gasfloods is nonmonotonic with enrichment for this fluid system in an almost homogeneous Berea core. Multiphase flow in the near-miscible floods leads to less gravity override compared to the FCM floods. In the heterogeneous core studied, the heterogeneity is very strong and the capillary forces do not prevent bypassing. The capillary forces, in fact, reduce oil recovery by diminishing mass transfer from the bypassed regions.

  15. Spatial scanning spectroelectrochemistry. Study of the electrodeposition of Pd nanoparticles at the liquid/liquid interface.

    PubMed

    Izquierdo, Daniel; Martinez, Alberto; Heras, Aranzazu; Lopez-Palacios, Jesus; Ruiz, Virginia; Dryfe, Robert A W; Colina, Alvaro

    2012-07-03

    Spatial scanning spectroelectrochemistry is a new analytical technique that provides spectral information at different distances from an electrified liquid/liquid interface where an electrochemical process takes place. As a proof of concept, we have studied two different electrochemical processes at the electrified liquid/liquid interface: (1) Ru(bpy)(3)(2+) transfer through the water/1,2-dichloroethane interface and (2) electrodeposition of Pd nanoparticles at the water/1,2-dichloroethane interface. The instrumental setup developed consists of a movable slit for the light beam to sample at well-defined positions on both sides of the interface, providing important information about the chemical process occurring. If the slit is scanned at different distances from the interface during an electrochemical experiment, a complete picture of the reactions and equilibria in the diffusion layer can be obtained. For example, in the case of the Ru(bpy)(3)(2+), the experiments show clearly how the complex is transferred from one phase to the other. In the case of electrosynthesis of Pd nanoparticles, it is demonstrated that nanoparticles are not only deposited at the interface but diffuse to the aqueous bulk solution. These in situ observations were confirmed by ex situ experiments using transmission electron microscopy.

  16. Observing Mass Transfer in a Neglected Interacting Binary Star

    NASA Astrophysics Data System (ADS)

    Reed, Phillip A.

    2011-05-01

    The eclipsing and interacting binary star R Arae is a very interesting system that has unfortunately been neglected. The few spectroscopic studies of the system report badly blended absorption lines that indicate mass transfer, but until now there has been no orbital period study to conclusively show a real period change resulting from mass transfer. In this study, new data are combined with those found in the available literature and in the database of the American Association of Variable Star Observers to construct the first ephemeris curve for R Ara, which spans more than a century since its discovery in 1894. Average orbital period change and conservative mass transfer rates are presented.

  17. Mass transfer coefficients determination from linear gradient elution experiments.

    PubMed

    Pfister, David; Morbidelli, Massimo

    2015-01-02

    A procedure to estimate mass transfer coefficients in linear gradient elution chromatography is presented and validated by comparison with experimental data. Mass transfer coefficients are traditionally estimated experimentally through the van Deemter plot, which represents the HETP as a function of the fluid velocity. Up to now, the HETP was obtained under isocratic elution conditions. Unfortunately, isocratic elution experiments are often not suitable for large biomolecules which suffer from severe mass transfer hindrances. Yamamoto et al. were the first to propose a semi-empirical equation to relate HETPs measured from linear gradient elution experiments to those obtained under isocratic conditions [7]. Based on his pioneering work, the approach presented in this work aims at providing an experimental procedure supported by simple equations to estimate reliable mass transfer parameters from linear gradient elution chromatographic experiments. From the resolution of the transport model, we derived a rigorous analytical expression for the HETP in linear gradient elution chromatography.

  18. Heat and Mass Transfer in an L Shaped Porous Medium

    NASA Astrophysics Data System (ADS)

    Salman Ahmed, N. J.; Azeem; Yunus Khan, T. M.

    2017-08-01

    This article is an extension to the heat transfer in L-shaped porous medium by including the mass diffusion. The heat and mass transfer in the porous domain is represented by three coupled partial differential equations representing the fluid movement, energy transport and mass transport. The equations are converted into algebraic form of equations by the application of finite element method that can be conveniently solved by matrix method. An iterative approach is adopted to solve the coupled equations by setting suitable convergence criterion. The results are discussed in terms of heat transfer characteristics influenced by physical parameters such as buoyancy ratio, Lewis number, Rayleigh number etc. It is found that these physical parameters have significant effect on heat and mass transfer behavior of L-shaped porous medium.

  19. Liquid-liquid critical point: an analytical approach

    NASA Astrophysics Data System (ADS)

    Daanoun, A.

    2006-09-01

    Theoretical simulations and experimental studies have showed that many systems (like liquid metals) can exhibit two phase transitions: gas-liquid and liquid-liquid. Consequently the fluid phase of these systems presents two critical points, namely the usual gas-liquid (G-L) critical point and the liquid-liquid critical point that results from a phase transition between two liquids of different densities: a low density liquid (LDL) and a high density liquid (HDL). The van der Waals theory for simple fluids [Phys. Rev. E 50, 2913 (1994)] is based on taking a system with purely repulsive forces as a reference, is able to describe two stable first-order phase transitions between fluids of different densities. The particles in our system interact via a total pair potential, which splits into a repulsive VR and a density-dependent attractive VA part.

  20. Polymer single crystal membrane from liquid/liquid interface

    NASA Astrophysics Data System (ADS)

    Wang, Wenda; Li, Christopher; Soft Matter Research Group-Drexel University Team

    2013-03-01

    Vesicles, mimicking the structure of cell membrane at the molecular scale, are small membrane-enclosed sacks that can store or transport substances. The weak mechanical properties and the nature of environment-sensitivity of the current available vesicles: liposomes, polymersomes, colloidsomes limit their applications as an excellent candidate for targeting delivery of drugs/genes in biomedical engineering and treatment. Recently, we developed an emulsion-based method to grow curved polymer single crystals. Varying the polymer concentration and/or the emulsification conditions (such as surfactant concentration, water-oil volume ratio), curved crystals with different sizes and different openness could be obtained. This growing process was attributed to polymer crystal growth along the liquid/liquid interface. In addition, the liquid/liquid interfacial crystal growth is promising for synthesis of enclosed hollow sphere.

  1. Correlation of liquid-film cooling mass transfer data.

    NASA Technical Reports Server (NTRS)

    Gater, R. A.; L'Ecuyer, M. R.

    1972-01-01

    An empirical correlation proposed by Gater and Ecuyer (1970) for liquid-film cooling mass transfer, accounting for film roughness and entrainment effects, is extended to include liquid films of arbitrary length. A favorable comparison between the predicted results and the experimental data of Kinney et al. (1952) and Emmons and Warner (1964) shows the utility of the mass transfer correlation for predictions over a wide range of experimental parameters.

  2. Morphology of Liquid-Liquid Phase Separated Aerosols.

    PubMed

    Qiu, Yuqing; Molinero, Valeria

    2015-08-26

    The morphology of liquid-liquid phase separated aerosols has a strong impact on their rate of gas and water uptake, and the type and rate of heterogeneous reactions in the atmosphere. However, it is extremely challenging to experimentally distinguish different morphologies (core-shell or partial wetting) of aerosols and to quantify the extent of wetting between the two phases. The aim of this work is to quantitatively predict the morphology of liquid-liquid aerosols from fundamental physical properties of the aerosol phases. We determine the equilibrium structure of liquid-liquid phase separated aerosols through free energy minimization and predict that the contact angle between the two liquids in the aerosol depends on the composition but not the amount of each phase. We demonstrate that for aerosols of diameter larger than ∼100 nm, the equilibrium contact angle can be accurately predicted from the surface tensions of each liquid with the vapor and between the two liquids through an expression that is identical to Young's equation. The internal structure of smaller, ultrafine aerosols depends also on the value of the line tension between the two liquids and the vapor. The thermodynamic model accurately predicts the experimental morphology, core-shell or partial wetting, of all aerosols for which surface tensions are provided in the literature, and provides contact angles that cannot be accurately determined with state of the art experimental methods. We find that the contact angle of model atmospheric aerosols is rarely higher than 30°. We validate the thermodynamic predictions through molecular simulations of nonane-water droplets, and use the simulation data to compute line tension values that are in good agreement with theory and the analysis from experimental data in water-nonane droplets. Our finding of a simple analytical equation to compute the contact angle of liquid-liquid droplets should have broad application for the prediction of the morphology of

  3. Control and Automation of Fluid Flow, Mass Transfer and Chemical Reactions in Microscale Segmented Flow

    NASA Astrophysics Data System (ADS)

    Abolhasani, Milad

    Flowing trains of uniformly sized bubbles/droplets (i.e., segmented flows) and the associated mass transfer enhancement over their single-phase counterparts have been studied extensively during the past fifty years. Although the scaling behaviour of segmented flow formation is increasingly well understood, the predictive adjustment of the desired flow characteristics that influence the mixing and residence times, remains a challenge. Currently, a time consuming, slow and often inconsistent manual manipulation of experimental conditions is required to address this task. In my thesis, I have overcome the above-mentioned challenges and developed an experimental strategy that for the first time provided predictive control over segmented flows in a hands-off manner. A computer-controlled platform that consisted of a real-time image processing module within an integral controller, a silicon-based microreactor and automated fluid delivery technique was designed, implemented and validated. In a first part of my thesis I utilized this approach for the automated screening of physical mass transfer and solubility characteristics of carbon dioxide (CO2) in a physical solvent at a well-defined temperature and pressure and a throughput of 12 conditions per hour. Second, by applying the segmented flow approach to a recently discovered CO2 chemical absorbent, frustrated Lewis pairs (FLPs), I determined the thermodynamic characteristics of the CO2-FLP reaction. Finally, the segmented flow approach was employed for characterization and investigation of CO2-governed liquid-liquid phase separation process. The second part of my thesis utilized the segmented flow platform for the preparation and shape control of high quality colloidal nanomaterials (e.g., CdSe/CdS) via the automated control of residence times up to approximately 5 minutes. By introducing a novel oscillatory segmented flow concept, I was able to further extend the residence time limitation to 24 hours. A case study of a

  4. Influence of pluronic F68 on oxygen mass transfer.

    PubMed

    Sieblist, Christian; Jenzsch, Marco; Pohlscheidt, Michael

    2013-01-01

    Pluronic F68 is one of the most used shear protecting additives in cell culture cultivations. It is well known from literature that such surface-active surfactants lower the surface tension at the gas-liquid interface, which influences the mass transfer. In this study, the effect of Pluronic F68 on oxygen mass transfer in aqueous solutions was examined. Therefore, the gassing in/gassing out method and bubble size measurements were used. At low concentrations of 0.02 g/L, a 50% reduction on mass transfer was observed for all tested spargers and working conditions. An explanation of the observed effects by means of Higbie's penetration or Dankwerts surface renewal theory was applied. It could be demonstrated that the suppressed movement of the bubble surface layer is the main cause for the significant drop down of the kL a-values. For Pluronic F68 concentrations above 0.1 g/L, it was observed that it comes to changes in bubble appearance and bubble size strongly dependent on the sparger type. By using the bubble size measurement data, it could be shown that only small changes in mass transfer coefficient (kL ) take place above the critical micelle concentration. Further changes on overall mass transfer at higher Pluronic F68 concentrations are mainly based on increasing of gas holdup and, more importantly, by increasing of the surface area available for mass transfer.

  5. Local Mass and Heat Transfer on a Turbine Blade Tip

    DOE PAGES

    Jin, P.; Goldstein, R. J.

    2003-01-01

    Locmore » al mass and heat transfer measurements on a simulated high-pressure turbine blade-tip surface are conducted in a linear cascade with a nonmoving tip endwall, using a naphthalene sublimation technique. The effects of tip clearance (0.86–6.90% of chord) are investigated at various exit Reynolds numbers (4–7 × 10 5 ) and turbulence intensities (0.2 and 12.0%). The mass transfer on the tip surface is significant along its pressure edge at the smallest tip clearance. At the two largest tip clearances, the separation bubble on the tip surface can cover the whole width of the tip on the second half of the tip surface. The average mass-transfer rate is highest at a tip clearance of 1.72% of chord. The average mass-transfer rate on the tip surface is four and six times as high as on the suction and the pressure surface, respectively. A high mainstream turbulence level of 12.0% reduces average mass-transfer rates on the tip surface, while the higher mainstream Reynolds number generates higher local and average mass-transfer rates on the tip surface.« less

  6. Simultaneous liquid-liquid microextraction/methylation for the determination of haloacetic acids in drinking waters by headspace gas chromatography.

    PubMed

    Cardador, M J; Serrano, A; Gallego, M

    2008-10-31

    A novel analytical method that combines simultaneous liquid-liquid microextraction/methylation and headspace gas chromatography-mass spectrometry for the determination of nine haloacetic acids (HAAs) in water was reported. A mechanistic model on the basis of mass transfer with chemical reaction in which methylation of HAAs was accomplished in n-pentane-water (150 microl-10 ml) two-phase system with a tetrabutylammonium salt as phase transfer catalyst was proposed. Derivatisation with dimethylsulphate was completed in 3 min by shaking at room temperature. The methyl ester derivatives and the organic phase were completely volatilised by static headspace technique, being the gaseous phase analysed. Parameters related to the extraction/methylation and headspace generation of HAAs were studied and the results were compared with methyl haloacetate standards to establish the yield of each step. The thermal instability of HAAs, by degradation to their respective halogenated hydrocarbon by decarboxylation, and the possible hydrolysation of the methyl esters were rigorously controlled in the whole process to obtain a reliable and robust method. The proposed method yielded detection limits very low which ranges from 0.02 to 0.4 microg l(-1) and a relative standard deviation of ca. 7.5%. Finally, the method was validated with the US Environmental Protection Agency (EPA) method 552.2 for the analysis of HAAs in drinking and swimming pool water samples containing concentrations of HAAs that must be higher than 10 microg l(-1) due to the fact that this method is less sensitive than the proposed one.

  7. Geoelectrical Measurement of Multi-Scale Mass Transfer Parameters

    SciTech Connect

    Day-Lewis, Frederick David; Singha, Kamini; Johnson, Timothy C.; Haggerty, Roy; Binley, Andrew; Lane, John W.

    2014-11-25

    Mass transfer affects contaminant transport and is thought to control the efficiency of aquifer remediation at a number of sites within the Department of Energy (DOE) complex. An improved understanding of mass transfer is critical to meeting the enormous scientific and engineering challenges currently facing DOE. Informed design of site remedies and long-term stewardship of radionuclide-contaminated sites will require new cost-effective laboratory and field techniques to measure the parameters controlling mass transfer spatially and across a range of scales. In this project, we sought to capitalize on the geophysical signatures of mass transfer. Previous numerical modeling and pilot-scale field experiments suggested that mass transfer produces a geoelectrical signature—a hysteretic relation between sampled (mobile-domain) fluid conductivity and bulk (mobile + immobile) conductivity—over a range of scales relevant to aquifer remediation. In this work, we investigated the geoelectrical signature of mass transfer during tracer transport in a series of controlled experiments to determine the operation of controlling parameters, and also investigated the use of complex-resistivity (CR) as a means of quantifying mass transfer parameters in situ without tracer experiments. In an add-on component to our grant, we additionally considered nuclear magnetic resonance (NMR) to help parse mobile from immobile porosities. Including the NMR component, our revised study objectives were to: 1. Develop and demonstrate geophysical approaches to measure mass-transfer parameters spatially and over a range of scales, including the combination of electrical resistivity monitoring, tracer tests, complex resistivity, nuclear magnetic resonance, and materials characterization; and 2. Provide mass-transfer estimates for improved understanding of contaminant fate and transport at DOE sites, such as uranium transport at the Hanford 300 Area. To achieve our objectives, we implemented a 3

  8. Mass transfer between debris discs during close stellar encounters

    NASA Astrophysics Data System (ADS)

    Jílková, Lucie; Hamers, Adrian S.; Hammer, Michael; Portegies Zwart, Simon

    2016-04-01

    We study mass transfers between debris discs during stellar encounters. We carried out numerical simulations of close flybys of two stars, one of which has a disc of planetesimals represented by test particles. We explored the parameter space of the encounters, varying the mass ratio of the two stars, their pericentre and eccentricity of the encounter, and its geometry. We find that particles are transferred to the other star from a restricted radial range in the disc and the limiting radii of this transfer region depend on the parameters of the encounter. We derive an approximate analytic description of the inner radius of the region. The efficiency of the mass transfer generally decreases with increasing encounter pericentre and increasing mass of the star initially possessing the disc. Depending on the parameters of the encounter, the transfer particles have a specific distribution in the space of orbital elements (semimajor axis, eccentricity, inclination, and argument of pericentre) around their new host star. The population of the transferred particles can be used to constrain the encounter through which it was delivered. We expect that many stars experienced transfer among their debris discs and planetary systems in their birth environment. This mechanism presents a formation channel for objects on wide orbits of arbitrary inclinations, typically having high eccentricity but possibly also close to circular (eccentricities of about 0.1). Depending on the geometry, such orbital elements can be distinct from those of the objects formed around the star.

  9. Secular dynamics in hierarchical three-body systems with mass loss and mass transfer

    SciTech Connect

    Michaely, Erez; Perets, Hagai B.

    2014-10-20

    Recent studies have shown that secular evolution of triple systems can play a major role in the evolution and interaction of their inner binaries. Very few studies explored the stellar evolution of triple systems, and in particular the mass-loss phase of the evolving stellar components. Here we study the dynamical secular evolution of hierarchical triple systems undergoing mass loss. We use the secular evolution equations and include the effects of mass loss and mass transfer, as well as general relativistic effects. We present various evolutionary channels taking place in such evolving triples, and discuss both the effects of mass loss and mass transfer in the inner binary system, as well as the effects of mass loss/transfer from an outer third companion. We discuss several distinct types/regimes of triple secular evolution, where the specific behavior of a triple system can sensitively depend on its hierarchy and the relative importance of classical and general relativistic effects. We show that the orbital changes due to mass-loss and/or mass-transfer processes can effectively transfer a triple system from one dynamical regime to another. In particular, mass loss/transfer can both induce and quench high-amplitude (Lidov-Kozai) variations in the eccentricity and inclination of the inner binaries of evolving triples. They can also change the system dynamics from an orderly periodic behavior to a chaotic one, and vice versa.

  10. Internal mass transfer in hollow fiber supported liquid membranes

    SciTech Connect

    Urtiaga, A.M.; Irabien, J.A. )

    1993-03-01

    The study of mass transfer in hollow fiber supported liquid membranes is justified by a large number of separation processes. The analysis starts from the definition of an overall permeability coefficient which is a lumped parameter of a particular system and process conditions which gathers both mass transfer and operation parameters. By applying the film theory the contribution of the interfacial mass-transfer coefficient due to the inner boundary layer and the contribution of the supported liquid membrane permeability coefficient can be separated and analyzed. The study yields overall permeability coefficients that can be compared with those expected from hollow fiber design equations suggested earlier. The second approach considers the continuity mass conservation equation and the associated boundary conditions for the solute in the inner fluid. The analysis by means of the fundamental equations separates the effects of the operation variables such as the hydrodynamic conditions and length and diameter of the fibers from the mass-transfer properties of the system, described by the wall Sherwood number. The scope of the present work is to compare both methods of describing a hollow fiber supported liquid membrane module, analyzing the influence of the internal mass transfer on the design of such systems. In the experimental system under consideration, the simultaneous separation-concentration of phenol from aqueous solutions with hollow fiber supported liquid membrane modules is performed. The influence of the flow rate of the inner aqueous phase on the phenol separation rate has been studied.

  11. Numerical study on passive convective mass transfer enhancement

    NASA Astrophysics Data System (ADS)

    Aravind, G. P.; Muhammed Rafi, K. M.; Deepu, M.

    2017-04-01

    Passive mixing mechanisms are widely used for heat and mass transfer enhancement. Vortices generated in flowfield lead to gradients that favour convective mass transfer. Computations on enhancement of convective mass transfer of sublimating solid fuel by baroclinic torque generated vortices in the wake of a swept ramp placed in high speed flow is presented here. Advection Upstream Splitting Method (AUSM) based computational scheme employed in the present study, to solve compressible turbulent flow field involving species transport, could capture the complex flow features resulted by vortex boundary layer and shock boundary layer interactions. Convective mass transfer is found to get improved in regions near boundary layer by horseshoe vortex and further transported to other regions by counter rotating vortex pair. Vortices resulted by flow expansion near aft wall of wedge and recompression wave-boundary layer interactions also promotes convective mass transport. Extensive computations have been carried out to reveal the role of vortices dominance at various lateral sweep angles in promotion of convective mass transfer in turbulent boundary layer.

  12. Monolithic supports with unique geometries and enhanced mass transfer.

    SciTech Connect

    Stuecker, John Nicholas; Ferrizz, Robert Matthew; Cesarano, Joseph, III; Miller, James Edward

    2004-01-01

    The catalytic combustion of natural gas has been the topic of much research over the past decade. Interest in this technology results from a desire to decrease or eliminate the emissions of harmful nitrogen oxides (NOX) from gas turbine power plants. A low-pressure drop catalyst support, such as a ceramic monolith, is ideal for this high-temperature, high-flow application. A drawback to the traditional honeycomb monoliths under these operating conditions is poor mass transfer to the catalyst surface in the straight-through channels. 'Robocasting' is a unique process developed at Sandia National Laboratories that can be used to manufacture ceramic monoliths with alternative 3-dimensional geometries, providing tortuous pathways to increase mass transfer while maintaining low pressure drops. This report details the mass transfer effects for novel 3-dimensional robocast monoliths, traditional honeycomb-type monoliths, and ceramic foams. The mass transfer limit is experimentally determined using the probe reaction of CO oxidation over a Pt / {gamma}-Al{sub 2}O{sub 3} catalyst, and the pressure drop is measured for each monolith sample. Conversion versus temperature data is analyzed quantitatively using well-known dimensionless mass transfer parameters. The results show that, relative to the honeycomb monolith support, considerable improvement in mass transfer efficiency is observed for robocast samples synthesized using an FCC-like geometry of alternating rods. Also, there is clearly a trade-off between enhanced mass transfer and increased pressure drop, which can be optimized depending on the particular demands of a given application.

  13. Unsteady Mass transfer Across the Sediment-Water Interface

    NASA Astrophysics Data System (ADS)

    McCluskey, Alexander; Grant, Stanley; Stewardson, Michael

    2017-04-01

    Fluxes across the sediment-water interface (SWI) are of high ecological significance, as they promote biogeochemical processes that support benthic ecosystems within the hyporheic zone. The SWI marks a boundary between the turbulent water column (typically modelled by Navier Stokes equations) and the interstitial pore fluids in the sediment column, which are typically laminar (and modelled by Darcy's law). Although models of these two flow regimes are generally not coupled, flow in the turbulent boundary layer is affected by the sediment permeability and a slip velocity at the SWI, which decays exponentially into the streambed across a characteristic mixing length. Momentum is transferred across this region (known as the Brinkman layer) through the penetration of coherent structures and turbulent mixing, however, these turbulent structures also promote turbulent mass transfer. Mass transfer within the hyporheic zone can be conceptualised in terms of: (1) the downwelling of solutes from the stream; (2) retention of solutes in the sediment; and (3) the upwelling of solutes back into the stream. Recent work by the authors has shown that a mass transfer coefficient can be defined where a downwelling-upwelling unit cell exists across a concentration gradient. Such unit cells are generated at the SWI by pressure variation from: (1) steady-state influences, such as stream geometry and velocity variation; and (2) unsteady pressure waves produced by coherent turbulent structures. With this definition, mass transfer coefficients can be defined for: steady exchange, by adopting the Elliott and Brooks [1997] advective pumping model; and unsteady exchange, induced by streamwise propagation of upwelling-downwelling unit cells migrating downstream with a characteristic celerity associated with turbulent eddies. We hypothesize that beneath the Brinkman layer (where Laplace equation applies) these mass transfer coefficients can be summed to yield the total mass flux. Although, it

  14. Vortex-assisted liquid-liquid microextraction for the rapid screening of short-chain chlorinated paraffins in water.

    PubMed

    Chang, Chia-Yu; Chung, Wu-Hsun; Ding, Wang-Hsien

    2016-01-01

    The rapid screening of trace levels of short-chain chlorinated paraffins in various aqueous samples was performed by a simple and reliable procedure based on vortex-assisted liquid-liquid microextraction combined with gas chromatography and electron capture negative ionization mass spectrometry. The optimal vortex-assisted liquid-liquid microextraction conditions for 20 mL water sample were as follows: extractant 400 μL of dichloromethane; vortex extraction time of 1 min at 2500 × g; centrifugation of 3 min at 5000 × g; and no ionic strength adjustment. Under the optimum conditions, the limit of quantitation was 0.05 μg/L. Precision, as indicated by relative standard deviations, was less than 9% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was above 91%. The vortex-assisted liquid-liquid microextraction with gas chromatography and electron capture negative ionization mass spectrometry method was successfully applied to quantitatively extract short-chain chlorinated paraffins from samples of river water and the effluent of a wastewater treatment plant, and the concentrations ranged from 0.8 to 1.6 μg/L.

  15. Multicomponent NAPL source dissolution: evaluation of mass-transfer coefficients.

    PubMed

    Mobile, Michael A; Widdowson, Mark A; Gallagher, Daniel L

    2012-09-18

    Mass transfer rate coefficients were quantified by employing an inverse modeling technique to high-resolution aqueous phase concentration data observed following an experimental release of a multicomponent nonaqueous phase liquid (NAPL) at a field site. A solute transport model (SEAM3D) was employed to simulate advective-dispersive transport over time coupled to NAPL dissolution. Model calibration was demonstrated by accurately reproducing the observed breakthrough times and peak concentrations at multiple observation points, observed mass discharge at pumping wells, and the reported mass depletions for three soluble NAPL constituents. Vertically variable NAPL mass transfer coefficients were derived for each constituent using an optimized numerical solute transport model, ranging from 0.082 to 2.0 day(-1) across all constituents. Constituent-specific coefficients showed a positive correlation with liquid-phase diffusion coefficients. Application of a time-varying mass transfer coefficient as NAPL mass depleted showed limited sensitivity during which over 80% of the most soluble NAPL constituent dissolved from the source. Long-term simulation results, calibrated to the experimental data and rendered in terms of mass discharge versus source mass depletion, exhibited multistage behavior.

  16. Electroviscoelasticity of liquid/liquid interfaces: fractional-order model.

    PubMed

    Spasic, Aleksandar M; Lazarevic, Mihailo P

    2005-02-01

    A number of theories that describe the behavior of liquid-liquid interfaces have been developed and applied to various dispersed systems, e.g., Stokes, Reiner-Rivelin, Ericksen, Einstein, Smoluchowski, and Kinch. A new theory of electroviscoelasticity describes the behavior of electrified liquid-liquid interfaces in fine dispersed systems and is based on a new constitutive model of liquids. According to this model liquid-liquid droplet or droplet-film structure (collective of particles) is considered as a macroscopic system with internal structure determined by the way the molecules (ions) are tuned (structured) into the primary components of a cluster configuration. How the tuning/structuring occurs depends on the physical fields involved, both potential (elastic forces) and nonpotential (resistance forces). All these microelements of the primary structure can be considered as electromechanical oscillators assembled into groups, so that excitation by an external physical field may cause oscillations at the resonant/characteristic frequency of the system itself (coupling at the characteristic frequency). Up to now, three possible mathematical formalisms have been discussed related to the theory of electroviscoelasticity. The first is the tension tensor model, where the normal and tangential forces are considered, only in mathematical formalism, regardless of their origin (mechanical and/or electrical). The second is the Van der Pol derivative model, presented by linear and nonlinear differential equations. Finally, the third model presents an effort to generalize the previous Van der Pol equation: the ordinary time derivative and integral are now replaced with the corresponding fractional-order time derivative and integral of order p<1.

  17. Curvature dependence of the interfacial heat and mass transfer coefficients

    NASA Astrophysics Data System (ADS)

    Glavatskiy, K. S.; Bedeaux, D.

    2014-03-01

    Nucleation is often accompanied by heat transfer between the surroundings and a nucleus of a new phase. The interface between two phases gives an additional resistance to this transfer. For small nuclei the interfacial curvature is high, which affects not only equilibrium quantities such as surface tension, but also the transport properties. In particular, high curvature affects the interfacial resistance to heat and mass transfer. We develop a framework for determining the curvature dependence of the interfacial heat and mass transfer resistances. We determine the interfacial resistances as a function of a curvature. The analysis is performed for a bubble of a one-component fluid and may be extended to various nuclei of multicomponent systems. The curvature dependence of the interfacial resistances is important in modeling transport processes in multiphase systems.

  18. Limiting current technique in the research of mass/heat transfer in nanofluid

    NASA Astrophysics Data System (ADS)

    Wilk, J.; Grosicki, S.

    2016-09-01

    In the paper the authors focused on the application of the electrochemical limiting diffusion current technique to the study of mass transfer in nanofluid flow. As mass and heat transfer are analogical phenomena, analysing mass transfer helps understand heat transfer processes in nanofluids. The paper begins with a short review of the available literature on the subject followed by the authors' results of mass transfer coefficient measurements and the conclusions concerning mass/heat transfer enhancement in nanofluids.

  19. Agitating mass transfer with a warped disc's shadow

    NASA Astrophysics Data System (ADS)

    Cambier, H.

    2015-10-01

    For compact objects fed by Roche lobe overflow, accretion-generated X-rays irradiating the donor star can alter gas flow towards the Lagrange point thus varying mass transfer. The latest work specific to this topic consists of simple yet insightful two-dimensional hydrodynamics simulations stressing the role of global flow. To explore how a time-varying disc shadow affects mass transfer, I generalize the geometry, employ a robust hydrodynamics solver, and use phase space analysis near the nozzle to include coriolis lift there. Without even exposing the nozzle, a warped disc's shadow can drive mass transfer cycles by shifting the equatorial edges of the irradiation patches in turns: drawing in denser ambient gas before sweeping it into the nozzle. Other important effects remain missing in two-dimensional models, which I discuss along with prospects for more detailed yet efficient models.

  20. Heat and mass transfer analysis of a desiccant dehumidifier matrix

    SciTech Connect

    Pesaran, A.A.

    1986-07-01

    This report documents the SERI Single-Blow Test Facility's design, fabrication, and testing for characterizing desiccant dehumidifiers for solar cooling applications. The first test article, a silica-gel parallel-plate dehumidifier with highly uniform passages, was designed and fabricated. Transient heat and mass transfer data and pressure drop data across the dehumidifier were obtained. Available heat and mass transfer models were extended to the parallel-place geometry, and the experimental data were compared with model predictions. Pressure drop measurements were also compared with model predictions of the fully developed laminar flow theory. The comparisons between the lumped-capacitance model and the experimental data were satisfactory. The pressure drop data compared satisfactorily with the theory (within 15%). A solid-side resistance model that is more detailed and does not assume symmetrical diffusion in particles was recommended for performance. This study has increased our understanding of the heat and mass transfer in silica gel parallel-plate dehumidifiers.

  1. FEHM: finite element heat and mass transfer code

    SciTech Connect

    Zyvoloski, G.; Dash, Z.; Kelkar, S.

    1988-03-01

    The finite element heat and mass (FEHM) transfer code is a computer code developed to simulate geothermal and hot dry rock reservoirs. It is also applicable to natural-state studies of geothermal systems and ground-water flow. It solves the equations of heat and mass transfer for multiphase flow in porous and permeable media using the finite element method. The code also has provisions for a noncoupled tracer; that is, the tracer solutions do not affect the heat and mass transfer solutions. It can simulate two-dimensional, two-dimensional radial, or three-dimensional geometries. A summary of the equations in the model, the numerical solution procedure, and model verification and validation are provided in this report. A user's guide and sample problems are included in the appendices. 17 refs., 10 figs., 4 tabs.

  2. Liquid-liquid equilibria for ternary polymer mixtures

    NASA Astrophysics Data System (ADS)

    Oh, Suk Yung; Bae, Young Chan

    2011-01-01

    A molecular thermodynamic model for multicomponent systems based on a closed-packed lattice model is presented based on two contributions; entropy and energy contribution. The calculated liquid-liquid equilibria of ternary chainlike mixtures agreed with Monte Carlo simulation results. The proposed model can satisfactorily predict Types 0, 1, 2 and 3 phase separations of the Treybal classification. The model parameters obtained from the binary systems were used to directly predict real ternary systems and the calculated results correlated well with experimental data using few adjustable parameters. Specific interactions in associated binary systems were considered using a secondary lattice.

  3. Harnessing Poly(ionic liquid)s for Sensing Applications.

    PubMed

    Guterman, Ryan; Ambrogi, Martina; Yuan, Jiayin

    2016-07-01

    The interest in poly(ionic liquid)s for sensing applications is derived from their strong interactions to a variety of analytes. By combining the desirable mechanical properties of polymers with the physical and chemical properties of ILs, new materials can be created. The tunable nature of both ionic liquids and polymers allows for incredible diversity, which is exemplified in their broad applicability. In this article we examine the new field of poly(ionic liquid) sensors by providing a detailed look at the current state-of-the-art sensing devices for solvents, gases, biomolecules, pH, and anions.

  4. Ionic-liquid-based dispersive liquid-liquid microextraction combined with magnetic solid-phase extraction for the determination of aflatoxins B1 , B2 , G1 , and G2 in animal feeds by high-performance liquid chromatography with fluorescence detection.

    PubMed

    Zhao, Jiao; Zhu, Yan; Jiao, Yang; Ning, Jinyan; Yang, Yaling

    2016-10-01

    A novel two-step extraction technique combining ionic-liquid-based dispersive liquid-liquid microextraction with magnetic solid-phase extraction was developed for the preconcentration and separation of aflatoxins in animal feedstuffs before high-performance liquid chromatography coupled with fluorescence detection. In this work, ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate was used as the extractant in dispersive liquid-liquid microextraction, and hydrophobic pelargonic acid modified Fe3 O4 magnetic nanoparticles as an efficient adsorbent were applied to retrieve the aflatoxins-containing ionic liquid. Notably, the target of magnetic nanoparticles was the ionic liquid rather than the aflatoxins. Because of the rapid mass transfer associated with the dispersive liquid-liquid microextraction and magnetic solid phase steps, fast extraction could be achieved. The main parameters affecting the extraction recoveries of aflatoxins were investigated and optimized. Under the optimum conditions, vortexing at 2500 rpm for 1 min in the dispersive liquid-liquid microextraction and magnetic solid-phase extraction and then desorption by sonication for 2 min with acetonitrile as eluent. The recoveries were 90.3-103.7% with relative standard deviations of 3.2-6.4%. Good linearity was observed with correlation coefficients ranged from 0.9986 to 0.9995. The detection limits were 0.632, 0.087, 0.422 and 0.146 ng/mL for aflatoxins B1 , B2, G1, and G2, respectively. The results were also compared with the pretreatment method carried out by conventional immunoaffinity columns.

  5. Calculation of Mass Transfer Coefficients in a Crystal Growth Chamber through Heat Transfer Measurements

    SciTech Connect

    Bell, J H; Hand, L A

    2005-04-21

    The growth rate of a crystal in a supersaturated solution is limited by both reaction kinetics and the local concentration of solute. If the local mass transfer coefficient is too low, concentration of solute at the crystal-solution interface will drop below saturation, leading to a defect in the growing crystal. Here, mass transfer coefficients are calculated for a rotating crystal growing in a supersaturated solution of potassium diphosphate (KDP) in water. Since mass transfer is difficult to measure directly, the heat transfer coefficient of a scale model crystal in water is measured using temperature-sensitive paint (TSP). To the authors' knowledge this is the first use of TSP to measure temperatures in water. The corresponding mass transfer coefficient is then calculated using the Chilton- Colburn analogy. Measurements were made for three crystal sizes at two running conditions each. Running conditions include periodic reversals of rotation direction. Heat transfer coefficients were found to vary significantly both across the crystal faces and over the course of a rotation cycle, but not from one face to another. Mean heat transfer coefficients increased with both crystal size and rotation rate. Computed mass transfer coefficients were broadly in line with expectations from the full-scale crystal growth experiments. Additional experiments show that continuous rotation of the crystal results in about a 30% lower heat transfer compared to rotation with periodic reversals. The continuous rotation case also shows a periodic variation in heat transfer coefficient of about 15%, with a period about 1/20th of the rotation rate.

  6. Mass transfer and disc formation in AGB binary systems

    NASA Astrophysics Data System (ADS)

    Chen, Zhuo; Frank, Adam; Blackman, Eric G.; Nordhaus, Jason; Carroll-Nellenback, Jonathan

    2017-07-01

    We investigate mass transfer and the formation of discs in binary systems using a combination of numerical simulations and theory. We consider six models distinguished by binary separation, secondary mass and outflow mechanism. Each system consists of an asymptotic giant branch (AGB) star and an accreting secondary. The AGB star loses its mass via a wind. In one of our six models, the AGB star incurs a short period of outburst. In all cases, the secondary accretes part of the ejected mass and also influences the mass-loss rate of the AGB star. The ejected mass may remain gravitationally bound to the binary system and form a circumbinary disc, or contribute to an accretion disc around the secondary. In other cases, the ejecta will escape the binary system. The accretion rate on to the secondary changes non-linearly with binary separation. In our closest binary simulations, our models exemplify the wind Roche lobe overflow while in our wide binary cases, the mass transfer exhibits Bondi-Hoyle accretion. The morphologies of the outflows in the binary systems are varied. The variety may provide clues to how the late AGB phase influences planetary nebula shaping. We employ the adaptive-mesh-refinement code astrobear for our simulations and include ray tracing, radiation transfer, cooling and dust formation. To attain the highest computational efficiency and the most stable results, all simulations are run in the corotating frame.

  7. Analysis of mass transfer performance in an air stripping tower

    SciTech Connect

    Chung, T.W.; Lai, C.H.; Wu, H.

    1999-10-01

    The carryover of working solution in a traditional stripping tower is of serious concern in real applications. A U-shaped spray tower to prevent carryover has been designed to study the stripping of water vapor from aqueous desiccant solutions of 91.8 to 95.8 wt% triethylene glycol. In this study, water vapor was removed from the diluted desiccant solution by heating the solution and stripping it with the ambient air. Therefore, the solution was concentrated to a desired concentration. This spray tower was capable of handling air flow rates from 3.2 to 5.13 kg/min and liquid flow rates from 1.6 to 2.76 kg/min. Since the literature data on air stripping towers are limited, studies on the mass transfer coefficient and other mass transfer parameters were carried out in this study. Under the operating conditions, the overall mass transfer coefficient calculated from the experimental data varied from 0.053 to 0.169 mol/m{sup 3}{center{underscore}dot}s. These corresponded to heights of a transfer unit of 2.3 to 0.71 m, respectively. The rates of stripping in this spray tower were typically varied from 2.28 to 12.15 kg H{sub 2}O/h. A correlation of the mass transfer coefficient for the air stripping process was also developed in this study.

  8. Mass transfer apparatus and method for separation of gases

    SciTech Connect

    Blount, Gerald C.

    2015-10-13

    A process and apparatus for separating components of a source gas is provided in which more soluble components of the source gas are dissolved in an aqueous solvent at high pressure. The system can utilize hydrostatic pressure to increase solubility of the components of the source gas. The apparatus includes gas recycle throughout multiple mass transfer stages to improve mass transfer of the targeted components from the liquid to gas phase. Separated components can be recovered for use in a value added application or can be processed for long-term storage, for instance in an underwater reservoir.

  9. Solvent Extraction: Structure of the Liquid-Liquid Interface Containing a Diamide Ligand.

    PubMed

    Scoppola, Ernesto; Watkins, Erik B; Campbell, Richard A; Konovalov, Oleg; Girard, Luc; Dufrêche, Jean-Francois; Ferru, Geoffroy; Fragneto, Giovanna; Diat, Olivier

    2016-08-01

    Knowledge of the (supra)molecular structure of an interface that contains amphiphilic ligand molecules is necessary for a full understanding of ion transfer during solvent extraction. Even if molecular dynamics already yield some insight in the molecular configurations in solution, hardly any experimental data giving access to distributions of both extractant molecules and ions at the liquid-liquid interface exist. Here, the combined application of X-ray and neutron reflectivity measurements represents a key milestone in the deduction of the interfacial structure and potential with respect to two different lipophilic ligands. Indeed, we show for the first time that hard trivalent cations can be repelled or attracted by the extractant-enriched interface according to the nature of the ligand.

  10. Synergism by co-assembly at the origin of ion selectivity in liquid-liquid extraction

    SciTech Connect

    Dourdain, S.; Hofmeister, I.; Dufreche, J.F.; Turgis, R.; Pellet-Rostaing, S.; Zemb, T.; Pecheur, O.; Leydier, A.; Jestin, J.; Testard, F.

    2012-08-15

    In liquid-liquid extraction, synergism emerges when for a defined formulation of the solvent phase, there is an increase of distribution coefficients for some cations in a mixture. To characterize the synergistic mechanisms, we determine the free energy of mixed co-assembly in aggregates. Aggregation in any point of a phase diagram can be followed not only structurally by SANS, SAXS, and SLS, but also thermodynamically by determining the concentration of monomers coexisting with reverse aggregates. Using the industrially used couple HDEHP/TOPO forming mixed reverse aggregates, and the representative couple U/Fe, we show that there is no peculiarity in the aggregates microstructure at the maximum of synergism. Nevertheless, the free energy of aggregation necessary to form mixed aggregates containing extracted ions in their polar core is comparable to the transfer free energy difference between target and nontarget ions, as deduced from the synergistic selectivity peak. (authors)

  11. Copper phthalocyanine films deposited by liquid-liquid interface recrystallization technique (LLIRCT).

    PubMed

    Patil, K R; Sathaye, S D; Hawaldar, R; Sathe, B R; Mandale, A B; Mitra, A

    2007-11-15

    The simple recrystallization process is innovatively used to obtain the nanoparticles of copper phthalocyanine by a simple method. Liquid-liquid interface recrystallization technique (LLIRCT) has been employed successfully to produce small sized copper phthalocyanine nanoparticles with diameter between 3-5 nm. The TEM-SAED studies revealed the formation of 3-5 nm sized with beta-phase dominated mixture of alpha and beta copper phthalocyanine nanoparticles. The XRD, SEM, and the UV-vis studies were further carried out to confirm the formation of copper phthalocyanine thin films. The cyclic voltametry (CV) studies conclude that redox reaction is totally reversible one electron transfer process. The process is attributed to Cu(II)/Cu(I) redox reaction.

  12. Emulsification at the Liquid/Liquid Interface: Effects of Potential, Electrolytes and Surfactants.

    PubMed

    Chowdhury, Mehrin; Kataky, Ritu

    2016-01-04

    Emulsification of oils at liquid/liquid interfaces is of fundamental importance across a range of applications, including detergency. Adsorption and partitioning of the anionic surface active ions at the interface between two immiscible solutions is known to cause predictable chaos at the transfer potential region of the surfactant. In this work, the phenomenon that leads to the chaotic behaviour shown by sodium dodecylbenzene sulfonate (SDBS) at the water/1,2-dichloroethane interface is applied to commercial surfactants and aqueous/glyceryl trioleate interface. Electrochemical methods, electrocapillary curves, optical microscopy and conductivity measurements demonstrated that at 1.5 mm of SDBS, surfactants are adsorbed at the interface and assemble into micelles, leading to interfacial instability. As the concentration of the anionic surfactant was enhanced to 8 and 13.4 mm, the Marangoni effect and the interfacial emulsification became more prominent. The chaotic behaviour was found to be dependent on the surfactant concentration and the electrolytes present.

  13. Flow-Dependent Mass Transfer May Trigger Endothelial Signaling Cascades

    PubMed Central

    Vandrangi, Prashanthi; Sosa, Martha; Shyy, John Y.-J.; Rodgers, Victor G. J.

    2012-01-01

    It is well known that fluid mechanical forces directly impact endothelial signaling pathways. But while this general observation is clear, less apparent are the underlying mechanisms that initiate these critical signaling processes. This is because fluid mechanical forces can offer a direct mechanical input to possible mechanotransducers as well as alter critical mass transport characteristics (i.e., concentration gradients) of a host of chemical stimuli present in the blood stream. However, it has recently been accepted that mechanotransduction (direct mechanical force input), and not mass transfer, is the fundamental mechanism for many hemodynamic force-modulated endothelial signaling pathways and their downstream gene products. This conclusion has been largely based, indirectly, on accepted criteria that correlate signaling behavior and shear rate and shear stress, relative to changes in viscosity. However, in this work, we investigate the negative control for these criteria. Here we computationally and experimentally subject mass-transfer limited systems, independent of mechanotransduction, to the purported criteria. The results showed that the negative control (mass-transfer limited system) produced the same trends that have been used to identify mechanotransduction-dominant systems. Thus, the widely used viscosity-related shear stress and shear rate criteria are insufficient in determining mechanotransduction-dominant systems. Thus, research should continue to consider the importance of mass transfer in triggering signaling cascades. PMID:22558132

  14. Simultaneous heat and mass transfer in a porous medium

    NASA Astrophysics Data System (ADS)

    Siang, H.

    1981-11-01

    Based upon the principle of irreversible thermodynamics, the macroscopic conservation laws of mass, momentum and energy, and equilibrium sorption of the porous concrete system, a set of basic equations for simultaneous mass and heat transfer is developed. An implicit finite difference technique is employed to solve this set of nonlinear partial differential equations. Numerical examples, using the theory developed, are illustrated to deepen the general understanding of the drying, thermal characteristics and related phenomena of hydrated concrete. The developed theoretical model is made nondimensional and an order of magnitude analysis is performed to elucidate the transport phenomenum of heat and mass occurring in a concrete body. In addition to diffusion, both the capillary and evaporation-condensation mechanisms, which are strongly affected by the topology of the porous concrete system, are important in the heat and mass transfer processes.

  15. A Simple Organic Solvent-Free Liquid-Liquid Microextraction Method for the Determination of Potentially Toxic Metals as 2-(5-Bromo-2-pyridylazo)-5-(diethylamino)phenol Complex from Food and Biological Samples.

    PubMed

    Barfi, Behruz; Rajabi, Maryam; Asghari, Alireza

    2016-04-01

    An organic solvent-free method was developed to extract some potentially toxic metals, as complexed with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol, from different real samples prior to their determination by microsampling flame atomic absorption spectrometry. The method, named ionic liquid-based ultrasound-enhanced air-assisted liquid-liquid microextraction (IL-USE-AALLME), is based upon withdrawing and pushing out a mixture of an aqueous sample and an IL (as the extraction solvent) for several times into a conical test tube using a single syringe, placed in an ultrasound bath (as the enhancing mass transfer agent) during the extraction process. Different effective parameters were studied, and at the optimized conditions, limits of detection, linear dynamic ranges, and enrichment factors were ranged from 0.9 to 2.2 μg L(-1), 3.0 to 1023 μg L(-1), and 20 ± 2 to 22 ± 2, respectively. After optimization, the method was successfully applied to determine Pb(2+), Cu(2+), Co(2+), Ni(2+), and Cr(3+) in different biological (hair and nail), vegetable (coriander, parsley, and tarragon), fruit juice (apple, orange, and peach), and water (tap, mineral, and wastewater) samples. The proposed method was compared with two other IL-based and disperser solvent-free methods (i.e., IL-based air-assisted liquid-liquid microextraction and IL-based ultrasound-assisted emulsification microextraction) to demonstrate its performance.

  16. The liquid-liquid phase transition in silicon revealed by snapshots of valence electrons.

    PubMed

    Beye, Martin; Sorgenfrei, Florian; Schlotter, William F; Wurth, Wilfried; Föhlisch, Alexander

    2010-09-28

    The basis for the anomalies of water is still mysterious. Quite generally tetrahedrally coordinated systems, also silicon, show similar thermodynamic behavior but lack--like water--a thorough explanation. Proposed models--controversially discussed--explain the anomalies as a remainder of a first-order phase transition between high and low density liquid phases, buried deeply in the "no man's land"--a part of the supercooled liquid region where rapid crystallization prohibits any experimental access. Other explanations doubt the existence of the phase transition and its first-order nature. Here, we provide experimental evidence for the first-order-phase transition in silicon. With ultrashort optical pulses of femtosecond duration we instantaneously heat the electronic system of silicon while the atomic structure as defined by the much heavier nuclear system remains initially unchanged. Only on a picosecond time scale the energy is transferred into the atomic lattice providing the energy to drive the phase transitions. With femtosecond X-ray pulses from FLASH, the free-electron laser at Hamburg, we follow the evolution of the valence electronic structure during this process. As the relevant phases are easily distinguishable in their electronic structure, we track how silicon melts into the low-density-liquid phase while a second phase transition into the high-density-liquid phase only occurs after the latent heat for the first-order phase transition has been transferred to the atomic structure. Proving the existence of the liquid-liquid phase transition in silicon, the hypothesized liquid-liquid scenario for water is strongly supported.

  17. Combined heat and mass transfer in absorption processes

    SciTech Connect

    Grossman, G.

    1982-01-01

    The approach to theoretical analysis of the combined heat and mass transfer process taking place in absorption systems is described. The two tranfer phenomena are strongly coupled here. The purpose of the analysis is to relate, quantitatively, the heat and mass transfer coefficients to the physical properties of the working fluids and to the geometry of the system. The preferred configuration is that of a falling film of liquid on a metallic surface which serves to transfer heat from the absorbent in contact with the vapor of the absorbate. The model developed may be solved for laminar, turbulent, or transition flow regimes. The results of the solution describe the development of the thermal and concentration boundary layers and the variation of the temperatures, concentrations, and heat and mass fluxes. These quantities in their normalized, dimensionless form depend on two characteristic parameters of the system: the Lewis number Le and the dimensionless heat of absorption lambda. The length in the direction of flow is normalized with respect to the Peclet number and the film thickness. Heat and mass transfer coefficients for the system were calculated. The Sherwood number for mass transfer from the vapor-liquid interface to the bulk of the film reaches a constant value of 3.63 with fully developed boundary layers for both the adiabatic and constant temperature wall. The Nusselt number for heat transfer from the interface to the bulk reaches under the same conditions values of 3.63 and 2.67 for the adiabatic and constant temperature wall, respectively. The Nusselt number for heat tranfer from the bulk to the wall reaches 1.60.

  18. Liquid/Liquid Interfacial Synthesis of a Click Nanosheet.

    PubMed

    Rapakousiou, Amalia; Sakamoto, Ryota; Shiotsuki, Ryo; Matsuoka, Ryota; Nakajima, Ukyo; Pal, Tigmansu; Shimada, Rintaro; Hossain, Amran; Masunaga, Hiroyasu; Horike, Satoshi; Kitagawa, Yasutaka; Sasaki, Sono; Kato, Kenichi; Ozawa, Takeaki; Astruc, Didier; Nishihara, Hiroshi

    2017-06-22

    A liquid/liquid interfacial synthesis is employed, for the first time, to synthesize a covalent two-dimensional polymer nanosheet. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) between a three-way terminal alkyne and azide at a water/dichloromethane interface generates a 1,2,3-triazole-linked nanosheet. The resultant nanosheet, with a flat and smooth texture, has a maximum domain size of 20 μm and minimum thickness of 5.3 nm. The starting monomers in the organic phase and the copper catalyst in the aqueous phase can only meet at the liquid/liquid interface as a two-dimensional reaction space; this allows them to form the two-dimensional polymer. The robust triazole linkage generated by irreversible covalent-bond formation allows the nanosheet to resist hydrolysis under both acidic and alkaline conditions, and to endure pyrolysis up to more than 300 °C. The coordination ability of the triazolyl group enables the nanosheet to act as a reservoir for metal ions, with an affinity order of Pd(2+) >Au(3+) >Cu(2+) . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Models for a liquid-liquid phase transition

    NASA Astrophysics Data System (ADS)

    Buldyrev, S. V.; Franzese, G.; Giovambattista, N.; Malescio, G.; Sadr-Lahijany, M. R.; Scala, A.; Skibinsky, A.; Stanley, H. E.

    2002-02-01

    We use molecular dynamics simulations to study two- and three-dimensional models with the isotropic double-step potential which in addition to the hard core has a repulsive soft core of larger radius. Our results indicate that the presence of two characteristic repulsive distances (hard core and soft core) is sufficient to explain liquid anomalies and a liquid-liquid phase transition, but these two phenomena may occur independently. Thus liquid-liquid transitions may exist in systems like liquid metals, regardless of the presence of the density anomaly. For 2D, we propose a model with a specific set of hard core and soft core parameters, that qualitatively reproduces the phase diagram and anomalies of liquid water. We identify two solid phases: a square crystal (high density phase), and a triangular crystal (low density phase) and discuss the relation between the anomalies of liquid and the polymorphism of the solid. Similarly to real water, our 2D system may have the second critical point in the metastable liquid phase beyond the freezing line. In 3D, we find several sets of parameters for which two fluid-fluid phase transition lines exist: the first line between gas and liquid and the second line between high-density liquid (HDL) and low-density liquid (LDL). In all cases, the LDL phase shows no density anomaly in 3D. We relate the absence of the density anomaly with the positive slope of the LDL-HDL phase transition line.

  20. Optofluidic router based on tunable liquid-liquid mirrors.

    PubMed

    Müller, Philipp; Kopp, Daniel; Llobera, Andreu; Zappe, Hans

    2014-02-21

    We present an electrically tunable 1 × 5 optofluidic router for on-chip light routing. The device can redirect light from an optical input channel into five output channels by exploiting total internal reflection (TIR) at a liquid-liquid interface. The liquid-liquid mirrors, demonstrated for the first time, are tuned using integrated electrowetting-on-dielectrics (EWOD) actuators. The router is assembled from two chips fabricated by standard MEMS techniques. Through a combination of microfluidic with micro-optical components on chip, reliable light routing is achieved with switching times of [1.5-3.3] s, efficiencies of coupling into channels of up to 12%, optical cross-talk as low as -24 dB, a required drive voltage of 50 V, and a low power consumption of <5 mW, using a device 12 × 13 × 2 mm(3) in size. The optofluidic approach enables addressing of multiple channels over a broad wavelength range. Such optical routing capabilities are important for lab-on-chip devices focusing on optical spectroscopy, optical detection, or even optical manipulation. When integrated with external light sources and a low-cost disposable photonic lab-on-a-chip, the router could thus lead to novel laboratory measurement systems.

  1. Understanding the liquid-liquid (water-hexane) interface

    NASA Astrophysics Data System (ADS)

    Murad, Sohail; Puri, Ishwar K.

    2017-10-01

    Nonequilibrium molecular dynamics simulations are employed to investigate the interfacial thermal resistance of nanoscale hexane-water interfaces subject to an applied heat flux. Our studies show that these liquid-liquid interfaces exhibit behavior significantly dissimilar to that of solid-liquid and solid-vapor interfaces. Notably, the thermal resistance of a hexane-water interface is contingent on the interfacial temperature gradient alone with negligible dependence on the mean interfacial temperature, while the solid-liquid dependent strongly on the interfacial temperature. Application of a heat flux also increases the interface thickness significantly as compared to an equilibrium isothermal interface. Since liquid-liquid interfaces have been proposed for diverse applications, e.g., sensors for wastewater treatment and for extraction of toxic ions from water, they can be designed to be wider by applying a heat flux. This may allow the interface to be used for other applications not possible currently because of the very limited thickness of the interface in isothermal systems.

  2. N-body Simulation of Binary Star Mass Transfer

    NASA Astrophysics Data System (ADS)

    Hutyra, Taylor; Sumpter, William

    2017-01-01

    Over 70% of the stars in our galaxy are multiple star systems, many of which are two stars that orbit around a common center of mass. The masses of the individual stars can be found using Newton’s and Kepler’s Laws. This allows astronomers to use these systems as astrophysical laboratories to study properties and processes of stars and galaxies. Among the many types observed, the dynamics of contact systems are the most interesting because they exhibit mass transfer, which changes the composition and function of both stars. The process by which this mass exchange takes place is not well understood. The lack of extensive mass transfer analysis, inadequate theoretical models, and the large time scale of this process are reasons for our limited understanding. In this work, a model was made to give astronomers a method for gaining a deeper knowledge and visual intuition of how the mass transfer between binary stars takes place. We have built the foundations for a simulation of arbitrary systems, which we plan to elaborate on in the future to include thermodynamics and nuclear processes.

  3. TWIN BINARIES: STUDIES OF STABILITY, MASS TRANSFER, AND COALESCENCE

    SciTech Connect

    Lombardi, J. C.; Holtzman, W.; Gearity, K.; Dooley, K. L.; Kalogera, V.; Rasio, F. A.

    2011-08-20

    Motivated by suggestions that binaries with almost equal-mass components ('twins') play an important role in the formation of double neutron stars and may be rather abundant among binaries, we study the stability of synchronized close and contact binaries with identical components in circular orbits. In particular, we investigate the dependency of the innermost stable circular orbit on the core mass, and we study the coalescence of the binary that occurs at smaller separations. For twin binaries composed of convective main-sequence stars, subgiants, or giants with low-mass cores (M{sub c} {approx}< 0.15M, where M is the mass of a component), a secular instability is reached during the contact phase, accompanied by a dynamical mass transfer instability at the same or at a slightly smaller orbital separation. Binaries that come inside this instability limit transfer mass gradually from one component to the other and then coalesce quickly as mass is lost through the outer Lagrangian points. For twin giant binaries with moderate to massive cores (M{sub c} {approx}> 0.15M), we find that stable contact configurations exist at all separations down to the Roche limit, when mass shedding through the outer Lagrangian points triggers a coalescence of the envelopes and leaves the cores orbiting in a central tight binary. In addition to the formation of binary neutron stars, we also discuss the implications of our results for the production of planetary nebulae with double degenerate central binaries.

  4. Multiscale computations of mass accumulation effect on mass transfer in bubbly flow

    NASA Astrophysics Data System (ADS)

    Aboulhasanzadeh, Bahman; Tryggvason, Gretar

    2014-11-01

    Mass transfer in bubbly flow generally takes place on a much smaller length and time scale than the length and time scale of the momentum flow, resulting in a thin mass boundary layer around the bubbles. We developed a multiscale model to solve a boundary layer equation for the mass boundary layer next to the bubble interface, assuming zero mass concentration in the far field, which couples with the rest of domain using a source/sink term. Here, we extend our model to account for non-zero concentration next to the mass boundary layer. Comparison of simple case studies in 1D and 2D problems show good agreement between the fully resolved solution and the solution on a much coarser grid using our model. We study the effect of mass accumulation in a domain and also the effect of bubble moving into the wake of another bubble on the mass transfer. This study was funded by NSF Grant CBET-1132410.

  5. Geoelectrical Measurement of Multi-Scale Mass Transfer Parameters

    SciTech Connect

    Day-Lewis, Frederick; Singha, Kamini; Haggerty, Roy; Johnson, Tim; Binley, Andrew; Lane, John

    2014-01-16

    Mass transfer affects contaminant transport and is thought to control the efficiency of aquifer remediation at a number of sites within the Department of Energy (DOE) complex. An improved understanding of mass transfer is critical to meeting the enormous scientific and engineering challenges currently facing DOE. Informed design of site remedies and long-term stewardship of radionuclide-contaminated sites will require new cost-effective laboratory and field techniques to measure the parameters controlling mass transfer spatially and across a range of scales. In this project, we sought to capitalize on the geophysical signatures of mass transfer. Previous numerical modeling and pilot-scale field experiments suggested that mass transfer produces a geoelectrical signature—a hysteretic relation between sampled (mobile-domain) fluid conductivity and bulk (mobile + immobile) conductivity—over a range of scales relevant to aquifer remediation. In this work, we investigated the geoelectrical signature of mass transfer during tracer transport in a series of controlled experiments to determine the operation of controlling parameters, and also investigated the use of complex-resistivity (CR) as a means of quantifying mass transfer parameters in situ without tracer experiments. In an add-on component to our grant, we additionally considered nuclear magnetic resonance (NMR) to help parse mobile from immobile porosities. Including the NMR component, our revised study objectives were to: 1. Develop and demonstrate geophysical approaches to measure mass-transfer parameters spatially and over a range of scales, including the combination of electrical resistivity monitoring, tracer tests, complex resistivity, nuclear magnetic resonance, and materials characterization; and 2. Provide mass-transfer estimates for improved understanding of contaminant fate and transport at DOE sites, such as uranium transport at the Hanford 300 Area. To achieve our objectives, we implemented a 3

  6. Dissociation and Mass Transfer Coefficients for Ammonia Volatilization Models

    USDA-ARS?s Scientific Manuscript database

    Process-based models are being used to predict ammonia emissions from manure sources, but their accuracy has not been fully evaluated for cattle manure. Laboratory trials were conducted to measure the dissociation and mass transfer coefficients for ammonia volatilization from media of buffered ammon...

  7. Atmospheric composition affects heat- and mass-transfer processes

    NASA Technical Reports Server (NTRS)

    Blakely, R. L.; Nelson, W. G.

    1970-01-01

    For environmental control system functions sensitive to atmospheric composition, components are test-operated in helium-oxygen and nitrogen-oxygen mixtures, pure oxygen, and air. Transient heat- and mass-transfer tests are conducted for carbon dioxide adsorption on molecular sieve and for water vapor adsorption on silica gel.

  8. Transient natural convection heat and mass transfer in crystal growth

    NASA Technical Reports Server (NTRS)

    Han, Samuel S.

    1988-01-01

    A numerical analysis of transient combined heat and mass transfer across a rectangular cavity is performed by a numerical method based on the SIMPLE algorithm. The physical parameters are selected to represent a range of possible crystal growth in solutions. Numerical results are compared with available experimental data to confirm the accuracy of the results. Good qualitative agreements are obtained for the average mass transfer rate across the cavity. Also, qualitative agreements are observed for the global development of thermal and solute fields. It is found that the thermal and solute fields become highly oscillatory when the thermal and solute Grashof numbers are large. Oscillations are probably caused by a number of different instability mechanisms. By reducing the gravity some of these instabilities were made to disappear at the lower Grashof numbers. Transient temperature and solute distribution near the crystal growing surface are highly non-uniform at the higher Grashof numbers. These non-uniformities are less severe in the reduced gravity environments but still exist. The effects of convection on the rate of average mass transfer are more than one order of magnitude higher than those of conduction in the range of Grashof numbers studied. Dependency of mass transfer rate on the Grashof number indicates that the convection effects many not be negligible even in the microgravity environments for the range of parameters investigated.

  9. A Course in Advanced Topics in Heat and Mass Transfer.

    ERIC Educational Resources Information Center

    Shaeiwitz, Joseph A.

    1983-01-01

    A three or four semester-hour graduate course was designed to provide basic instruction in heat/mass transfer topics relevant to chemical engineering problems and to train students to develop mathematical descriptions for new situations encountered in problem-solving. Course outline and list of references used in the course are provided. (JM)

  10. Transient natural convection heat and mass transfer in crystal growth

    NASA Technical Reports Server (NTRS)

    Han, Samuel S.

    1990-01-01

    A numerical analysis of transient combined heat and mass transfer across a rectangular cavity is performed. The physical parameters are selected to represent a range of possible crystal growth in solutions. Good agreements with measurement data are observed. It is found that the thermal and solute fields become highly oscillatory when the thermal and solute Grashof numbers are large.

  11. Laser ablation sample transfer for mass spectrometry imaging.

    PubMed

    Park, Sung-Gun; Murray, Kermit K

    2015-01-01

    Infrared laser ablation sample transfer (IR-LAST) is a novel ambient sampling technique for mass spectrometry. In this technique, a pulsed mid-IR laser is used to ablate materials that are collected for mass spectrometry analysis; the material can be a solid sample or deposited on a sample target. After collection, the sample can be further separated or analyzed directly by mass spectrometry. For IR-LAST sample transfer tissue imaging using MALDI mass spectrometry, a tissue section is placed on a sample slide and material transferred to a target slide by scanning the tissue sample under a focused laser beam using transmission-mode (back side) IR laser ablation. After transfer, the target slide is analyzed using MALDI imaging. The spatial resolution is approximately 400 μm and limited by the spread of the laser desorption plume. IR-LAST for MALDI imaging provides several new capabilities including ambient sampling, area to spot concentration of ablated material, multiple ablation and analysis from a single section, and direct deposition on matrix-free nanostructured targets.

  12. A Course in Advanced Topics in Heat and Mass Transfer.

    ERIC Educational Resources Information Center

    Shaeiwitz, Joseph A.

    1983-01-01

    A three or four semester-hour graduate course was designed to provide basic instruction in heat/mass transfer topics relevant to chemical engineering problems and to train students to develop mathematical descriptions for new situations encountered in problem-solving. Course outline and list of references used in the course are provided. (JM)

  13. Interphase mass transfer between fluids in subsurface formations: A review

    NASA Astrophysics Data System (ADS)

    Agaoglu, Berken; Copty, Nadim K.; Scheytt, Traugott; Hinkelmann, Reinhard

    2015-05-01

    This paper presents a review of the state-of-the-art on interphase mass transfer between immiscible fluids in porous media with focus on the factors that have significant influence on this process. In total close to 300 papers were reviewed focusing to a large extent on the literature relating to NAPL contamination of the subsurface. The large body of work available on this topic was organized according to the length scale of the conducted studies, namely the pore, meso and field scales. The interrelation of interphase mass transfer at these different scales is highlighted. To gain further insight into interphase mass transfer, published studies were discussed and evaluated in terms of the governing flow configurations defined in terms of the wettability and mobility of the different phases. Such organization of the existing literature enables the identification of the interfacial domains that would have significant impact on interphase mass transfer. Available modeling approaches at the various length scales are discussed with regard to current knowledge on the physics of this process. Future research directions are also suggested.

  14. LUT observations of the mass-transferring binary AI Dra

    NASA Astrophysics Data System (ADS)

    Liao, Wenping; Qian, Shengbang; Li, Linjia; Zhou, Xiao; Zhao, Ergang; Liu, Nianping

    2016-06-01

    Complete UV band light curve of the eclipsing binary AI Dra was observed with the Lunar-based Ultraviolet Telescope (LUT) in October 2014. It is very useful to adopt this continuous and uninterrupted light curve to determine physical and orbital parameters of the binary system. Photometric solutions of the spot model are obtained by using the W-D (Wilson and Devinney) method. It is confirmed that AI Dra is a semi-detached binary with secondary component filling its critical Roche lobe, which indicates that a mass transfer from the secondary component to the primary one should happen. Orbital period analysis based on all available eclipse times suggests a secular period increase and two cyclic variations. The secular period increase was interpreted by mass transfer from the secondary component to the primary one at a rate of 4.12 ×10^{-8}M_{⊙}/yr, which is in agreement with the photometric solutions. Two cyclic oscillations were due to light travel-time effect (LTTE) via the presence of two cool stellar companions in a near 2:1 mean-motion resonance. Both photometric solutions and orbital period analysis confirm that AI Dra is a mass-transferring binary, the massive primary is filling 69 % of its critical Roche lobe. After the primary evolves to fill the critical Roche lobe, the mass transfer will be reversed and the binary will evolve into a contact configuration.

  15. Evaporation from flowing channels ( mass-transfer formulas).

    USGS Publications Warehouse

    Fulford, J.M.; Sturm, T.W.

    1984-01-01

    Stability-dependent and Dalton-type mass transfer formulas are determined from experimental evaporation data in ambient and heated channels and are shown to have similar performance in prediction of evaporation. The formulas developed are compared with those proposed by other investigators for lakes and flowing channels. -from ASCE Publications Information

  16. Turbulent mass transfer in the furnace of high output boilers

    SciTech Connect

    Noskievic, P.; Kolat, P.; Novacek, A.

    1995-12-31

    The up-to-date identification methods for the evaluation of combustion process quality provide a picture of what is taking place in the furnace. The Energetics Department of VSB-TU Ostrava concentrates its attention on untraditional methods which proceed from an analysis of turbulent transfer phenomena, especially the transfer of mass in the furnace of pulverized boilers. Particularly in the region of burners, this mass transfer influences the quality of the combustion process as well as the formation of solid and gaseous emissions. Measurements of combustion aerodynamics in the furnace of high output boilers are part of the Czech Clean Coal Technology program. A complex approach to these problems could lead to a decrease of pollutants released.

  17. Heat and Mass Transfer Model in Freeze-Dried Medium

    NASA Astrophysics Data System (ADS)

    Alfat, Sayahdin; Purqon, Acep

    2017-07-01

    There are big problems in agriculture sector every year. One of the major problems is abundance of agricultural product during the peak of harvest season that is not matched by an increase in demand of agricultural product by consumers, this causes a wasted agricultural products. Alternative way was food preservation by freeze dried method. This method was already using heat transfer through conduction and convection to reduce water quality in the food. The main objective of this research was to design a model heat and mass transfer in freeze-dried medium. We had two steps in this research, the first step was design of medium as the heat injection site and the second was simulate heat and mass transfer of the product. During simulation process, we use physical property of some agriculture product. The result will show how temperature and moisture distribution every second. The method of research use finite element method (FEM) and will be illustrated in three dimensional.

  18. Modelling of heat and mass transfer processes in neonatology.

    PubMed

    Ginalski, Maciej K; Nowak, Andrzej J; Wrobel, Luiz C

    2008-09-01

    This paper reviews some of our recent applications of computational fluid dynamics (CFD) to model heat and mass transfer problems in neonatology and investigates the major heat and mass transfer mechanisms taking place in medical devices such as incubators and oxygen hoods. This includes novel mathematical developments giving rise to a supplementary model, entitled infant heat balance module, which has been fully integrated with the CFD solver and its graphical interface. The numerical simulations are validated through comparison tests with experimental results from the medical literature. It is shown that CFD simulations are very flexible tools that can take into account all modes of heat transfer in assisting neonatal care and the improved design of medical devices.

  19. Performance Characterization of a Microchannel Liquid/Liquid Heat Exchanger Throughout an Extended Duration Life Test

    NASA Technical Reports Server (NTRS)

    Sheth, Rubik B.; Stephan, Ryan A.; Hawkins-Reynolds Ebony

    2011-01-01

    Liquid/Liquid Heat Exchangers (L/L HX) are an integral portion of any spacecraft active thermal control system. For this study the X-38 L/L HX was used as a baseline. As detailed in a previous ICES manuscript, NASA paired with Pacific Northwest National Laboratory to develop a Microchannel L/L HX (MHX). This microchannel HX was designed to meet the same performance characteristics as the aforementioned X-38 HX. The as designed Microchannel HX has a 26% and 60% reduction in mass and volume, respectively. Due to the inherently smaller flow passages the design team was concerned about fouling affecting performance during extended missions. To address this concern, NASA has developed a test stand and is currently performing an 18 month life test on the MHX. This report will detail the up-to-date performance of the MHX during life testing.

  20. Dispersive liquid-liquid microextraction of phenolic compounds from vegetable oils using a magnetic ionic liquid.

    PubMed

    Zhu, Shuqiang; Wang, Lijun; Su, Along; Zhang, Haixia

    2017-08-01

    A novel method was developed for the determination of two endocrine-disrupting chemicals, bisphenol A and 4-nonylphenol, in vegetable oil by dispersive liquid-liquid microextraction followed by ultra high performance liquid chromatography with tandem mass spectrometry. Using a magnetic liquid as the microextraction solvent, several key parameters were optimized, including the type and volume of the magnetic liquid, extraction time, amount of dispersant, and the type of reverse extractant. The detection limits for bisphenol A and 4-nonylphenol were 0.1 and 0.06 μg/kg, respectively. The recoveries were 70.4-112.3%, and the relative standard deviations were less than 4.2%. The method is simple for the extraction of bisphenol A and 4-nonylphenol from vegetable oil and suitable for routine analysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. CFD simulation on the turbulent mixing flow performance of the liquid-liquid ejector

    NASA Astrophysics Data System (ADS)

    An, W. Z.; Bie, H. Y.; Liu, C. C.; Hao, Z. R.

    2016-05-01

    In order to study the flow performance of the liquid-liquid ejector, 3D ejector simulation models were established to investigate the influences of suction angle, suction number and working condition on the ejector performance. The simulation results showed that when the suction angle was 60°, the total pressure was in equilibrium state. The double suction ejector would induced more vortexes in the suction chamber than that of the single suction ejector, and the turbulent intensity of the fluid inside the ejector was bigger, however, it also caused much more loss in energy. When the working pressure was lower than 0.6 MPa, the liquid entrainment ratio increased rapidly. Once the working pressure reached 0.6 MPa, the liquid entrainment ratio basically remained unchanged. The mass flow rate of the suction medium increased with the increasing of suction pressure, and the differential pressure between the suction pressure and the working pressure at the nozzle also increased simultaneously.

  2. [Determination of sildenafil and vardenafil in human plasma by high performance liquid chromatography coupled with liquid-liquid-liquid microextraction].

    PubMed

    Zhang, Zhaohui; Kang, Shaoying; Xu, Minjie; Ma, Ming; Chen, Bo; Yao, Shouzhuo

    2005-07-01

    High performance liquid chromatography coupled with liquid-liquid-liquid microextraction was developed for the simultaneous determination of sildenafil and vardenafil in human plasma. The effects of extraction solvent, the volume of organic solvent, dropsize of acceptor phase, stirring rate and extraction time on the enrichment factors of analytes were investigated. The optimized experimental conditions, 300 microL toluene as the organic phase, 2 microL 0.2 mol/L HCl as the acceptor phase, 600 r/min of the stirring rate, and 40 min of the extraction time, were gotten. Under these conditions, high enrichment factors were obtained. The linear range of studied analytes was from 5 microg/L to 1.0 mg/L. The relative standard deviation was lower than 5%. The limits of detection were 1 microg/L for sildenafil and 0.5 microg/L for vardenafil at signal-to-noise ratio of 3. The method with little solvent consumption may provide high analyte preconcentration and excellent sample clean-up, and it is a sensitive and suitable method for simultaneous determination of the above two substances in human plasma.

  3. Mass and heat transfer model of Tubular Solar Still

    SciTech Connect

    Ahsan, Amimul; Fukuhara, Teruyuki

    2010-07-15

    In this paper, a new mass and heat transfer model of a Tubular Solar Still (TSS) was proposed incorporating various mass and heat transfer coefficients taking account of the humid air properties inside the still. The heat balance of the humid air and the mass balance of the water vapor in the humid air were formulized for the first time. As a result, the proposed model enabled to calculate the diurnal variations of the temperature, water vapor density and relative humidity of the humid air, and to predict the hourly condensation flux besides the temperatures of the water, cover and trough, and the hourly evaporation flux. The validity of the proposed model was verified using the field experimental results carried out in Fukui, Japan and Muscat, Oman in 2008. The diurnal variations of the calculated temperatures and water vapor densities had a good agreement with the observed ones. Furthermore, the proposed model can predict the daily and hourly production flux precisely. (author)

  4. V794 Aql: evolution at high mass transfer rate

    NASA Astrophysics Data System (ADS)

    Orio, Marina

    2014-09-01

    V794 Aql, a VYScl or nova-like star in which a white dwarf, accretes at very high mass transfer rate mdot (~10(-8) solar masses) from a main sequence binary companion. Very few interacting white dwarf binaries show clear physical manifestation of such high mass transfer rate, which is very important to understand how recurrent novae and type I supernovae occur. Periodic "low states" at all wavelengths from optical to X-rays can be explained with a limit cycle that regulates the mdot through a physical mechanisms that could be due to a number of root causes: irradiation induced wind from the secondary and its periodic halt, spots on the secondary, the magnetic field of the WD. We propose to obtain a HETG spectrum that will clarify how these systems evolve.

  5. Fem Formulation for Heat and Mass Transfer in Porous Medium

    NASA Astrophysics Data System (ADS)

    Azeem; Soudagar, Manzoor Elahi M.; Salman Ahmed, N. J.; Anjum Badruddin, Irfan

    2017-08-01

    Heat and mass transfer in porous medium can be modelled using three partial differential equations namely, momentum equation, energy equation and mass diffusion. These three equations are coupled to each other by some common terms that turn the whole phenomenon into a complex problem with inter-dependable variables. The current article describes the finite element formulation of heat and mass transfer in porous medium with respect to Cartesian coordinates. The problem under study is formulated into algebraic form of equations by using Galerkin's method with the help of two-node linear triangular element having three nodes. The domain is meshed with smaller sized elements near the wall region and bigger size away from walls.

  6. Transport phenomena of crystal growth—heat and mass transfer

    NASA Astrophysics Data System (ADS)

    Rudolph, Peter

    2010-07-01

    Selected fundamentals of transport processes and their importance for crystal growth are given. First, principal parameters and equations of heat and mass transfer, like thermal flux, radiation and diffusion are introduced. The heat- and mass- balanced melt-solid and solution-solid interface velocities are derived, respectively. The today's significance of global numeric simulation for analysis of thermo-mechanical stress and related dislocation dynamics within the growing crystal is shown. The relation between diffusion and kinetic regime is discussed. Then, thermal and solutal buoyancy-driven and Marangoni convections are introduced. Their important interplay with the diffusion boundary layer, component and particle incorporation as well as morphological interface stability is demonstrated. Non-steady crystallization phenomena (striations) caused by convective fluctuations are considered. Selected results of global 3D numeric modeling are shown. Finally, advanced methods to control heat and mass transfer by external forces, such as accelerated container rotation, ultrasonic vibration and magnetic fields are discussed.

  7. Modeling liquid-liquid phase transitions and quasicrystal formation

    NASA Astrophysics Data System (ADS)

    Skibinsky, Anna

    In this thesis, studies which concern two different subjects related to phase transitions in fluids and crystalline solids are presented. Condensed matter formation, structure, and phase transitions are modeled using molecular dynamics simulations of simple discontinuous potentials with attractive and repulsive interactions. Novel phase diagrams are proposed for quasicrystals, crystals, and liquids. In the first part of the thesis, the formation of a quasicrystal in a two dimensional monodisperse system is investigated using molecular dynamics simulations of hard sphere particles interacting via a two-dimensional square-well potential. It is found that for certain values of the square-well parameters more than one stable crystalline phase can form. By quenching the liquid phase at a very low temperature, an amorphous phase is obtained. When this the amorphous phase is heated, a quasicrystalline structure with five-fold symmetry forms. From estimations of the Helmholtz potentials of the stable crystalline phases and of the quasicrystal, it is concluded that within a specific temperature range, the observed quasicrystal phase can be the stable phase. The second part of the thesis concerns a study of the liquid-liquid phase transition for a single-component system in three dimensions, interacting via an isotropic potential with a repulsive soft-core shoulder at short distance and an attractive well at an intermediate distance. The potential is similar to potentials used to describe such liquid systems as colloids, protein solutions, or liquid metals. It is shown that the phase diagram for such a potential can have two lines of first-order fluid-fluid phase transitions: one separating a gas and a low-density liquid (LDL), and another between the LDL and a high-density liquid (HDL). Both phase transition lines end in a critical point, a gas-LDL critical point and, depending on the potential parameters, either a gas-HDL critical point or a LDL-HDL critical point. A

  8. Dispersive liquid-liquid microextraction combined with microwave-assisted derivatization for determining lipoic acid and its metabolites in human urine.

    PubMed

    Tsai, Chia-Ju; Chen, Yen-Ling; Feng, Chia-Hsien

    2013-10-04

    This study explored dispersive liquid-liquid microextraction for extraction and concentration of lipoic acid in human urine. To improve the detection of lipoic acid by both capillary liquid chromatography (CapLC) with UV detection and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS), microwave-assisted derivatization with 4-bromomethyl-6,7-dimethoxycoumarin was performed to render lipoic acid chromophores for UV detection and also high ionization efficiency in MALDI. All parameters that affected lipoic acid extraction and derivatization from urine were investigated and optimized. In the analyses of human urine samples, the two methods had a linear range of 0.1-20 μM with a correlation coefficient of 0.999. The detection limits of CapLC-UV and MALDI-TOF MS were 0.03 and 0.02 μM (S/N ≧ 3), respectively. The major metabolites of lipoic acid, including 6,8-bismethylthio-octanoic acid, 4,6-bismethylthio-hexanoic acid, and 2,4-bismethylthio-butanoic acid were also extracted by dispersive liquid-liquid microextraction and detected by MALDI-TOF MS. The minor metabolites (undetectable by MALDI-TOF MS), bisnorlipoic acid and tetranorlipoic acid were also extracted by dispersive liquid-liquid microextraction and identified with an LTQ Orbitrap mass spectrometer. After dispersive liquid-liquid microextraction and microwave-assisted derivatization, all lipoic acid derivatizations and metabolites were structurally confirmed by LTQ Orbitrap.

  9. Simultaneous convective heat and mass transfer in impingement ink drying

    SciTech Connect

    Can, M.

    1998-08-01

    Effective and economical drying of thin ink films is essential in the printing, packaging and coating industries. In evaporative drying, high heat and mass transfer rates are commonly achieved by means of high velocity impinging air jets. To provide data for dryer design a program of research has been implemented to study the heat and mass transfer processes which underlie the drying of thin ink films. The heat transfer situation under impinging air jets is outlined and some experimental results are presented. Optimization of nozzle arrays for impinging air jets is analyzed for practical applications. A non-contact infra-red technique for continuously monitoring the ink drying process is described and drying curves for an ink based on a single solvent (4-Methyl-2-pentanol-MIBC) are presented. Heat and mass transfer theory has been used to predict drying times in the constant rate drying period. These predictions have been compared with experimentally determined drying times. This research has served to confirm the fundamental importance of the drying curve as a basis for dryer design.

  10. Overall Heat and Mass Transfer Coefficient of Water Vapor Adsorption

    NASA Astrophysics Data System (ADS)

    Hamamoto, Yoshinori; Mori, Hideo; Godo, Masazumi; Miura, Kunio; Watanabe, Yutaka; Ishizawa, Toshihiko; Takatsuka, Takeshi

    A fundamental investigation was performed to develop a compact and simple desiccant ventilation unit which is one of the main components of a novel energy saving air-conditioning system. Water vapor in the air is adsorbed and/or desorbed to be controlled the humidity of supply air through a unit of an adsorbent rotor. A numerical simulation helps to understand the phenomena of heat and mass transfer in the rotor block. Overall transfer coefficients were estimated by performing both experiment and calculation. It was examined that the transient overall equivalent heat and mass transfer coefficient was not constant. It seems that both film fluid and diffusion resistance govern the coefficients in the block, and the influence of air flow on the time averaged coefficients is estimated by a considering the laminar forced convection from a flat plate. There is little difference of the coefficient between adsorption and desorption process. The correlation and fitting parameters are presented for prediction of the overall heat and mass transfer coefficients. The estimation accuracy was improved.

  11. Highly pressurized partially miscible liquid-liquid flow in a micro-T-junction. I. Experimental observations

    NASA Astrophysics Data System (ADS)

    Qin, Ning; Wen, John Z.; Ren, Carolyn L.

    2017-04-01

    This is the first part of a two-part study on a partially miscible liquid-liquid flow (liquid carbon dioxide and deionized water) which is highly pressurized and confined in a microfluidic T-junction. Our main focuses are to understand the flow regimes as a result of varying flow conditions and investigate the characteristics of drop flow distinct from coflow, with a capillary number, C ac , that is calculated based on the continuous liquid, ranging from 10-3 to 10-2 (10-4 for coflow). Here in part I, we present our experimental observation of drop formation cycle by tracking drop length, spacing, frequency, and after-generation speed using high-speed video and image analysis. The drop flow is chronologically composed of a stagnating and filling stage, an elongating and squeezing stage, and a truncating stage. The common "necking" time during the elongating and squeezing stage (with C ac˜10-3 ) for the truncation of the dispersed liquid stream is extended, and the truncation point is subsequently shifted downstream from the T-junction corner. This temporal postponement effect modifies the scaling function reported in the literature for droplet formation with two immiscible fluids. Our experimental measurements also demonstrate the drop speed immediately following their generations can be approximated by the mean velocity from averaging the total flow rate over the channel cross section. Further justifications of the quantitative analysis by considering the mass transfer at the interface of the two partially miscible fluids are provided in part II.

  12. Mass Transfer via Low Velocity Impacts into Regolith

    NASA Astrophysics Data System (ADS)

    Jarmak, Stephanie; Colwell, Josh E.; Brisset, Julie; Dove, Adrienne

    2016-10-01

    The study of low velocity collisions (<1 m/s) is essential to understand the growth and formation of aggregates in a number of environments in planetary systems. The Collisions Into Dust Experiment (COLLIDE) and Physics of Regolith Impacts in Microgravity Experiment (PRIME) experiments produced observations of mass transfer from regolith onto an impactor at these velocities in microgravity. We have subsequently carried out ground-based experiments in which a cm-scale sphere impacts and rebounds from a bed of granular material in 1-g laboratory conditions at low impact speeds with the aid of a spring. This allows impacts at v<1 m/s and ensures rebound of the impactor, with the spring providing enough force to overcome gravity. Preliminary results from an impact of a brass impactor into sand (200-500 μm) produced a monolayer of granular material onto the impactor, but the grains are not cohesive enough to allow a significant mass transfer under these conditions. Further experiments with a range of regolith properties, impactor composition and surface properties, impact velocities, and atmospheric conditions will be performed in the laboratory to study the effects of each of these properties on the contact transfer of regolith onto the impactor. Further microgravity experiments with PRIME and in a small drop tower are planned to then study bulk mass transfer with conditions informed by the ground-based experiments. Impacts with the COLLIDE and PRIME microgravity experiments showed mass transfer at speeds < 40 cm/s into JSC-1 lunar regolith simulant and quartz sand targets. We will present the free-fall and laboratory results and implications for the collisional evolution of dust, pebbles and boulders in the protoplanetary disk as well as particles in planetary ring systems.

  13. Solidification of floating organic droplet in dispersive liquid-liquid microextraction as a green analytical tool.

    PubMed

    Mansour, Fotouh R; Danielson, Neil D

    2017-08-01

    Dispersive liquid-liquid microextraction (DLLME) is a special type of microextraction in which a mixture of two solvents (an extracting solvent and a disperser) is injected into the sample. The extraction solvent is then dispersed as fine droplets in the cloudy sample through manual or mechanical agitation. Hence, the sample is centrifuged to break the formed emulsion and the extracting solvent is manually separated. The organic solvents commonly used in DLLME are halogenated hydrocarbons that are highly toxic. These solvents are heavier than water, so they sink to the bottom of the centrifugation tube which makes the separation step difficult. By using solvents of low density, the organic extractant floats on the sample surface. If the selected solvent such as undecanol has a freezing point in the range 10-25°C, the floating droplet can be solidified using a simple ice-bath, and then transferred out of the sample matrix; this step is known as solidification of floating organic droplet (SFOD). Coupling DLLME to SFOD combines the advantages of both approaches together. The DLLME-SFOD process is controlled by the same variables of conventional liquid-liquid extraction. The organic solvents used as extractants in DLLME-SFOD must be immiscible with water, of lower density, low volatility, high partition coefficient and low melting and freezing points. The extraction efficiency of DLLME-SFOD is affected by types and volumes of organic extractant and disperser, salt addition, pH, temperature, stirring rate and extraction time. This review discusses the principle, optimization variables, advantages and disadvantages and some selected applications of DLLME-SFOD in water, food and biomedical analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Electrovariable gold nanoparticle films at liquid-liquid interfaces: from redox electrocatalysis to Marangoni-shutters.

    PubMed

    Gschwend, Grégoire C; Smirnov, Evgeny; Peljo, Pekka; Girault, Hubert H

    2017-07-01

    Control over the physical properties of nanoparticle assemblies at a liquid-liquid interface is a key technological advancement to realize the dream of smart electrovariable nanosystems. Electrified interfaces, such as the interface between two immiscible electrolytes solutions (ITIES), are almost an ideal platform for realizing this dream. Here, we show that the Galvani potential difference across soft interfaces can be effectively used to manipulate: (i) the reactivity of gold nanoparticle assemblies through varying the Fermi level (both chemically and electrochemically); (ii) the location distribution of the nanoparticles at the liquid-liquid interface. In the first case, in addition to our previous studies on electron transfer reactions (ET) across the ITIES, we used intensity modulated photocurrent spectroscopy (IMPS) to study the kinetics of photo-induced electrochemical reactions at the ITIES. As expected, the direct adsorption of gold nanoparticles at the interface modifies the kinetics of the ET reaction (so-called, interfacial redox electrocatalysis), however it did not lead to an increased photocurrent by "plasmonic enhancement". Rather, we found that the product separation depends on double layer effects while the product recombination is controlled by the Galvani potential difference between the two phases. In the second case, we demonstrated that polarizing the ITIES caused migration of gold nanoparticles from the middle region of the cell to its periphery. We called such systems "Marangoni-type shutters". This type of electrovariable plasmonic system did not experience diffusion limitation in terms of the adsorption/desorption of nanoparticles and the entire movement of nanoparticle assemblies happened almost instantly (within a second). It opens a fresh view on electrovariable plasmonics and presents new opportunities to create smart nanosystems at the ITIES driven with an electric field.

  15. Evaporative Mass Transfer Behavior of a Complex Immiscible Liquid

    PubMed Central

    McColl, Colleen M.; Johnson, Gwynn R.; Brusseau, Mark L.

    2010-01-01

    A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult’s law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium. PMID:18614196

  16. Evaporative mass transfer behavior of a complex immiscible liquid.

    PubMed

    McColl, Colleen M; Johnson, Gwynn R; Brusseau, Mark L

    2008-09-01

    A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult's law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium.

  17. Heat and mass transfer in porous cavity: Assisting flow

    SciTech Connect

    Badruddin, Irfan Anjum; Quadir, G. A.

    2016-06-08

    In this paper, investigation of heat and mass transfer in a porous cavity is carried out. The governing partial differential equations are non-dimensionalised and solved using finite element method. The left vertical surface of the cavity is maintained at constant temperature and concentration which are higher than the ambient temperature and concentration applied at right vertical surface. The top and bottom walls of the cavity are adiabatic. Heat transfer is assumed to take place by natural convection and radiation. The investigation is carried out for assisting flow when buoyancy and gravity force act in same direction.

  18. Rates of mass, momentum, and energy transfer at the magnetopause

    NASA Technical Reports Server (NTRS)

    Hill, T. W.

    1979-01-01

    Empirical estimates of the global rates of transfer of solar wind mass, tangential momentum, and energy at the Earth's magnetopause are presented for comparison against model estimates based on the four principal mechanisms that have been proposed to explain such transfer. The comparisons, although not quite conclusive, strongly favor a model that incorporates some combination of direct magnetic connection and anomalous cross field diffusion. An additional global constraint, the rate at which magnetic flux is cycled through the magnetospheric convection system, strongly suggests that direct magnetic connection plays a significant if not dominant role in the solar wind/magnetosphere interaction.

  19. Recent developments in dispersive liquid-liquid microextraction.

    PubMed

    Saraji, Mohammad; Boroujeni, Malihe Khalili

    2014-03-01

    During the past 7 years and since the introduction of dispersive liquid-liquid microextraction (DLLME), the method has gained widespread acceptance as a simple, fast, and miniaturized sample preparation technique. Owing to its simplicity of operation, rapidity, low cost, high recovery, and low consumption of organic solvents and reagents, it has been applied for determination of a vast variety of organic and inorganic compounds in different matrices. This review summarizes the DLLME principles, historical developments, and various modes of the technique, recent trends, and selected applications. The main focus is on recent technological advances and important applications of DLLME. In this review, six important aspects in the development of DLLME are discussed: (1) the type of extraction solvent, (2) the type of disperser solvent, (3) combination of DLLME with other extraction methods, (4) automation of DLLME, (5) derivatization reactions in DLLME, and (6) the application of DLLME for metal analysis. Literature published from 2010 to April 2013 is covered.

  20. Deformation of liquid-liquid interfaces by a rotating rod

    NASA Astrophysics Data System (ADS)

    Zhao, C. W.; Gentric, C.; Dietrich, N.; Ma, Y. G.; Li, Huai Z.

    2017-07-01

    The present study aims at investigating the deformation mechanism of liquid-liquid interfaces by both the experimental and numerical approaches. The experiments reveal that the topology of an initial flat interface composed of Newtonian aqueous and Newtonian oil phases can be modulated as climbing or descending along a rotating rod according to the ratio of the kinematic viscosity between these two liquid phases. The measurements of the fluid flow fields by particle image velocimetry highlight the relationship between the appearance of the Taylor-Couette instability in the less viscous phase and the interface's orientation. The increasing rod rotation speed expands the Taylor-Couette vortices and then intensifies the magnitude of the interface deformation. The numerical simulation by the volume of fluid method is in qualitative agreement with the experimental results, in particular the interface shape and the qualitative influence of different parameters, even under very high rotation speeds of the rod.

  1. Liquid-liquid-solid transition in viscoelastic liquids

    PubMed Central

    Zubelewicz, Aleksander

    2013-01-01

    Liquid-liquid-solid transitions (LLST) are known to occur in confined liquids, exist in supercooled liquids and emerge in liquids driven from equilibrium. Molecular dynamics (MD) simulations claim many successes in forecasting the phenomena. The transitions are also studied in the framework of thermodynamics based methods and minimalistic models. In here, the proposed approach is derived in the framework of continuum and includes spatial and temporal dynamic heterogeneities; the approach is meant to capture the material behavior at small scales. We conjecture that the liquid-like and solid-like behaviors are dissimilar enough for the two to be governed by different constitutive relations. In this way, we gain additional degree of freedom, which is found essential when predicting the transitional phenomena. As a result, we derive the LLST criteria for liquids in equilibrium, during steady flow and at transient conditions. Lastly, we forecast short-lived LLSTs in human blood during cardiac cycle. PMID:23429528

  2. Thermal energy storage with liquid-liquid systems

    SciTech Connect

    Santana, E.A.; Stiel, L.I.

    1989-03-01

    The use of liquid-liquid mixtures for heat and cool storage applications has been investigated. Suitable mixtures exhibit large changes in the heat of mixing above and below the critical solution temperature of the system. Analytical procedures have been utilized to determine potential energy storage capabilities of systems with upper or lower critical solution temperatures. It has been found that aqueous systems with lower critical solution temperatures in a suitable range can result in large increases in the effective heat capacity in the critical region. For cool storage with a system of this type, the cooling process results in a transformation from two liquid phases to a single phase. Heats of mixing have been measured with a flow calorimeter system for a number of potential mixtures, and the results are summarized.

  3. Liquid-Liquid Phase Transition in Nanoconfined Silicon Carbide.

    PubMed

    Wu, Weikang; Zhang, Leining; Liu, Sida; Ren, Hongru; Zhou, Xuyan; Li, Hui

    2016-03-02

    We report theoretical evidence of a liquid-liquid phase transition (LLPT) in liquid silicon carbide under nanoslit confinement. The LLPT is characterized by layering transitions induced by confinement and pressure, accompanying the rapid change in density. During the layering transition, the proportional distribution of tetracoordinated and pentacoordinated structures exhibits remarkable change. The tricoordinated structures lead to the microphase separation between silicon (with the dominant tricoordinated, tetracoordinated, and pentacoordinated structures) and carbon (with the dominant tricoordinated structures) in the layer close to the walls. A strong layer separation between silicon atoms and carbon atoms is induced by strong wall-liquid forces. Importantly, the pressure confinement phase diagram with negative slopes for LLPT lines indicates that, under high pressure, the LLPT is mainly confinement-induced, but under low pressure, it becomes dominantly pressure-induced.

  4. Microrheology and Particle Dynamics at Liquid-Liquid Interfaces

    NASA Astrophysics Data System (ADS)

    Song, Yanmei

    The rheological properties at liquid-liquid interfaces are important in many industrial processes such as manufacturing foods, pharmaceuticals, cosmetics, and petroleum products. This dissertation focuses on the study of linear viscoelastic properties at liquid-liquid interfaces by tracking the thermal motion of particles confined at the interfaces. The technique of interfacial microrheology is first developed using one- and two-particle tracking, respectively. In one-particle interfacial microrheology, the rheological response at the interface is measured from the motion of individual particles. One-particle interfacial microrheology at polydimethylsiloxane (PDMS) oil-water interfaces depends strongly on the surface chemistry of different tracer particles. In contrast, by tracking the correlated motion of particle pairs, two-particle interfacial microrheology significantly minimizes the effects from tracer particle surface chemistry and particle size. Two-particle interfacial microrheology is further applied to study the linear viscoelastic properties of immiscible polymer-polymer interfaces. The interfacial loss and storage moduli at PDMS-polyethylene glycol (PEG) interfaces are measured over a wide frequency range. The zero-shear interfacial viscosity, estimated from the Cross model, falls between the bulk viscosities of two individual polymers. Surprisingly, the interfacial relaxation time is observed to be an order of magnitude larger than that of the PDMS bulk polymers. To explore the fundamental basis of interfacial nanorheology, molecular dynamics (MD) simulations are employed to investigate the nanoparticle dynamics. The diffusion of single nanoparticles in pure water and low-viscosity PDMS oils is reasonably consistent with the prediction by the Stokes-Einstein equation. To demonstrate the potential of nanorheology based on the motion of nanoparticles, the shear moduli and viscosities of the bulk phases and interfaces are calculated from single

  5. Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

    2010-08-01

    Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system

  6. Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

    2010-05-01

    Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of the phase diagram. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation

  7. Chiral interactions of the drug propranolol and α1-acid-glycoprotein at a micro liquid-liquid interface.

    PubMed

    Lopes, Paula; Kataky, Ritu

    2012-03-06

    The investigation of chiral interactions of drugs with plasma proteins is of fundamental importance for drug efficacy and toxicity studies. In this paper, we demonstrate a simple liquid-liquid interface procedure for investigating chiral interactions. Chiral discrimination of the enantiomers of a basic drug, propranolol, was achieved at a micro liquid-liquid interface, using α(1)-acid-glycoprotein (AGP) as a chiral acute phase plasma protein. When the protein is added to an aqueous phase containing the enantiomers of propranalol hydrochloride, the binding of (S)- and (R)-propranolol hydrochloride to the protein results in a decrease in the cyclic voltammetry (CV) and differential pulse voltammetry (DPV) current responses corresponding to the decrease in transfer of propranolol at an aqueous-1,2-dichloroethane interface. This decrease is a consequence of the complexation of the drug and the protein. The complex drug-protein does not transfer across the interface nor changes the transfer potential of the uncomplexed form of propranolol enantiomers. The bound concentration of propranolol enantiomers in the presence of AGP was found to be greater for (S)-propranolol than (R)-propranolol for solutions containing constant concentrations of AGP (50 μM). Scatchard analysis yielded association constants of 2.7 and 1.3 × 10(5) M(-1) for (S)- and (R)-propranolol, respectively.

  8. The role of curvature effects in liquid-liquid extraction: assessing organic phase mesoscopic properties from MD simulations.

    PubMed

    Duvail, Magali; van Damme, Steven; Guilbaud, Philippe; Chen, Yushu; Zemb, Thomas; Dufrêche, Jean-François

    2017-08-23

    The bending rigidity of small reverse aggregates involved in liquid-liquid extraction processes has been investigated by molecular dynamics simulations. Simulations of a common extractant (DMDOHEMA) with four hydrophobic chains in explicit solvent (n-heptane) and in vacuum have been performed to determine the effect of solvent penetration on film stiffness. Elastic film bending energy that is needed for mesoscopic modelling of transfer of species between complex fluids is harmonic in terms of curvature (Helfrich formalism) and the packing parameter only if the solvent is explicitly taken into account. In terms of the packing parameter of the real molecular film constituting the reverse water in oil aggregates and taking into account molecular volume, area and film thickness (that is in agreement with Tanford's model), the bending rigidity is calculated to be about 16 kBT per extractant molecule (about 40 kJ mol(-1)), which is smaller than the free energy of transfer from an isolated "monomer" molecule to a weak aggregate, but of the order of magnitude of the free energy of transfer used in liquid-liquid extraction processes.

  9. Blood flow and mass transfer regulation of coagulation

    PubMed Central

    Rana, Kuldeepsinh; Neeves, Keith B.

    2016-01-01

    Blood flow regulates coagulation and fibrin formation by controlling the transport, or mass transfer, of zymogens, co-factors, enzymes, and inhibitors to, from, and within a growing thrombus. The rate of mass transfer of these solutes relative to their consumption or production by coagulation reactions determines, in part, the rate of thrombin generation, fibrin deposition, and thrombi growth. Experimental studies on the influence of blood flow on specific coagulation reactions are reviewed here, along with a theoretical framework that predicts how flow influences surface-bound coagulation binding and enzymatic reactions. These flow-mediated transport mechanisms are also used to interpret the role of binding site densities and injury size on initiating coagulation and fibrin deposition. The importance of transport of coagulation proteins within the interstitial spaces of thrombi is shown to influence thrombi architecture, growth, and arrest. PMID:27133256

  10. Chemical separations by bubble-assisted interphase mass-transfer.

    PubMed

    Boyd, David A; Adleman, James R; Goodwin, David G; Psaltis, Demetri

    2008-04-01

    We show that when a small amount of heat is added close to a liquid-vapor interface of a captive gas bubble in a microchannel, interphase mass-transfer through the bubble can occur in a controlled manner with only a slight change in the temperature of the fluid. We demonstrate that this method, which we refer to as bubble-assisted interphase mass-transfer (BAIM), can be applied to interphase chemical separations, e.g., simple distillation, without the need for high temperatures, vacuum, or active cooling. Although any source of localized heating could be used, we illustrate BAIM with an all-optical technique that makes use of the plasmon resonance in an array of nanoscale metal structures that are incorporated into the channel to produce localized heating of the fluid when illuminated by a stationary low-power laser.

  11. Geoelectrical inference of mass transfer parameters using temporal moments

    USGS Publications Warehouse

    Day-Lewis, F. D.; Singha, K.

    2008-01-01

    We present an approach to infer mass transfer parameters based on (1) an analytical model that relates the temporal moments of mobile and bulk concentration and (2) a bicontinuum modification to Archie's law. Whereas conventional geochemical measurements preferentially sample from the mobile domain, electrical resistivity tomography (ERT) is sensitive to bulk electrical conductivity and, thus, electrolytic solute in both the mobile and immobile domains. We demonstrate the new approach, in which temporal moments of collocated mobile domain conductivity (i.e., conventional sampling) and ERT-estimated bulk conductivity are used to calculate heterogeneous mass transfer rate and immobile porosity fractions in a series of numerical column experiments. Copyright 2008 by the American Geophysical Union.

  12. Mass-transfer in close binary and their companions

    NASA Astrophysics Data System (ADS)

    Liao, Wenping; Qian, Shengbang; Zhu, Liying; Li, Linjia

    2016-07-01

    Secular and/or cyclical orbital period variations of close binaries can be derived by analyzing the (O-C) diagram. The secular variations are usually explained as mass transfer between components, while the most plausible explanation of the cyclic period changes is the light-travel time effect (LTTE) through the presence of a third body. Mass transfer and additional companions in close binary systems are important for understanding the formation and evolution of the systems. Here, UV light curves of several close binaries based on the Lunar-based Ultraviolet Telescope (LUT) observations are presented and analyzed with the Wilson-Devinney (W-D) method. Then, based on those light-curve solutions and new analysis of the orbital period variations, the multiplicity, geometrical structure and evolution state of targets are discussed.

  13. Modelling mass transfer during venting/soil vapour extraction: Non-aqueous phase liquid/gas mass transfer coefficient estimation

    NASA Astrophysics Data System (ADS)

    Esrael, D.; Kacem, M.; Benadda, B.

    2017-07-01

    We investigate how the simulation of the venting/soil vapour extraction (SVE) process is affected by the mass transfer coefficient, using a model comprising five partial differential equations describing gas flow and mass conservation of phases and including an expression accounting for soil saturation conditions. In doing so, we test five previously reported quations for estimating the non-aqueous phase liquid (NAPL)/gas initial mass transfer coefficient and evaluate an expression that uses a reference NAPL saturation. Four venting/SVE experiments utilizing a sand column are performed with dry and non-saturated sand at low and high flow rates, and the obtained experimental results are subsequently simulated, revealing that hydrodynamic dispersion cannot be neglected in the estimation of the mass transfer coefficient, particularly in the case of low velocities. Among the tested models, only the analytical solution of a convection-dispersion equation and the equation proposed herein are suitable for correctly modelling the experimental results, with the developed model representing the best choice for correctly simulating the experimental results and the tailing part of the extracted gas concentration curve.

  14. Vaporization of Graphitic Materials at High Mass Transfer Rates

    DTIC Science & Technology

    1976-03-01

    graphite 2. Carbon sublimation 3. High temperature carbon response 4. Sublimation kinetics |ITR\\CT fCanllim an rararaa «14a II nacaaaair an« Htnlllr *r...8217»’» numbmi) iThe thermochemical sublimation response of ATJ-S graphite in both low and high mass transfer convective environments was studied... sublimation effects com- pared to JANAF equilibrium sublimation predictions. Extrapolation of the inferred kinetic sublimation effects to the high

  15. Mass transfer ways of ultraviolet printing ink ingredients into foodstuffs.

    PubMed

    Jung, T; Simat, T J; Altkofer, W

    2010-07-01

    The case of isopropylthioxanthone (ITX) showed conclusively that the ingredients of ultraviolet printing inks may migrate into packaged foodstuffs. For multilayered materials like beverage cartons, the only way that mass transfer can occur is by the so-called set-off effect. In contrast, in the case of rigid plastics like yoghurt cups, two other methods of mass transfer, permeation and gas phase, have to be considered. In cooperation with producers of ink, plastic cups and yoghurt, a project was conducted in order to elucidate the mass transfer of ink ingredients. In addition, the influence of storage time and the age of ultraviolet lamps on the migration level was examined. The suitability of 50% ethanol as a simulant for yoghurt was also tested. ITX was chosen as a model migrant, as it is easily detectable. Furthermore, the migration of two other substances, the photo-initiator 2-methyl-4'-(methylthio)-2-morpholinopropiophenone (MTMP) and the amine synergist ethyl-4-(dimethylamino)benzoate (EDAB), which may be used in combination with ITX, was studied. Before being filled with yoghurt or 50% ethanol, the printed cups were stored under different contact conditions, with and without contact between the inner layer and the printed surfaces, in order to distinguish between the possible mass transfer ways. All analyses were performed by means of high performance liquid chromatography with diode array and fluorescence detection (HPLC-DAD/FLD). It was shown that contamination with ITX and EDAB occurs via set-off and that the degree of migration increases with lamp age and storage time of the unfilled cups. Migration of MTMP was not detectable. The results show that besides the careful selection of the appropriate raw materials for printing ink, a close monitoring of the process also plays a major role in migration control. In addition, the results proved that 50% ethanol is a suitable simulant for yoghurt.

  16. Heat and mass transfer in volcano-hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Scott, S. W.

    2015-12-01

    Hydrothermal systems re-distribute heat and mass derived from subsurface magma bodies over large temporal and spatial scales. Numerical models of fluid flow and heat transfer provide a quantitative basis for understanding the thermo-hydrological structure and transient behavior of volcano-hydrothermal systems. At the brittle-ductile transition around a magma body, the rate of conductive heat transfer from the impermeable intrusion is balanced by the rate of advective heat transfer by the fluid. Using the Complex Systems Modeling Platform (CSMP++) to model fluid flow up to near-magmatic conditions, we examine the effect of geologic factors such as host rock permeability, magma emplacement depth, the temperature conditions of the brittle-ductile transition, and rock/magma thermal conductivity on the rates of heat and mass transfer around magma bodies. Additionally, we investigate the role of these factors on the thermo-hydrological structure of the hydrothermal system, including patterns of phase separation, gravity-driven phase segregation, and fluid mixing. Passive tracers are included in the fluid flow models to simulate the input of magmatic volatiles into hydrothermal fluids and their fractionation between the liquid and vapor phases. Ultimately, we compare our model results against measured heat and gas fluxes from volcano-hydrothermal systems to help inform the interpreation of these measurements.

  17. Combined heat and mass transfer device for improving separation process

    DOEpatents

    Tran, T.N.

    1999-08-24

    A two-phase small channel heat exchange matrix simultaneously provides for heat transfer and mass transfer between the liquid and vapor phases of a multi-component mixture at a single, predetermined location within a separation column, significantly improving the thermodynamic efficiency of the separation process. The small channel heat exchange matrix is composed of a series of channels having a hydraulic diameter no greater than 5.0 millimeters for conducting a two-phase coolant. In operation, the matrix provides the liquid-vapor contacting surfaces within the separation column, such that heat and mass are transferred simultaneously between the liquid and vapor phases. The two-phase coolant allows for a uniform heat transfer coefficient to be maintained along the length of the channels and across the surface of the matrix. Preferably, a perforated, concave sheet connects each channel to an adjacent channel to facilitate the flow of the liquid and vapor phases within the column and to increase the liquid-vapor contacting surface area. 12 figs.

  18. Combined heat and mass transfer device for improving separation process

    DOEpatents

    Tran, Thanh Nhon

    1999-01-01

    A two-phase small channel heat exchange matrix simultaneously provides for heat transfer and mass transfer between the liquid and vapor phases of a multi-component mixture at a single, predetermined location within a separation column, significantly improving the thermodynamic efficiency of the separation process. The small channel heat exchange matrix is composed of a series of channels having a hydraulic diameter no greater than 5.0 millimeters for conducting a two-phase coolant. In operation, the matrix provides the liquid-vapor contacting surfaces within the separation column, such that heat and mass are transferred simultaneously between the liquid and vapor phases. The two-phase coolant allows for a uniform heat transfer coefficient to be maintained along the length of the channels and across the surface of the matrix. Preferably, a perforated, concave sheet connects each channel to an adjacent channel to facilitate the flow of the liquid and vapor phases within the column and to increase the liquid-vapor contacting surface area.

  19. Mass transfer controlled by fracturing in micritic carbonate rocks

    NASA Astrophysics Data System (ADS)

    Richard, James; Coulon, Michel; Gaviglio, Patrick

    2002-05-01

    The fractured Coniacian chalk from the Omey area (Paris Basin, France) displays strong evidence of modifications controlled by brittle deformation. Fracturing is associated with important changes in pore space (decrease in total porosity and pore interconnection, change in distribution of pore access diameters and capillary characteristics), nannofacies (gradual evolution from a point-contact fabric to a welded, interlocked or coalescent fabric) and chemical composition (Sr concentration decrease). These modifications result from fluid-rock interaction that control significant mass transfer (percentage of secondary calcite >50%). Sr is a remarkable indicator of these mass transfers. Sr analyses allowed us to prove that the deformed zone (26.7 m) is wider than the fractured zone (11.3 m). They also indicate that the footwall block is less affected than the hanging wall block. A physicochemical model of the deformation mechanism is proposed. It shows that a cyclic process of fracturing controls the temporal evolution of the fluid saturation and fluid pressure and, consequently, the mass transfer.

  20. Predicting heat and mass transfer in fractured porous media (Invited)

    NASA Astrophysics Data System (ADS)

    Geiger, S.; Cortis, A.; Emmanuel, S.

    2010-12-01

    Fractures are abundant in the subsurface and affect many relevant single- and multi-phase transport processes such as gas and oil extraction, contaminant transport, or geothermal reservoir engineering. However, making reliable predictions of heat and mass transfer in fractured porous media is an outstanding challenge due to its multi-scale nature and the orders-of-magnitude varations in transport rates. Direct high-resolution simulations provide fundamental insights into the local advective and diffusive transport processes in fractured porous media. However, this approach is intractable for inverse simulations because of its high computational requirements. Continuous Time Random Walks on the other hand are a viable alternative and general way to model heat and mass transfer in structurally complex and multi-scale geological media, particularly for inverse problems. But they do not offer the same insights into local transport processes as direct numerical simulations. Here we combine both approaches to simulate the detailed transport processes occurring during heat and mass transfer in fractured porous media and analyse how these affect the breakthrough curves used to calibrate the Continuous Time Random Walks. We show that heat transport in fractured porous media can be anomalous, i.e. characterised by early breakthrough and long tailing, like it is well known for solute transport. We also demonstrate that a careful analysis of the solute breakthrough curves can yield insights into the heterogeneity of the fracture pattern and the transport occurring between fracture and matrix as well as within the matrix and fractures.

  1. In-line coupled single drop liquid-liquid-liquid microextraction with capillary electrophoresis for determining fluoroquinolones in water samples.

    PubMed

    Springer, Valeria H; Lista, Adriana G

    2015-07-01

    A simple in-line single drop liquid-liquid-liquid microextraction (SD-LLLME) coupled with CE for the determination of two fluoroquinolones was developed. The method is capable to quantify trace amount of analytes in water samples and to improve the sensitivity of CE detection. For the SD-LLLME, a thin layer of organic phase was used to separate a drop of 0.1 M NaOH hanging at the inlet of the capillary from the aqueous donor phase. By this way, the analytes were extracted to the acceptor phase through the organic layer based on their acidic/basic dissociation equilibrium. The drop was immersed into the organic phase during 10 min for extraction and then it is directly injected into the capillary for the analysis. Parameters such as type and volume of organic solvent phase, aqueous donor, and acceptor phases and extraction time and temperature were optimized. The enrichment factor was calculated, resulting 40-fold for enrofloxacin (ENR) and sixfold for ciprofloxacin (CIP). The linear range were 20-400 μg/L for ENR and 60-400 μg/L for CIP. The detection limits were 10.1 μg/L and 55.3 μg/L for ENR and CIP, respectively, and a good reproducibility was obtained (4.4% for ENR and 5.6% for CIP). Two real water samples were analysed applying the new method and the obtained results presented satisfactory recovery percentages (90-100.3%). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Mass transfer model for two-layer TBP oxidation reactions

    SciTech Connect

    Laurinat, J.E.

    1994-09-28

    To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments. Three cases were investigated: (1) transfer of water into the TBP layer with sparging of both the aqueous and TBP layers, (2) transfer of water into the TBP layer with sparging of just the TBP layer, and (3) transfer of butanol into the aqueous layer with sparging of both layers. The TBP layer was comprised of 99% pure TBP (spiked with butanol for the butanol transfer experiments), and the aqueous layer was comprised of either water or an aluminum nitrate solution. The liquid layers were air sparged to simulate the mixing due to the evolution of gases generated by oxidation reactions. A plastic tube and a glass frit sparger were used to provide different size bubbles. Rates of mass transfer were measured using infrared spectrophotometers provided by SRTC/Analytical Development.

  3. Proton Transfer Time-of-Flight Mass Spectrometer

    SciTech Connect

    Watson, Thomas B

    2016-03-01

    The Proton Transfer Reaction Mass Spectrometer (PTRMS) measures gas-phase compounds in ambient air and headspace samples before using chemical ionization to produce positively charged molecules, which are detected with a time-of-flight (TOF) mass spectrometer. This ionization method uses a gentle proton transfer reaction method between the molecule of interest and protonated water, or hydronium ion (H3O+), to produce limited fragmentation of the parent molecule. The ions produced are primarily positively charged with the mass of the parent ion, plus an additional proton. Ion concentration is determined by adding the number of ions counted at the molecular ion’s mass-to-charge ratio to the number of air molecules in the reaction chamber, which can be identified according to the pressure levels in the reaction chamber. The PTRMS allows many volatile organic compounds in ambient air to be detected at levels from 10–100 parts per trillion by volume (pptv). The response time is 1 to 10 seconds.

  4. Mass transfer to blood flowing through arterial stenosis

    NASA Astrophysics Data System (ADS)

    Sarifuddin; Chakravarty, Santabrata; Mandal, Prashanta Kumar; Andersson, Helge I.

    2009-03-01

    The present investigation deals with a mathematical model representing the mass transfer to blood streaming through the arteries under stenotic condition. The mass transport refers to the movement of atherogenic molecules, that is, blood-borne components, such as oxygen and low-density lipoproteins from flowing blood into the arterial walls or vice versa. The blood flowing through the artery is treated to be Newtonian and the arterial wall is considered to be rigid having differently shaped stenoses in its lumen arising from various types of abnormal growth or plaque formation. The nonlinear unsteady pulsatile flow phenomenon unaffected by concentration-field of the macromolecules is governed by the Navier-Stokes equations together with the equation of continuity while that of mass transfer is controlled by the convection-diffusion equation. The governing equations of motion accompanied by appropriate choice of the boundary conditions are solved numerically by MAC(Marker and Cell) method and checked numerical stability with desired degree of accuracy. The quantitative analysis carried out finally includes the respective profiles of the flow-field and concentration along with their distributions over the entire arterial segment as well. The key factors like the wall shear stress and Sherwood number are also examined for further qualitative insight into the flow and mass transport phenomena through arterial stenosis. The present results show quite consistency with several existing results in the literature which substantiate sufficiently to validate the applicability of the model under consideration.

  5. Mass Transfer Model of Desulfurization in the Electroslag Remelting Process

    NASA Astrophysics Data System (ADS)

    Hou, Dong; Jiang, Zhou-Hua; Dong, Yan-Wu; Li, Yang; Gong, Wei; Liu, Fu-Bin

    2017-06-01

    Experimental and theoretical studies have been carried out to investigate the effects of the slag on desulfurization during the electroslag remelting (ESR) process with a focus of developing a mass transfer model to understand the mechanism of desulfurization. Stainless steel 1Cr21Ni5Ti was used as the electrode and remelted with two different kinds of slags using a 50-kg ESR furnace. The contents of sulfur along the axial direction of product ingots were analyzed. It was found that the sulfur content of 350 ppm in the electrode is reduced to 71 to 95 ppm in the ingot by remelting with the slag containing 5 wt pct of CaO, and lowered more to 47 to 59 ppm with another slag having 20 wt pct CaO. On the basis of the penetration and film theories, the theoretical model developed in this work well elucidates the kinetics of desulfurization revealing the mechanism of sulfur transfer during the ESR process. The calculation results obtained from the model agree well with the experimental results. The model indicates that when sulfur content in electrode is given, there is a corresponding minimum value of sulfur content in the ingot due to the kinetics limit. This lowest sulfur content cannot be further reduced even with increasing L S (sulfur distribution coefficient between metal and slag phases) or decreasing sulfur content in the slag. Constant addition of extra amount of CaO to the molten slag with the increase of sulfur content in the slag during the remelting process can improve the macrosegregation of sulfur distributed along the axial direction of ESR ingots. Since the rate-determining steps of the sulfur mass transfer lie in the metal phase, adding calcium as deoxidizer can change mass transfer of sulfur and thus promote desulfurization further during the ESR process.

  6. Mass Transfer Model of Desulfurization in the Electroslag Remelting Process

    NASA Astrophysics Data System (ADS)

    Hou, Dong; Jiang, Zhou-Hua; Dong, Yan-Wu; Li, Yang; Gong, Wei; Liu, Fu-Bin

    2017-02-01

    Experimental and theoretical studies have been carried out to investigate the effects of the slag on desulfurization during the electroslag remelting (ESR) process with a focus of developing a mass transfer model to understand the mechanism of desulfurization. Stainless steel 1Cr21Ni5Ti was used as the electrode and remelted with two different kinds of slags using a 50-kg ESR furnace. The contents of sulfur along the axial direction of product ingots were analyzed. It was found that the sulfur content of 350 ppm in the electrode is reduced to 71 to 95 ppm in the ingot by remelting with the slag containing 5 wt pct of CaO, and lowered more to 47 to 59 ppm with another slag having 20 wt pct CaO. On the basis of the penetration and film theories, the theoretical model developed in this work well elucidates the kinetics of desulfurization revealing the mechanism of sulfur transfer during the ESR process. The calculation results obtained from the model agree well with the experimental results. The model indicates that when sulfur content in electrode is given, there is a corresponding minimum value of sulfur content in the ingot due to the kinetics limit. This lowest sulfur content cannot be further reduced even with increasing L S (sulfur distribution coefficient between metal and slag phases) or decreasing sulfur content in the slag. Constant addition of extra amount of CaO to the molten slag with the increase of sulfur content in the slag during the remelting process can improve the macrosegregation of sulfur distributed along the axial direction of ESR ingots. Since the rate-determining steps of the sulfur mass transfer lie in the metal phase, adding calcium as deoxidizer can change mass transfer of sulfur and thus promote desulfurization further during the ESR process.

  7. Heat and mass transfer and hydrodynamics in swirling flows (review)

    NASA Astrophysics Data System (ADS)

    Leont'ev, A. I.; Kuzma-Kichta, Yu. A.; Popov, I. A.

    2017-02-01

    Research results of Russian and foreign scientists of heat and mass transfer in whirling flows, swirling effect, superficial vortex generators, thermodynamics and hydrodynamics at micro- and nanoscales, burning at swirl of the flow, and technologies and apparatuses with the use of whirling currents for industry and power generation were presented and discussed at the "Heat and Mass Transfer in Whirling Currents" 5th International Conference. The choice of rational forms of the equipment flow parts when using whirling and swirling flows to increase efficiency of the heat-power equipment and of flow regimes and burning on the basis of deep study of the flow and heat transfer local parameters was set as the main research prospect. In this regard, there is noticeable progress in research methods of whirling and swirling flows. The number of computational treatments of swirling flows' local parameters has been increased. Development and advancement of the up to date computing models and national productivity software are very important for this process. All experimental works are carried out with up to date research methods of the local thermoshydraulic parameters, which enable one to reveal physical mechanisms of processes: PIV and LIV visualization techniques, high-speed and infrared photography, high speed registration of parameters of high-speed processes, etc. There is a problem of improvement of researchers' professional skills in the field of fluid mechanics to set adequately mathematics and physics problems of aerohydrodynamics for whirling and swirling flows and numerical and pilot investigations. It has been pointed out that issues of improvement of the cooling system and thermal protection effectiveness of heat-power and heat-transfer equipment units are still actual. It can be solved successfully using whirling and swirling flows as simple low power consumption exposing on the flow method and heat transfer augmentation.

  8. A Simple and Universal Gel Permeation Chromatography Technique for Precise Molecular Weight Characterization of Well-Defined Poly(ionic liquid)s

    SciTech Connect

    He, Hongkun; Zhong, Mingjiang; Adzima, Brian; Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof

    2013-03-20

    Poly(ionic liquid)s (PILs) are an important class of technologically relevant materials. However, characterization of well-defined polyionic materials remains a challenge. Herein, we have developed a simple and versatile gel permeation chromatography (GPC) methodology for molecular weight (MW) characterization of PILs with a variety of anions. PILs with narrow MW distributions were synthesized via atom transfer radical polymerization, and the MWs obtained from GPC were further confirmed via nuclear magnetic resonance end group analysis.

  9. Restrained Ion Population Transfer: A Novel Ion Transfer Method for Mass Spectrometry.

    SciTech Connect

    Kaiser, Nathan K.; Skulason, Gunnar; Weisbrod, Chad R.; Wu, Si; Zhang, Kai; Prior, David C.; Buschbach, Michael A.; Anderson, Gordon A.; Bruce, James E.

    2008-06-30

    With modern Fourier transform ion cyclotron resonance (ICR) mass spectrometers, ions are created and accumulated exterior to the mass analyzer. The ion accumulation event takes place in a region of higher pressure which allows ions to be thermally cooled before being given kinetic energy and accelerated toward the ICR cell where they are to be decelerated and re-trapped. When gated trapping is used to collect ions in the ICR cell for analysis, mass discrimination can occur due to time-of-flight effects. Also, trapping ions with large axial kinetic energy can decrease the performance of the ICR instrument when compared to the analysis of thermally-cooled ions located at the trap center. Therefore, it is desirable to limit the energy imparted in the ions within the ICR cell as well as minimize time-of-flight effects. The approach presented here for ion transfer called restrained ion population transfer or RIPT provides complete axial control of an ion population throughout the entire transfer sequence from the accumulation region to the ICR cell. This is accomplished by utilization of a number of quadrupole segments arranged in series with independent control of the dc bias voltage applied to each segment of the quadrupole ion guide. This approach circumvents problems associated with time-of-flight effects and minimizes the energy imparted to the ions allowing transfer of the cooled ion packet from the ion accumulation region to the ICR cell. Initial data are presented to illustrate feasibility of restrained ion population transfer. RIPT was also modeled with SIMION 7.0 and simulation results that support our feasibility studies of the ions transfer process are presented.

  10. Effects of mass transfer between Martian satellites on surface geology

    NASA Astrophysics Data System (ADS)

    Nayak, Michael; Nimmo, Francis; Udrea, Bogdan

    2016-03-01

    Impacts on planetary bodies can lead to both prompt secondary craters and projectiles that reimpact the target body or nearby companions after an extended period, producing so-called "sesquinary" craters. Here we examine sesquinary cratering on the moons of Mars. We model the impact that formed Voltaire, the largest crater on the surface of Deimos, and explore the orbital evolution of resulting high-velocity ejecta across 500 years using four-body physics and particle tracking. The bulk of mass transfer to Phobos occurs in the first 102 years after impact, while reaccretion of ejecta to Deimos is predicted to continue out to a 104 year timescale (cf. Soter, S. [1971]. Studies of the Terrestrial Planets. Cornell University). Relative orbital geometry between Phobos and Deimos plays a significant role; depending on the relative true longitude, mass transfer between the moons can change by a factor of five. Of the ejecta with a velocity range capable of reaching Phobos, 25-42% by mass reaccretes to Deimos and 12-21% impacts Phobos. Ejecta mass transferred to Mars is <10%. We find that the characteristic impact velocity of sesquinaries on Deimos is an order of magnitude smaller than those of background (heliocentric) hypervelocity impactors and will likely result in different crater morphologies. The time-averaged flux of Deimos material to Phobos can be as high as 11% of the background (heliocentric) direct-to-Phobos impactor flux. This relatively minor contribution suggests that spectrally red terrain on Phobos (Murchie, S., Erard, S. [1996]. Icarus 123, 63-86) is not caused by Deimos material. However the high-velocity ejecta mass reaccreted to Deimos from a Voltaire-sized impact is comparable to the expected background mass accumulated on Deimos between Voltaire-size events. Considering that the high-velocity ejecta contains only 0.5% of the total mass sent into orbit, sesquinary ejecta from a Voltaire-sized impact could feasibly resurface large parts of the Moon

  11. Mathematical model of mass transfer at electron beam treatment

    NASA Astrophysics Data System (ADS)

    Konovalov, Sergey V.; Sarychev, Vladimir D.; Nevskii, Sergey A.; Kobzareva, Tatyana Yu.; Gromov, Victor E.; Semin, Alexander P.

    2017-01-01

    The paper proposes a model of convective mass transfer at electron beam treatment with beams in titanium alloys subjected to electro-explosion alloying by titanium diboride powder. The proposed model is based on the concept that treatment with concentrated flows of energy results in the initiation of vortices in the melted layer. The formation mechanism of these vortices rooted in the idea that the availability of temperature drop leads to the initiation of the thermo-capillary convection. For the melted layer of metal the equations of the convective heat transfer and boundary conditions in terms of the evaporated material are written. The finite element solution of these equations showed that electron-beam treatment results in the formation of multi-vortex structure that in developing captures all new areas of material. It leads to the fact that the strengthening particles are observed at the depth increasing many times the depth of their penetration according to the diffusion mechanism. The distribution of micro-hardness at depth and the thickness of strengthening zone determined from these data supported the view that proposed model of the convective mass transfer describes adequately the processes going on in the treatment with low-energy high-current electron beam.

  12. Influence of mass transfer on bubble plume hydrodynamics.

    PubMed

    Lima Neto, Iran E; Parente, Priscila A B

    2016-03-01

    This paper presents an integral model to evaluate the impact of gas transfer on the hydrodynamics of bubble plumes. The model is based on the Gaussian type self-similarity and functional relationships for the entrainment coefficient and factor of momentum amplification due to turbulence. The impact of mass transfer on bubble plume hydrodynamics is investigated considering different bubble sizes, gas flow rates and water depths. The results revealed a relevant impact when fine bubbles are considered, even for moderate water depths. Additionally, model simulations indicate that for weak bubble plumes (i.e., with relatively low flow rates and large depths and slip velocities), both dissolution and turbulence can affect plume hydrodynamics, which demonstrates the importance of taking the momentum amplification factor relationship into account. For deeper water conditions, simulations of bubble dissolution/decompression using the present model and classical models available in the literature resulted in a very good agreement for both aeration and oxygenation processes. Sensitivity analysis showed that the water depth, followed by the bubble size and the flow rate are the most important parameters that affect plume hydrodynamics. Lastly, dimensionless correlations are proposed to assess the impact of mass transfer on plume hydrodynamics, including both the aeration and oxygenation modes.

  13. A mass transfer model for VOC emission from silage

    NASA Astrophysics Data System (ADS)

    Hafner, Sasha D.; Montes, Felipe; Rotz, C. Alan

    2012-07-01

    Silage has been shown to be an important source of emissions of volatile organic compounds (VOCs), which contribute to the formation of ground-level ozone. Measurements have shown that environmental conditions and silage properties strongly influence emission rates, making it difficult to assess the contribution of silage in VOC emission inventories. In this work, we present an analytical convection-diffusion-dispersion model for predicting emission of VOCs from silage. It was necessary to incorporate empirical relationships from wind tunnel trials for the response of mass transfer parameters to surface air velocity and silage porosity. The resulting model was able to accurately predict the effect of temperature on ethanol emission in wind tunnel trials, but it over-predicted alcohol and aldehyde emission measured using a mass balance approach from corn silage samples outdoors and within barns. Mass balance results confirmed that emission is related to gas-phase porosity, but the response to air speed was not clear, which was contrary to wind tunnel results. Mass balance results indicate that alcohol emission from loose silage on farms may approach 50% of the initial mass over six hours, while relative losses of acetaldehyde will be greater.

  14. Recent development and applications of dispersive liquid-liquid microextraction.

    PubMed

    Yan, Hongyuan; Wang, Hui

    2013-06-21

    Dispersive liquid-liquid microextraction (DLLME) is a modern sample pretreatment technique that is regarded as consilient with the current trends of modern analytical chemistry. DLLME is simple, inexpensive, environmentally friendly, and could offer high enrichment factors from a wide gap between acceptor and donor phases. As a consequence, DLLME has attracted considerable attention from researchers and, based on the numerous publications concerning DLLME, has been generally accepted in separation science since the technique's invention in 2006. However, several innate weaknesses of DLLME, which restrict the technique's use in certain fields, have led to various attempts or suggestions to improve this technique. The present review focuses on the recent advances made in DLLME; the selected papers that are discussed in this work represent modifications that fall into three main categories (exploration of new extraction solvents, disperser solvents and combination with other techniques). The recent applications of DLLME in environmental, food and biological samples are also summarised, covering almost all of the publications related to the technology from the beginning. In addition, the feasibility of future trends of DLLME is discussed.

  15. Evolution of dispersive liquid-liquid microextraction method.

    PubMed

    Rezaee, Mohammad; Yamini, Yadollah; Faraji, Mohammad

    2010-04-16

    Dispersive liquid-liquid microextraction (DLLME) has become a very popular environmentally benign sample-preparation technique, because it is fast, inexpensive, easy to operate with a high enrichment factor and consumes low volume of organic solvent. DLLME is a modified solvent extraction method in which acceptor-to-donor phase ratio is greatly reduced compared with other methods. In this review, in order to encourage further development of DLLME, its combination with different analytical techniques such as gas chromatography (GC), high-performance liquid chromatography (HPLC), inductively coupled plasma-optical emission spectrometry (ICP-OES) and electrothermal atomic absorption spectrometry (ET AAS) will be discussed. Also, its applications in conjunction with different extraction techniques such as solid-phase extraction (SPE), solidification of floating organic drop (SFO) and supercritical fluid extraction (SFE) are summarized. This review focuses on the extra steps in sample preparation for application of DLLME in different matrixes such as food, biological fluids and solid samples. Further, the recent developments in DLLME are presented. DLLME does have some limitations, which will also be discussed in detail. Finally, an outlook on the future of the technique will be given.

  16. Optimized Liquid-Liquid Extractive Rerefining of Spent Lubricants

    PubMed Central

    Kamal, Muhammad Ashraf; Khan, Fasihullah

    2014-01-01

    Central composite design methodology has been employed to model the sludge yield data obtained during liquid-liquid extractive rerefining of spent lubricants using an alcohol (1-butanol) and a ketone (methyl ethyl ketone) as prospective solvents. The study has resulted in two reasonably accurate multivariate process models that relate the sludge yield (R 2 = 0.9065 and 0.9072 for alcohol and ketone, resp.) to process variables (settling time t, operating temperature T, and oil to solvent ratio r). Construction of such models has allowed the maximization of the sludge yield (more than 8% and 3% in case of alcohol and ketone, resp.) so that the extraction of useable oil components from spent lubricants can economically be performed under extremely mild conditions (t = 16.7 h, T = 10°C, and r = 2) and fairly moderate conditions (t = 26.6 h, T = 10°C, and r = 5) established for the alcohol and ketone correspondingly. Based on these performance parameters alcohol appears to be superior over ketone for this extraction process. Additionally extractive treatment results in oil stocks with lesser quantity of environmentally hazardous polyaromatic hydrocarbons that are largely left in the separated sludge. PMID:24688388

  17. Optimized liquid-liquid extractive rerefining of spent lubricants.

    PubMed

    Kamal, Muhammad Ashraf; Naqvi, Syed Mumtaz Danish; Khan, Fasihullah

    2014-01-01

    Central composite design methodology has been employed to model the sludge yield data obtained during liquid-liquid extractive rerefining of spent lubricants using an alcohol (1-butanol) and a ketone (methyl ethyl ketone) as prospective solvents. The study has resulted in two reasonably accurate multivariate process models that relate the sludge yield (R (2) = 0.9065 and 0.9072 for alcohol and ketone, resp.) to process variables (settling time t, operating temperature T, and oil to solvent ratio r). Construction of such models has allowed the maximization of the sludge yield (more than 8% and 3% in case of alcohol and ketone, resp.) so that the extraction of useable oil components from spent lubricants can economically be performed under extremely mild conditions (t = 16.7 h, T = 10°C, and r = 2) and fairly moderate conditions (t = 26.6 h, T = 10°C, and r = 5) established for the alcohol and ketone correspondingly. Based on these performance parameters alcohol appears to be superior over ketone for this extraction process. Additionally extractive treatment results in oil stocks with lesser quantity of environmentally hazardous polyaromatic hydrocarbons that are largely left in the separated sludge.

  18. Liquid-Liquid phase transition in a single component system

    NASA Astrophysics Data System (ADS)

    Franzese, Giancarlo; Skibinsky, Anna; Buldyrev, Sergey; Stanley, H. Eugene

    2001-06-01

    Recent experimental results indicate that phosphorus, a single-component system, can have a high-density liquid (HDL) and a low-density liquid (LDL) phase. A first-order LDL-HDL transition line ending in a critical point is consistent with experimental data and Molecular Dynamics (MD) simulations for a variety of single-component systems such as water, silica and carbon, but a coherent and general interpretation of the LDL-HDL transition is lacking. By means of MD, we show that the LDL-HDL transition can be directly related to an interaction potential with an attractive part and with not one but `two' preferred short-range repulsive distances. This kind of interaction is common to other single-component materials in the liquid state, in particular liquid metals. For the fisrt time, we show that the LDL-HDL transition can occur in systems with no density anomaly, opening an experimental challenge to uncover a liquid-liquid transition in systems like liquid metals, regardless of the presence of the density anomaly.

  19. Generic mechanism for generating a liquid-liquid phase transition

    NASA Astrophysics Data System (ADS)

    Franzese, Giancarlo; Malescio, Gianpietro; Skibinsky, Anna; Buldyrev, Sergey V.; Stanley, H. Eugene

    2001-02-01

    Recent experimental results indicate that phosphorus-a single-component system-can have a high-density liquid (HDL) and a low-density liquid (LDL) phase. A first-order transition between two liquids of different densities is consistent with experimental data for a variety of materials, including single-component systems such as water, silica and carbon. Molecular dynamics simulations of very specific models for supercooled water, liquid carbon and supercooled silica predict a LDL-HDL critical point, but a coherent and general interpretation of the LDL-HDL transition is lacking. Here we show that the presence of a LDL and a HDL can be directly related to an interaction potential with an attractive part and two characteristic short-range repulsive distances. This kind of interaction is common to other single-component materials in the liquid state (in particular, liquid metals), and such potentials are often used to describe systems that exhibit a density anomaly. However, our results show that the LDL and HDL phases can occur in systems with no density anomaly. Our results therefore present an experimental challenge to uncover a liquid-liquid transition in systems like liquid metals, regardless of the presence of a density anomaly.

  20. Efficiency estimation of liquid-liquid hydrocyclones using trajectory analysis

    SciTech Connect

    Wolbert, D.; Ma, B.F.; Aurelle, Y.; Seureau, J.

    1995-06-01

    As the use of hydrocyclones for liquid-liquid separation becomes increasingly common, the need for a satisfactory method to assess their efficiency increases. Currently available efficiency theories were developed for liquid-solid separations, based on the velocity distributions inside a hydrocyclone. These theories, however, appear less suitable for emulsions where the dispersed phase is slightly lighter than the continuous phase, such as oil/water emulsions. An efficiency computations based on the analysis of the trajectories of the droplets is presented. Trajectories are characterized through a differential equation combining models for the three bulk velocity distributions (axial, radial, and tangential) and the settling velocity defined by Stokes` law. From the critical trajectory and given operating conditions, a characteristic droplet diameter d{sub 100} can be deduced that corresponds to the smallest droplet with a 100% efficiency. Other efficiencies are obtained by changing the initial condition for the trajectory equation. The efficiency results of different hydrocyclone configurations are compared with experimental results, and residual emulsion distributions are estimated.

  1. Surface nanodroplets for highly efficient liquid-liquid microextraction

    NASA Astrophysics Data System (ADS)

    Li, Miaosi; Lu, Ziyang; Yu, Haitao; Zhang, Xuehua

    2016-11-01

    Nanoscale droplets on a substrate are an essential element for a wide range of applications, such as laboratory-on-chip devices, simple and highly efficient miniaturized reactors for concentrating products, high-throughput single-bacteria or single-biomolecular analysis, encapsulation, and high-resolution imaging techniques. The solvent exchange process is a simple bottom-up approach for producing droplets at solid-liquid interfaces that are only several tens to hundreds of nanometers in height, or a few femtoliters in volume Oil nanodroplets can be produced on a substrate by solvent exchange in which a good solvent of oil is displaced by a poor solvent. Our previous work has significantly advanced understanding of the principle of solvent exchange, and the droplet size can be well-controlled by several parameters, including flow rates, flow geometry, gravitational effect and composition of solutions. In this work, we studied the microextraction effect of surface nanodroplets. Oil nanodroplets have been demonstrated to provide highly-efficient liquid-liquid microextraction of hydrophobic solute in a highly diluted solution. This effect proved the feasibility of nanodroplets as a platform for preconcentrating compounds for in situ highly sensitive microanalysis without further separation. Also the long lifetime and temporal stability of surface nanodroplets allow for some long-term extraction process and extraction without addition of stabilisers.

  2. Treatment of biomass gasification wastewaters using liquid-liquid extraction

    SciTech Connect

    Bell, N.E.

    1981-09-01

    Pacific Northwest Laboratory (PNL) investigated liquid-liquid extraction as a treatment method for biomass gasification wastewaters (BGW). Distribution coefficients for chemical oxygen demand (COD) removal were determined for the following solvents: methylisobutyl ketone (MIBK), n-butyl acetate, n-butanol, MIBK/n-butyl acetate (50:50 vol), MIBK/n-butanol (50:50 vol), tri-butyl phosphate, tri-n-octyl phosphine oxide (TOPO)/MIBK (10:90 wt), TOPO/kerosene (10:90 wt), kerosene, and toluene. The best distribution coefficient of 1.3 was given by n-butanol. Chemical analysis of the wastewater by gas chromatography (GC) showed acetic acid and propionic acid concentrations of about 4000 mg/1. Methanol, ethanol, and acetone were identified in trace amounts. These five compounds accounted for 45% of the measured COD of 29,000 mg/1. Because of the presence of carboxylic acids, pH was expected to affect extraction of the wastewater. At low pH the acids should be in the acidic form, which increased extraction by MIBK. Extraction by n-butanol was increased at high pH, where the acids should be in the ionic form.

  3. The Hottest, and Most Liquid, Liquid in the Universe

    NASA Astrophysics Data System (ADS)

    Rajagopal, Krishna

    2012-03-01

    What was the universe like microseconds after the big bang? At very high temperatures, protons and neutrons fall apart --- the quarks that are ordinarily confined within them are freed. Before experiments at the Relativistic Heavy Ion Collider started recreating little droplets of big bang matter, it was thought to be a tenuous gas-like plasma. Now we know from experiments at RHIC and at the Large Hadron Collider that at these extreme temperatures nature serves up hot quark soup --- the hottest liquid in the universe and the liquid that flows with the least dissipation. The only other comparably liquid liquid is the coldest liquid in the universe, namely the fluid made of trapped fermionic atoms at microKelvin rather than TeraKelvin temperatures. These are two examples of strongly coupled fluids without any apparent quasiparticle description, a feature that they share with other phases of matter like the strange metal phase of the cuprate superconductors that aren't conventionally thought of as liquids but that are equally challenging to understand. I will describe how physicists are using RHIC and LHC experiments --- as well as calculations done using dualities between liquids and black holes discovered in string theory --- to discern the properties of hot quark soup. In this domain, string theory is answering questions posed by laboratory experiments. I will describe the opportunities and challenges for coming experiments at RHIC and the LHC, chief among them being understanding how a liquid with no apparent particulate description emerges from quarks and gluons.

  4. Liquid-Liquid Phase Separation of Oil Bodies from Seeds.

    PubMed

    Nykiforuk, Cory L

    2016-01-01

    Fundamentally, oil bodies are discrete storage organelles found in oilseeds, comprising a hydrophobic triacylglycerol core surrounded by a half-unit phospholipid membrane and an outer shell of specialized proteins known as oleosins. Oil bodies possess a number of attributes that were exploited by SemBioSys Genetics to isolate highly enriched fractions of oil bodies through liquid-liquid phase separation for a number of commercial applications. The current chapter provides a general guide for the isolation of oil bodies from Arabidopsis and/or safflower seed, from which protocols can be refined for different oilseed sources. For SemBioSys Genetic's recombinant technology, therapeutic proteins were covalently attached to oleosins or fused in-frame with ligands which bound oil bodies, facilitating their recovery to high levels of purity during "upstream processing" of transformed seed. Core to this technology was oil body isolation consisting of simple manipulation including homogenization of seeds to free the oil bodies, followed by the removal of insoluble fractions, and phase separation to recover the oil bodies. During oil body enrichment (an increase in oil body content concomitant with removal of impurities), a number of options and tips are provided to aid researchers in the manipulation and monitoring of these robust organelles.

  5. Determination of Lead in Water Samples Using a New Vortex-Assisted, Surfactant-Enhanced Emulsification Liquid-Liquid Microextraction Combined with Graphite Furnace Atomic Absorption Spectrometry.

    PubMed

    Peng, Guilong; He, Qiang; Lu, Ying; Mmereki, Daniel; Pan, Weiliang; Tang, Xiaohui; Zhou, Guangming; Mao, Yufeng; Su, Xaioxuan

    2016-04-01

    A low toxic solvent-based vortex-assisted surfactant-enhanced emulsification liquid-liquid microextraction (LT-VSLLME) combined with graphite furnace atomic absorption spectrometry was developed for the extraction and determination of lead (Pb) in water samples. In the LT-VSLLME method, the extraction solvent was dispersed into the aqueous samples by the assistance of vortex agitator. Meanwhile, the addition of a surfactant, which acted as an emulsifier, could enhance the speed of the mass-transfer from aqueous samples to the extraction solvent. The influences of analytical parameters, including extraction solvent type and its volume, surfactant type and its volume, pH, concentration of chelating agent, salt effect and extraction time were investigated. Under the optimized conditions, a good relative standard deviation of 3.69% at 10 ng L(-1) was obtained. The calibration graph showed a linear pattern in the ranges of 5-30 ngL(-1), with a limit of detection of 0.76 ng L(-1). The linearity was obtained by five points in the concentration range of 5-30 ngL(-1). The enrichment factor was 320. The procedure was applied to wastewater and river water, and the accuracy was assessed through the analysis of the recovery experiments.

  6. Characterizing Mass Transfer at the Hanford 300 Area

    NASA Astrophysics Data System (ADS)

    Hall, L. H.

    2012-12-01

    Aquifer remediation efforts in the Hanford 300 Area in Washington have presented substantial challenges for the Department of Energy. Since the early 1940s, this site has been a receptacle for radiological and chemical wastes from nuclear weapons production, including high concentrations of uranium. Employing techniques to estimate and measure mass transfer in-situ will improve understanding of contaminant fate and transport at this site, and perhaps others. A field experiment was conducted with a combination of electrical resistivity tomography (ERT) and ionic tracer tests through a double-ring infiltrometer to quantify multirate mass-transfer and other transport parameters in the 300 Area. The tests included a series of injections into an infiltrating column of water. After saturating the column with fresh water at a constant head, bromide tracer solution with initial known concentration was injected for a specified amount of hours. This was followed by a continual fresh water injection during which time fluid samples were taken at varying depths along the probe to observe the tailing of the breakthrough curve during this purge. Throughout the experiment, ERT data collected along the column as well as along a transect perpendicular to the vertical sampling ports. These experiments will result in a model of the local vadose zone which will be calibrated using field data and modeled using HYDRUS 2D and its sequential inverse modeling feature. This program numerically solves the Richards equation for variably saturated water flow and advection-dispersion (AD) type equations for solute transport. It also considers dual-porosity type flow in the mobile and immobile domain. Additionally, mass transfer parameters will be modeled using a code which utilizes the AD equation and numerically solves for concentrations using Laplace Transforms. Analysis on governing processes and calibration of this code using field data will be used for additional verification on

  7. Direct geoelectrical evidence of mass transfer at the laboratory scale

    USGS Publications Warehouse

    Swanson, Ryan D.; Singha, Kamini; Day-Lewis, Frederick D.; Binley, Andrew; Keating, Kristina; Haggerty, Roy

    2012-01-01

    Previous field-scale experimental data and numerical modeling suggest that the dual-domain mass transfer (DDMT) of electrolytic tracers has an observable geoelectrical signature. Here we present controlled laboratory experiments confirming the electrical signature of DDMT and demonstrate the use of time-lapse electrical measurements in conjunction with concentration measurements to estimate the parameters controlling DDMT, i.e., the mobile and immobile porosity and rate at which solute exchanges between mobile and immobile domains. We conducted column tracer tests on unconsolidated quartz sand and a material with a high secondary porosity: the zeolite clinoptilolite. During NaCl tracer tests we collected nearly colocated bulk direct-current electrical conductivity (σb) and fluid conductivity (σf) measurements. Our results for the zeolite show (1) extensive tailing and (2) a hysteretic relation between σf and σb, thus providing evidence of mass transfer not observed within the quartz sand. To identify best-fit parameters and evaluate parameter sensitivity, we performed over 2700 simulations of σf, varying the immobile and mobile domain and mass transfer rate. We emphasized the fit to late-time tailing by minimizing the Box-Cox power transformed root-mean square error between the observed and simulated σf. Low-field proton nuclear magnetic resonance (NMR) measurements provide an independent quantification of the volumes of the mobile and immobile domains. The best-fit parameters based on σf match the NMR measurements of the immobile and mobile domain porosities and provide the first direct electrical evidence for DDMT. Our results underscore the potential of using electrical measurements for DDMT parameter inference.

  8. Direct geoelectrical evidence of mass transfer at the laboratory scale

    NASA Astrophysics Data System (ADS)

    Swanson, Ryan D.; Singha, Kamini; Day-Lewis, Frederick D.; Binley, Andrew; Keating, Kristina; Haggerty, Roy

    2012-10-01

    Previous field-scale experimental data and numerical modeling suggest that the dual-domain mass transfer (DDMT) of electrolytic tracers has an observable geoelectrical signature. Here we present controlled laboratory experiments confirming the electrical signature of DDMT and demonstrate the use of time-lapse electrical measurements in conjunction with concentration measurements to estimate the parameters controlling DDMT, i.e., the mobile and immobile porosity and rate at which solute exchanges between mobile and immobile domains. We conducted column tracer tests on unconsolidated quartz sand and a material with a high secondary porosity: the zeolite clinoptilolite. During NaCl tracer tests we collected nearly colocated bulk direct-current electrical conductivity (σb) and fluid conductivity (σf) measurements. Our results for the zeolite show (1) extensive tailing and (2) a hysteretic relation between σf and σb, thus providing evidence of mass transfer not observed within the quartz sand. To identify best-fit parameters and evaluate parameter sensitivity, we performed over 2700 simulations of σf, varying the immobile and mobile domain and mass transfer rate. We emphasized the fit to late-time tailing by minimizing the Box-Cox power transformed root-mean square error between the observed and simulated σf. Low-field proton nuclear magnetic resonance (NMR) measurements provide an independent quantification of the volumes of the mobile and immobile domains. The best-fit parameters based on σf match the NMR measurements of the immobile and mobile domain porosities and provide the first direct electrical evidence for DDMT. Our results underscore the potential of using electrical measurements for DDMT parameter inference.

  9. Solid lubricant mass contact transfer technology usage for vacuum ball bearings longevity increasing

    NASA Astrophysics Data System (ADS)

    Arzymatov, B.; Deulin, E.

    2016-07-01

    A contact mass transfer technological method of solid lubricant deposition on components of vacuum ball bearings is presented. Physics-mathematical model of process contact mass transfer is being considered. The experimental results of ball bearings covered with solid lubricant longevity in vacuum are presented. It is shown that solid lubricant of contact mass transfer method deposition is prospective for ball bearing longevity increasing.

  10. Transient mass transfer at the rotating disk electrode.

    NASA Technical Reports Server (NTRS)

    Nanis, L.; Klein, I.

    1972-01-01

    Transient mass transfer at the rotating disk has been investigated theoretically and experimentally for cathodic reduction of ferricyanide in the redox system ferricyanide-ferrocyanide with potassium hydroxide supporting electrolyte. It has been shown that overpotential-time predictions for the rotating disk are fitted very well for decay (current interruption) but poorly for build-up following switching on of constant current. As an explanation for this behavior, attention is directed to the inadequacy of the assumption that a radially independent concentration profile exists at the disk surface just at the start of galvanostatic current passage.

  11. Gas stream in Algol. [mass transfer in binary star systems

    NASA Technical Reports Server (NTRS)

    Cugier, H.; Chen, K.-Y.

    1977-01-01

    Additional absorption features in the red wings of the Mg II resonance lines near 2800 A are found in observations of Algol made from the Copernicus satellite. The absorption features were clearly seen only during a part of the primary eclipse, in the phase interval 0.90-0.03. The observations are interpreted as being produced by a stream of matter flowing from Algol B in the direction of Algol A. The measured Doppler shifts of the features give the value of 150 km/s as the characteristic velocity of matter in the stream. The mass transfer connected with the stream is estimated to be of the order of 10 to the -13th power solar mass per year.

  12. Turbulent mass transfer through a flat shear-free surface

    NASA Astrophysics Data System (ADS)

    Magnaudet, Jacques; Calmet, Isabelle

    2006-04-01

    Mass transfer through the flat shear-free surface of a turbulent open-channel flow is investigated over a wide range of Schmidt number (1 ≤ Sc ≤ 200) by means of large-eddy simulations using a dynamic subgrid-scale model. In contrast with situations previously analysed using direct numerical simulation, the turbulent Reynolds number Re is high enough for the near-surface turbulence to be fairly close to isotropy and almost independent of the structure of the flow in the bottom region (the statistics of the velocity field are identical to those described by I. Calmet & J. Magnaudet J. Fluid Mech. vol. 474, 2003, p. 355). The main statistical features of the concentration field are analysed in connection with the structure of the turbulent motion below the free surface, characterized by a velocity macroscale u and an integral length scale L. All near-surface statistical profiles are found to be Sc-independent when plotted vs. the dimensionless coordinate Sc({1) / 2}yu/nu (y is the distance to the surface and nu is the kinematic viscosity). Mean concentration profiles are observed to be linear throughout an inner diffusive sublayer whose thickness is about one Batchelor microscale, i.e. LSc({) - 1 / 2 }Re({) - 3 / 4}. In contrast, the concentration fluctuations are found to reach their maximum near the edge of the outer diffusive layer which scales as LSc({) - 1 / 2}Re({) - 1 / 2}. Instantaneous views of the near-surface isovalues of the concentration and vertical velocity are used to reveal the influence of the Schmidt number. In particular, it is observed that at high Schmidt number, the tiny concentration fluctuations that subsist in the diffusive sublayer just mirror the divergence of the two-component surface velocity field. Co-spectra of concentration and vertical velocity fluctuations indicate that the main contribution to the turbulent mass flux is provided by eddies whose horizontal size is close to L, which strongly supports the view that the mass

  13. Hornblendite delineates zones of mass transfer through the lower crust

    PubMed Central

    Daczko, Nathan R.; Piazolo, Sandra; Meek, Uvana; Stuart, Catherine A.; Elliott, Victoria

    2016-01-01

    Geochemical signatures throughout the layered Earth require significant mass transfer through the lower crust, yet geological pathways are under-recognized. Elongate bodies of basic to ultrabasic rocks are ubiquitous in exposures of the lower crust. Ultrabasic hornblendite bodies hosted within granulite facies gabbroic gneiss of the Pembroke Valley, Fiordland, New Zealand, are typical occurrences usually reported as igneous cumulate hornblendite. Their igneous features contrast with the metamorphic character of their host gabbroic gneiss. Both rock types have a common parent; field relationships are consistent with modification of host gabbroic gneiss into hornblendite. This precludes any interpretation involving cumulate processes in forming the hornblendite; these bodies are imposter cumulates. Instead, replacement of the host gabbroic gneiss formed hornblendite as a result of channeled high melt flux through the lower crust. High melt/rock ratios and disequilibrium between the migrating magma (granodiorite) and its host gabbroic gneiss induced dissolution (grain-scale magmatic assimilation) of gneiss and crystallization of mainly hornblende from the migrating magma. The extent of this reaction-replacement mechanism indicates that such hornblendite bodies delineate significant melt conduits. Accordingly, many of the ubiquitous basic to ultrabasic elongate bodies of the lower crust likely map the ‘missing’ mass transfer zones. PMID:27546342

  14. Hornblendite delineates zones of mass transfer through the lower crust.

    PubMed

    Daczko, Nathan R; Piazolo, Sandra; Meek, Uvana; Stuart, Catherine A; Elliott, Victoria

    2016-08-22

    Geochemical signatures throughout the layered Earth require significant mass transfer through the lower crust, yet geological pathways are under-recognized. Elongate bodies of basic to ultrabasic rocks are ubiquitous in exposures of the lower crust. Ultrabasic hornblendite bodies hosted within granulite facies gabbroic gneiss of the Pembroke Valley, Fiordland, New Zealand, are typical occurrences usually reported as igneous cumulate hornblendite. Their igneous features contrast with the metamorphic character of their host gabbroic gneiss. Both rock types have a common parent; field relationships are consistent with modification of host gabbroic gneiss into hornblendite. This precludes any interpretation involving cumulate processes in forming the hornblendite; these bodies are imposter cumulates. Instead, replacement of the host gabbroic gneiss formed hornblendite as a result of channeled high melt flux through the lower crust. High melt/rock ratios and disequilibrium between the migrating magma (granodiorite) and its host gabbroic gneiss induced dissolution (grain-scale magmatic assimilation) of gneiss and crystallization of mainly hornblende from the migrating magma. The extent of this reaction-replacement mechanism indicates that such hornblendite bodies delineate significant melt conduits. Accordingly, many of the ubiquitous basic to ultrabasic elongate bodies of the lower crust likely map the 'missing' mass transfer zones.

  15. Analysis of ultrafiltration and mass transfer in a bioartificial pancreas.

    PubMed

    Jaffrin, M Y; Reach, G; Notelet, D

    1988-02-01

    A bioartificial pancreas is an implantable device which contains insulin secreting cells (Langerhans islets), separated from the circulating blood by a semi-permeable membrane to avoid rejection. This paper describes the operation of such a device and evaluates the respective contributions of diffusion and ultrafiltration to the glucose and insulin mass transfer. It is shown that the pressure drop along the blood channel produces across the first half of the channel an ultrafiltration flux toward the islet compartment followed in the second half by an equal flux in reverse direction from islets to blood. The mass transfer analysis is carried out for an optimal geometry in which a U-shaped blood channel surrounds closely a very thin islet compartment formed by a folded flat membrane. A complete model of insulin release by this device is developed and is compared with in vitro data obtained with rats islets. Satisfactory kinetics is achieved with a polyacrylonitrile membrane used in hemodialysis. But the model shows that the membrane hydraulic permeability should be increased by a factor of 10 to significantly improve the performance.

  16. Parallel Mass Transfer Simulation of Nanoparticles Using Nonblocking Communications

    NASA Astrophysics Data System (ADS)

    Chantrapornchai (Phonpensri), Chantana; Dolwithayakul, Banpot; Gorlatch, Sergei

    This paper presents experiences and results obtained in optimizing parallelization of the mass transfer simulation in the High Gradient Magnetic Separation (HGMS) of nanoparticles using nonblocking communication techniques in the point-to-point and collective model. We study the dynamics of mass transfer statistically in terms of particle volume concentration and the continuity equation, which is solved numerically by using the finite-difference method to compute concentration distribution in the simulation domain at a given time. In the parallel simulation, total concentration data in the simulation domain are divided row-wise and distributed equally to a group of processes. We propose two parallel algorithms based on the row-wise partitioning: algorithms with nonblocking send/receive and nonblocking scatter/gather using the NBC library. We compare the performance of both versions by measuring their parallel speedup and efficiency. We also investigate the communication overhead in both versions. Our results show that the nonblocking collective communication can improve the performance of the simulation when the number of processes is large.

  17. Acoustic Streaming and Heat and Mass Transfer Enhancement

    NASA Technical Reports Server (NTRS)

    Trinh, E. H.; Gopinath, A.

    1996-01-01

    A second order effect associated with high intensity sound field, acoustic streaming has been historically investigated to gain a fundamental understanding of its controlling mechanisms and to apply it to practical aspects of heat and mass transfer enhancement. The objectives of this new research project are to utilize a unique experimental technique implementing ultrasonic standing waves in closed cavities to study the details of the generation of the steady-state convective streaming flows and of their interaction with the boundary of ultrasonically levitated near-spherical solid objects. The goals are to further extend the existing theoretical studies of streaming flows and sample interactions to higher streaming Reynolds number values, for larger sample size relative to the wavelength, and for a Prandtl and Nusselt numbers parameter range characteristic of both gaseous and liquid host media. Experimental studies will be conducted in support to the theoretical developments, and the crucial impact of microgravity will be to allow the neglect of natural thermal buoyancy. The direct application to heat and mass transfer in the absence of gravity will be emphasized in order to investigate a space-based experiment, but both existing and novel ground-based scientific and technological relevance will also be pursued.

  18. Gas Blowing: Mass Transfer in Gas and Melt

    NASA Astrophysics Data System (ADS)

    Sortland, Øyvind Sunde; Tangstad, Merete

    2014-09-01

    Metallurgical routes for solar grade silicon production are being developed as alternatives to chemical processes for their potential to achieve cost reductions, increased production volume, and reduced environmental and safety concerns. An important challenge in the development of metallurgical routes relates to the higher impurity concentrations in the silicon product, particularly for boron and other elements that are not efficiently segregated in solidification techniques. The reactive gas refining process is studied for its potential to remove boron below the solar grade silicon target concentration in a single step by blowing steam and hydrogen gas jets onto the melt surface. Boron in a silicon melt is extracted to HBO gas in parallel to active oxidation of silicon. The literature is not unified regarding the rate determining step in this process. Relevant theories and equations for gas blowing in induction furnaces are combined and used to explain mass transfer in experiments. Mass transfer in the melt and gas is investigated by comparing resistance and induction heating of the melt, and varying gas flow rate, crucible diameter, diameter of the gas lance, and the position of the gas lance above the melt surface. The rate of boron removal is found to increase with increasing gas flow rate and crucible diameter. A relatively high fraction of the reactive gas is utilized in the process, and supply of steam in the bulk gas is the only identified rate determining step.

  19. Hornblendite delineates zones of mass transfer through the lower crust

    NASA Astrophysics Data System (ADS)

    Daczko, Nathan R.; Piazolo, Sandra; Meek, Uvana; Stuart, Catherine A.; Elliott, Victoria

    2016-08-01

    Geochemical signatures throughout the layered Earth require significant mass transfer through the lower crust, yet geological pathways are under-recognized. Elongate bodies of basic to ultrabasic rocks are ubiquitous in exposures of the lower crust. Ultrabasic hornblendite bodies hosted within granulite facies gabbroic gneiss of the Pembroke Valley, Fiordland, New Zealand, are typical occurrences usually reported as igneous cumulate hornblendite. Their igneous features contrast with the metamorphic character of their host gabbroic gneiss. Both rock types have a common parent; field relationships are consistent with modification of host gabbroic gneiss into hornblendite. This precludes any interpretation involving cumulate processes in forming the hornblendite; these bodies are imposter cumulates. Instead, replacement of the host gabbroic gneiss formed hornblendite as a result of channeled high melt flux through the lower crust. High melt/rock ratios and disequilibrium between the migrating magma (granodiorite) and its host gabbroic gneiss induced dissolution (grain-scale magmatic assimilation) of gneiss and crystallization of mainly hornblende from the migrating magma. The extent of this reaction-replacement mechanism indicates that such hornblendite bodies delineate significant melt conduits. Accordingly, many of the ubiquitous basic to ultrabasic elongate bodies of the lower crust likely map the ‘missing’ mass transfer zones.

  20. Effect of confinement on the liquid-liquid phase transition of supercooled water.

    PubMed

    Brovchenko, I; Oleinikova, A

    2007-06-07

    We report on an observation of the phase transition between two liquid phases of supercooled confined water in simulations. The temperature of the liquid-liquid transition of water at zero pressure slightly decreases due to confinement in the hydrophobic pore. The hydrophilic confinement affects this temperature in the opposite direction and shifts the critical point of the liquid-liquid transition to a higher pressure. As a result, in a strongly hydrophilic pore the liquid-liquid phase transition becomes continuous at zero pressure, indicating the shift of its critical point from negative to a positive pressure. These findings indicate that experimental studies of water confined in the pores of various hydrophobicity/hydrophilicity may clarify the location of the liquid-liquid critical point of bulk water.

  1. Continuous gas/liquid–liquid/liquid flow synthesis of 4-fluoropyrazole derivatives by selective direct fluorination

    PubMed Central

    Breen, Jessica R; Yufit, Dmitrii S; Howard, Judith A K; Fray, Jonathan; Patel, Bhairavi

    2011-01-01

    Summary 4-Fluoropyrazole systems may be prepared by a single, sequential telescoped two-step continuous gas/liquid–liquid/liquid flow process from diketone, fluorine gas and hydrazine starting materials. PMID:21915207

  2. Evidence of contact epitaxy in the self-assembly of HgSe nanocrystals formed at a liquid-liquid interface.

    PubMed

    Maiti, Santanu; Sanyal, Milan K; Jana, Manoj K; Runge, Benjamin; Murphy, Bridget M; Biswas, Kanishka; Rao, C N R

    2017-03-08

    The grazing incidence x-ray scattering results presented here show that the self-assembly process of HgSe nanocrystals formed at a liquid-liquid interface is quite different along the in-plane direction and across the interface. In situ x-ray reflectivity and ex situ microscopy measurements suggest quantized out-of-plane growth for HgSe nanoparticles of a size of about [Formula: see text] nm initially. Grazing incidence small-angle x-ray scattering measurements for films transferred from the water-toluene interface at various stages of reaction show that these nanoparticles first form random clusters with an average radius of 2.2 nm, giving rise to equally spaced rings of several orders. Finally, these clusters self-organize into face-centered cubic superstructures, giving sharp x-ray diffraction peaks oriented normal to the liquid-liquid interface with more than 100 nm-coherent domains. We also observed the x-ray diffraction pattern of the HgSe crystalline phase, with the superlattice peaks in these grazing incidence measurements of the transferred films. The electron microscopy and atomic force microscopy results support the x-ray observation of the self-organization of HgSe nanocrystals into close-packed superlattices. These results show that capillary wave fluctuation promotes the oriented attachment of clusters at the liquid-liquid interface, giving direct experimental evidence of contact epitaxy.

  3. Mass transfer and transport in a geologic environment

    SciTech Connect

    Chambre, P.L.; Pigford, T.H.; Lee, W.W.L.; Ahn, J.; Kajiwara, S.; Kim, C.L.; Kimura, H.; Lung, H.; Williams, W.J.; Zavoshy, S.J.

    1985-04-01

    This report is in a continuing series of reports that present analytic solutions for the dissolution and hydrogeologic transport of radionuclides from geologic repositories of nuclear waste. Previous reports have dealt mainly with radionuclide transport in the far-field, away from the effects of the repository. In the present report, the emphasis is on near-field processes, the transfer and transport of radionuclides in the vicinity of the waste packages. The primary tool used in these analyses is mass transfer theory from chemical engineering. The thrust of our work is to develop methods for predicting the performance of geologic repositories. The subjects treated in the present report are: radionuclide transport from a spherical-equivalent waste form through a backfill; analysis of radionuclide transport through a backfill using a non-linear sorption isotherm; radionuclide transport from a prolate spheroid-equivalent waste form with a backfill; radionuclide transport from a spherical-equivalent waste form through a backfill, where the solubility, diffusivity and retardation coefficients are temperature dependent; a coupled near-field, far-field analysis where dissolution and migration rates are temperature dependent; transport of radionuclides from a point source in a three-dimensional flow field; and a general solution for the transport of radioactive chains in geologic media. There are several important results from the numerical evaluations. First, radioactive decay, higher sorption in the rock and the backfill steepens the gradient for mass transfer, and lead to higher dissolution rates. This is contrary to what was expected by some other workers, but is shown clearly in the analytical solutions. Second, the backfill serves to provide sorption sites so that there is a delay in the arrival of radionuclides in the rock, although this effect is not so important for the steady-state transport of long-lived radionuclides.

  4. Impact of surface roughness on liquid-liquid transition.

    PubMed

    Murata, Ken-Ichiro; Tanaka, Hajime

    2017-02-01

    Liquid-liquid transition (LLT) in single-component liquids is one of the most mysterious phenomena in condensed matter. So far, this problem has attracted attention mainly from the fundamental viewpoint. We report the first experimental study on an impact of surface nanostructuring on LLT by using a surface treatment called rubbing, which is the key technology for the production of liquid crystal displays. We find that this rubbing treatment has a significant impact on the kinetics of LLT of an isotropic molecular liquid, triphenyl phosphite. For a liquid confined between rubbed surfaces, surface-induced barrierless formation of the liquid II phase is observed even in a metastable state, where there should be a barrier for nucleation of the liquid II phase in bulk. Thus, surface rubbing of substrates not only changes the ordering behavior but also significantly accelerates the kinetics. This spatiotemporal pattern modulation of LLT can be explained by a wedge-filling transition and the resulting drastic reduction of the nucleation barrier. However, this effect completely disappears in the unstable (spinodal) regime, indicating the absence of the activation barrier even for bulk LLT. This confirms the presence of nucleation-growth- and spinodal decomposition-type LLT, supporting the conclusion that LLT is truly a first-order transition with criticality. Our finding also opens up a new way to control the kinetics of LLT of a liquid confined in a solid cell by structuring its surface on a mesoscopic length scale, which may contribute to making LLT useful for microfluidics and other industrial applications.

  5. Impact of surface roughness on liquid-liquid transition

    PubMed Central

    Murata, Ken-ichiro; Tanaka, Hajime

    2017-01-01

    Liquid-liquid transition (LLT) in single-component liquids is one of the most mysterious phenomena in condensed matter. So far, this problem has attracted attention mainly from the fundamental viewpoint. We report the first experimental study on an impact of surface nanostructuring on LLT by using a surface treatment called rubbing, which is the key technology for the production of liquid crystal displays. We find that this rubbing treatment has a significant impact on the kinetics of LLT of an isotropic molecular liquid, triphenyl phosphite. For a liquid confined between rubbed surfaces, surface-induced barrierless formation of the liquid II phase is observed even in a metastable state, where there should be a barrier for nucleation of the liquid II phase in bulk. Thus, surface rubbing of substrates not only changes the ordering behavior but also significantly accelerates the kinetics. This spatiotemporal pattern modulation of LLT can be explained by a wedge-filling transition and the resulting drastic reduction of the nucleation barrier. However, this effect completely disappears in the unstable (spinodal) regime, indicating the absence of the activation barrier even for bulk LLT. This confirms the presence of nucleation-growth– and spinodal decomposition–type LLT, supporting the conclusion that LLT is truly a first-order transition with criticality. Our finding also opens up a new way to control the kinetics of LLT of a liquid confined in a solid cell by structuring its surface on a mesoscopic length scale, which may contribute to making LLT useful for microfluidics and other industrial applications. PMID:28232957

  6. Inherent stability of central element coaxial liquid-liquid injectors

    NASA Technical Reports Server (NTRS)

    Stoddard, Frank J.

    1993-01-01

    Most TRW liquid bi-propellant rocket engines built over the past thirty-plus years have employed a central element coaxial pintle injector and have operated with liquid/liquid propellant injection. This injector is a patented design exclusive to TRW and has unique features that make the rocket engine combustion characteristics different from those of other types of injector engine designs. Its many benefits include excellent combustion performance, efficient deep throttling, adaptability to low cost manufacturing, and high reliability. Approximately 200 pintle injector engines of various sizes and operating on a variety of propellants have been flown without a single inflight failure. An especially important feature of the pintle injector engine is its apparent inherent combustion stability. In over thirty years of development, testing, and production, TRW has never experienced combustion instability in any of its pintle injector engine designs. This has been true of engines operating over a range of thrust from 5 to 250,000 lbs. on earth-storable hypergolic propellants and a large number of smaller engines operating on a variety of propellants (21 combinations) in long duration-firing, pulsing (down to 2 msec), and deep throttling (as much as 19:1) modes. Operating chamber pressures have ranged from 10 to 3,500 psia. This record is particularly impressive given that typical TRW design practice does not consider combustion instability as an issue and no pintle engine has ever employed stability-enhancing features, such as baffles or acoustically resonant chambers. In spite of this, TRW engines have operated stably in regimes not possible with other types of injectors. Various physical explanations and combustion process models for this favorable stability characteristic have been postulated. However, a definitive study that unequivocally establishes the important stabilizing mechanisms still remains to be conducted.

  7. Inherent stability of central element coaxial liquid-liquid injectors

    NASA Astrophysics Data System (ADS)

    Stoddard, Frank J.

    1993-11-01

    Most TRW liquid bi-propellant rocket engines built over the past thirty-plus years have employed a central element coaxial pintle injector and have operated with liquid/liquid propellant injection. This injector is a patented design exclusive to TRW and has unique features that make the rocket engine combustion characteristics different from those of other types of injector engine designs. Its many benefits include excellent combustion performance, efficient deep throttling, adaptability to low cost manufacturing, and high reliability. Approximately 200 pintle injector engines of various sizes and operating on a variety of propellants have been flown without a single inflight failure. An especially important feature of the pintle injector engine is its apparent inherent combustion stability. In over thirty years of development, testing, and production, TRW has never experienced combustion instability in any of its pintle injector engine designs. This has been true of engines operating over a range of thrust from 5 to 250,000 lbs. on earth-storable hypergolic propellants and a large number of smaller engines operating on a variety of propellants (21 combinations) in long duration-firing, pulsing (down to 2 msec), and deep throttling (as much as 19:1) modes. Operating chamber pressures have ranged from 10 to 3,500 psia. This record is particularly impressive given that typical TRW design practice does not consider combustion instability as an issue and no pintle engine has ever employed stability-enhancing features, such as baffles or acoustically resonant chambers. In spite of this, TRW engines have operated stably in regimes not possible with other types of injectors. Various physical explanations and combustion process models for this favorable stability characteristic have been postulated. However, a definitive study that unequivocally establishes the important stabilizing mechanisms still remains to be conducted.

  8. Vortex and air assisted liquid-liquid microextraction as a sample preparation method for high-performed liquid chromatography determinations.

    PubMed

    Hosseini, Mohammad; Heydari, Rouhollah; Alimoradi, Mohammad

    2014-12-01

    A novel, simple and sensitive method based on vortex and air assisted liquid-liquid microextraction (VAALLME) technique coupled with high-performance liquid chromatography (HPLC) has been developed for quantitative analysis of β-naphthol, naphthalene and anthracene as model analytes. Unlike the dispersive liquid-liquid microextraction (DLLME), dispersive solvent and centrifuging step were eliminated in proposed technique. In this technique, extraction solvent was dispersed into the aqueous sample solution by using vortex. Phase separation was achieved via motion of air bubbles from the bottom to top of the extraction tube, which promoted the analytes transfer into the supernatant organic phase. Influential parameters on the extraction efficiency such as type and volume of extraction solvent, salt type and its concentration, vortex and aeration times, and sample pH were evaluated and optimized. The calibration curves showed good linearity (r(2)>0.9947) and precision (RSD<5.0%) in the working concentration ranges. The limit of detection (LOD) for β-naphthol, naphthalene and anthracene were 10, 5.0 and 0.5 ng mL(-1), respectively. The recoveries were in the range of 97.0-102.0% with RSD values ranging from 2.2 to 5.2%. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. The reversibility and first-order nature of liquid-liquid transition in a molecular liquid

    NASA Astrophysics Data System (ADS)

    Kobayashi, Mika; Tanaka, Hajime

    2016-11-01

    Liquid-liquid transition is an intriguing phenomenon in which a liquid transforms into another liquid via the first-order transition. For molecular liquids, however, it always takes place in a supercooled liquid state metastable against crystallization, which has led to a number of serious debates concerning its origin: liquid-liquid transition versus unusual nano-crystal formation. Thus, there have so far been no single example free from such debates, to the best of our knowledge. Here we show experimental evidence that the transition is truly liquid-liquid transition and not nano-crystallization for a molecular liquid, triphenyl phosphite. We kinetically isolate the reverse liquid-liquid transition from glass transition and crystallization with a high heating rate of flash differential scanning calorimetry, and prove the reversibility and first-order nature of liquid-liquid transition. Our finding not only deepens our physical understanding of liquid-liquid transition but may also initiate a phase of its research from both fundamental and applications viewpoints.

  10. Combination of corona discharge ion mobility spectrometry with a novel reagent gas and two immiscible organic solvent liquid-liquid-liquid microextraction for analysis of clomipramine in biological samples.

    PubMed

    Saraji, Mohammad; Bidgoli, Ali Akbar Hajialiakbari; Khayamian, Taghi; Moradmand, Ali

    2011-12-02

    A novel and sensitive method based on combination of two immiscible organic solvents hollow fiber-based liquid-liquid-liquid microextraction and corona discharge ion mobility spectrometry (HF-LLLME-CD-IMS) was employed for the analysis of clomipramine in human urine and plasma. The effect of formic, acetic and propionic acid as the reagent gas (dopant) on the corona discharge ion mobility signal was investigated. The influence of dopant amount was also studied. Optimum mass flow rates of the dopants were 3.7, 1.1 and 1.0 μmol min(-1) for formic, acetic and propionic acid, respectively. Experimental parameters influencing the extraction efficiency of HF-LLLME, such as NaOH concentration as donor solution, ionic strength of the sample, stirring rate, and extraction time were investigated and optimized. Under the optimum conditions, analytical parameters such as linearity, precision and limit of detection were also evaluated. The linear dynamic range was from 1 to 100 μg L(-1) (r(2)=0.9980) and the limit of detection was 0.35 μg L(-1). Intra- and inter-day precisions were satisfactory with a relative standard deviation (RSD) of 5.9 and 6.7%, respectively. The proposed method was satisfactorily applied for the determination of clomipramine in human plasma and urine.

  11. Mass transfer in binary X-ray systems

    NASA Technical Reports Server (NTRS)

    Mccray, R.; Hatchett, S.

    1975-01-01

    The influence of X-ray heating on gas flows in binary X-ray systems is examined. A simple estimate is obtained for the evaporative wind flux from a stellar atmosphere due to X-ray heating which agrees with numerical calculations by Alme and Wilson (1974) but disagrees with calculations by Arons (1973) and by Basko and Sunyaev (1974) for the Her X-1/HZ Her system. The wind flux is sensitive to the soft X-ray spectrum. The self-excited wind mechanism does not work. Mass transfer in the Hercules system probably occurs by flow of the atmosphere of HZ Her through the gravitational saddle point of the system. The accretion gas stream is probably opaque with atomic density of not less than 10 to the 15th power per cu cm and is confined to a small fraction of 4(pi) steradians. Other binary X-ray systems are briefly discussed.

  12. Energetic correlation of local mass transfer in swirling pipe flow

    SciTech Connect

    Yapici, S.

    1999-04-01

    Mass transfer measurements in a decaying swirl flow in a pipe were carried out, using the electrochemical limiting diffusion current technique. The measurements were taken from local electrodes of 1 mm diameter without a developing concentration boundary layer around. Swirl was generated using short helical guide-vanes with vane angles between 15 and 60 at the outer edge of the vanes to the duct axis. The pressure drop measurements were also taken to perform an energy analysis. For a Reynolds number range of 1700--10,000, the overall energy correlation for a representative length of 36.5 diameter were evaluated to be Sh{sub s}(Sc){sup {minus}0.33} = 0.3705(1 + tan {theta}{sub o}){sup {minus}0.120} X{sup 0.236}, where {theta}{sub o} is the vane angle at the outer edge of the helical swirler and X is the energy dissipation parameter.

  13. Hydromagnetic free convection flow with Hall effect and mass transfer

    NASA Astrophysics Data System (ADS)

    Sahoo, Prasan Kumar

    2016-02-01

    The study of magnetohydrodynamics (MHD) deals with the flow of an electrically conducting fluid in the presence of an electromagnetic field, which has many applications in astrophysics, geophysics and engineering. Objective of the present study in this paper is to consider the effect of dissipation and Hall current on the MHD free convection flow with mass transfer in a porous vertical channel. An exact solution of the governing equations is obtained by solving the complex variables. The effect of Hall parameter (m), Hartmann number (M), and Concentration parameter (Sc) on the velocity and temperature of the fluid is studied. Simulation results show that the shear stress of primary and secondary velocity for the lower plate increases with increase in the strength of Hall parameter (m) and decreases with increase in Hartmann number (M) and concentration parameter (Sc).

  14. Modeling of Heat and Mass Transfer in Fusion Welding

    SciTech Connect

    Zhang, Wei

    2011-01-01

    In fusion welding, parts are joined together by melting and subsequent solidification. Although this principle is simple, complex transport phenomena take place during fusion welding, and they determine the final weld quality and performance. The heat and mass transfer in the weld pool directly affect the size and shape of the pool, the solidification microstructure, the formation of weld defects such as porosity and humping, and the temperature distribution in the fusion zone and heat-affected zone (HAZ). Furthermore, the temperature evolution affects the kinetics and extent of various solid-state phase transformations, which in turn determine the final weld microstructure and mechanical properties. The formation of residual stresses and distortion originates from the thermal expansion and contraction during welding heating and cooling, respectively.

  15. Mass transfer in chromatographic columns studied by PFG NMR.

    PubMed

    Tallarek, U; van Dusschoten, D; Van As, H; Guiochon, G; Bayer, E

    1998-01-01

    Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) is applied to study convective and diffusional transport in chromatographic columns packed with totally porous support particles. Here stagnant zones exist in the particle pores, and diffusional mass-transfer limitations between fluid molecules diffusing in the intraparticle pore network and flowing in the interparticle void space are detected quantitatively. Axial displacement probability distributions were measured for water over a range of Peclet numbers and observation times, with diffusion lengths between 0.15 and 0.91 times the average support particle diameter. The transition towards complete diffusional exchange is demonstrated, thereby also revealing the development of the classical convective dispersion process in a packed bed of (porous) particles.

  16. Mass transfer effects on the transmission of bubble screens

    NASA Astrophysics Data System (ADS)

    Fuster, Daniel; Bergamasco, Luca

    2016-11-01

    In this work we investigate, theoretically and numerically, the reflection and transmission properties of bubble screens excited by pressure wave pulses. We use modified expressions for the bubble resonance frequency and the damping factor in order to capture the influence of mass transfer on the reflection-transmission coefficients. In addition to the influence of variables such as the bubble radius and the averaged inter-bubble distance, the analysis reveals that in conditions close to the saturation line there exists a regime where the heat transport surrounding the bubble plays an important role on the bubble's response also influencing the reflection properties of the bubble screen. The linear analysis allows us to predict the critical vapor content beyond which liquid heat's transport controls the dynamic response of the bubbles. Numerical simulations show that these effects become especially relevant in the nonlinear regime. ANR Cachmap.

  17. Mass Transfer and Light Time Effect Studies for AU Serpentis

    NASA Astrophysics Data System (ADS)

    Amin, S. M.

    2015-02-01

    The orbital period changes of theWUMa eclipsing binary AU Ser are studied using the (O-C) method. We conclude that the period variation is due to mass transfer from the primary star to the secondary one at a very low and decreasing rate dP/dt = -8.872 × 10-8, superimposed on the sinusoidal variation due to a third body orbiting the binary with period 42.87 ± 3.16 years, orbital eccentricity e = 0.52±0.12 and a longitude of periastron passage ! = 133.7±15. On studying the magnetic activity, we have concluded that the Applegate mechanism failed to describe the cycling variation of the (O-C) diagram of AU Ser.

  18. Devices with extended area structures for mass transfer processing of fluids

    DOEpatents

    TeGrotenhuis, Ward E.; Wegeng, Robert S.; Whyatt, Greg A.; King, David L.; Brooks, Kriston P.; Stenkamp, Victoria S.

    2009-04-21

    A microchannel device includes several mass transfer microchannels to receive a fluid media for processing at least one heat transfer microchannel in fluid communication with a heat transfer fluid defined by a thermally conductive wall, and at several thermally conductive fins each connected to the wall and extending therefrom to separate the mass transfer microchannels from one another. In one form, the device may optionally include another heat transfer microchannel and corresponding wall that is positioned opposite the first wall and has the fins and the mass transfer microchannels extending therebetween.

  19. Drop oscillation and mass transfer in alternating electric fields. Progress report

    SciTech Connect

    Carleson, T.E.; Yang, W.

    1991-05-30

    After the second annual progress report to DOE in July 1990, we continued the experimental work for another liquid system. The mathematical model was also improved to include secondary effects due to drop deformation and charge redistribution on the deformed drop surface. Originally, we planned to study a mass transfer process after the hydrodynamic modelling. Due to difficulty in measuring drop concentration during oscillations, we decided to study a heat transfer process instead. Using the analogy between the mass transfer and the heat transfer, we can easily extend the results for the heat transfer study to the mass transfer problem.

  20. Diffusive heat and mass transfer in oscillatory pipe flow

    NASA Astrophysics Data System (ADS)

    Brereton, G. J.; Jalil, S. M.

    2017-07-01

    The enhancement of axial heat and mass transfer by laminar flow oscillation in pipes with axial gradients in temperature and concentration has been studied analytically for the cases of insulated and conducting walls. The axial diffusivity can exceed its molecular counterpart by many orders of magnitude, with a quadratic scaling on the pressure-gradient amplitude and the Prandtl or Schmidt number, and is a bimodal function of oscillatory frequency: quasi-steady behavior at low frequencies and a power-law decay at high frequencies. When the pipe wall is conductive and of sufficient thickness, and the flow oscillation is quasi-steady, the axial diffusivity may be enhanced by a further factor of about ten as a result of increased radial diffusion, for liquid and gas flows in pipes with walls with a wide range of thermal conductivities. Criteria for the wall thickness required to achieve this additional enhancement and for the limits placed on the validity of these solutions by viscous dissipation are also deduced. When the heat transfer per unit flow work achieved by oscillatory pipe flow is contrasted with that of a conventional parallel-flow heat exchanger, it is found to be of comparable size and the ratio of the two is shown to be a function only of the pipe geometry, heat-exchanger mean velocity, and fluid viscosity.

  1. 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.

  2. Computer simulation of liquid/liquid interfaces. I. Theory and application to octane/water

    NASA Astrophysics Data System (ADS)

    Zhang, Yuhong; Feller, Scott E.; Brooks, Bernard R.; Pastor, Richard W.

    1995-12-01

    Statistical ensembles for simulating liquid interfaces at constant pressure and/or surface tension are examined, and equations of motion for molecular dynamics are obtained by various extensions of the Andersen extended system approach. Valid ensembles include: constant normal pressure and surface area; constant tangential pressure and length normal to the interface; constant volume and surface tension; and constant normal pressure and surface tension. Simulations at 293 K and 1 atm normal pressure show consistent results with each other and with a simulation carried out at constant volume and energy. Calculated surface tensions for octane/water (61.5 dyn/cm), octane/vacuum (20.4 dyn/cm) and water/vacuum (70.2 dyn/cm) are in very good agreement with experiment (51.6, 21.7, and 72.8 dyn/cm, respectively). The practical consequences of simulating with two other approaches commonly used for isotropic systems are demonstrated on octane/water: applying equal normal and tangential pressures leads to an instability; and applying a constant isotropic pressure of 1 atm leads to a large positive normal pressure. Both results are expected for a system of nonzero surface tension. Mass density and water polarization profiles in the liquid/liquid and liquid/vapor interfaces are also compared.

  3. Microfluidic droplet-based liquid-liquid extraction: online model validation.

    PubMed

    Lubej, Martin; Novak, Uroš; Liu, Mingqiang; Martelanc, Mitja; Franko, Mladen; Plazl, Igor

    2015-05-21

    Droplet-based liquid-liquid extraction in a microchannel was studied, both theoretically and experimentally. A full 3D mathematical model, incorporating convection and diffusion in all spatial directions along with the velocity profile, was developed to depict the governing transport characteristics of droplet-based microfluidics. The finite elements method, as the most common macroscale simulation technique, was used to solve the set of differential equations regarding conservation of moment, mass and solute concentration in a two-domain system coupled by interfacial surface of droplet-based flow pattern. The model was numerically verified and validated online by following the concentrations of a solute in two phases within the microchannel. The relative azobenzene concentration profiles in a methanol/n-octane two-phase system at different positions along the channel length were retrieved by means of a thermal lens microscopic (TLM) technique coupled to a microfluidic system, which gave results of high spatial and temporal resolution. Very good agreement between model calculations and online experimental data was achieved without applying any fitting procedure to the model parameters.

  4. Impact of Porous Media and NAPL Spatial Variability at the Pore Scale on Interphase Mass Transfer

    NASA Astrophysics Data System (ADS)

    Copty, N. K.; Agaoglu, B.; Scheytt, T.

    2015-12-01

    Sherwood number expressions are often used to model NAPL dissolution in porous media. Such expressions are generally derived from meso-scale experiments and expressed in terms of fluid and porous medium properties averaged over some representative volume. In this work a pore network model is used to examine the influence of porous media and NAPL pore scale variability on interphase mass transfer. The focus was on assessing the impact of (i) NAPL saturation, (ii) interfacial area (iii) NAPL spatial distribution at the pore scale, (iv) grain size heterogeneity and (v) REV or domain size on the apparent interphase mass transfer. Variability of both the mass transfer coefficient that explicitly accounts for the interfacial area and the mass transfer coefficient that lumps the interfacial area was examined. It was shown that pore scale NAPL distribution and its orientation relative to the flow direction have significant impact on flow bypassing and the interphase mass transfer coefficient. This results in a complex non-linear relationship between interfacial area and the REV-based interphase mass transfer rate. In other words, explicitly accounting for the interfacial area does not eliminate the variability of the mass transfer coefficient. Moreover, grain size heterogeneity can also lead to a decrease in the interphase mass transfer. It was also shown that, even for explicitly defined flow patterns, changing the domain size over which the mass transfer process is average influences the extent of NAPL bypassing and dilution and, consequently, the interphase mass transfer.

  5. Mass Transfer of Nickel-Base Alloy Covered Electrode During Shielded Metal Arc Welding

    NASA Astrophysics Data System (ADS)

    Qin, Renyao; He, Guo

    2013-03-01

    The mass transfer in shielded metal arc welding of a group of nickel-base alloy covered electrodes according to AWS specification A5.11-A5.11M was investigated by directly measuring their deposited metal compositions. The results indicate that the chromium mass-transfer coefficient is in the range of 86 to 94 pct, iron in the range of 82 to 89 pct, manganese in the range of 60 to 73 pct, niobium in the range of 44 to 56 pct, and silicon in the range of 41 to 47 pct. The metal mass-transfer coefficient from the core wire is markedly higher than that from the coating. The basicity of slag, the metal contents in the flux coating, and the welding current together affect the mass transfer. As the basicity of slag increases, the mass-transfer coefficients of Mn, Fe, and Cr slightly increase, but those of Nb and Si decrease significantly. As the niobium and manganese contents increase in the coating, their mass-transfer coefficients also increase. However, iron is different. The content of iron in the coating in the range of 8 to 20 wt pct results in the optimal effective mass transfer. The lower, or higher, iron content leads to lower mass-transfer coefficient. As the welding current increases, the mass-transfer coefficients of niobium and manganese decrease, but chromium and silicon increase. Iron has the lowest mass-transfer coefficient when welded under the operating current of 100 A.

  6. Kinetics and mass-transfer phenomena in anaerobic granular sludge.

    PubMed

    Gonzalez-Gil, G; Seghezzo, L; Lettinga, G; Kleerebezem, R

    2001-04-20

    The kinetic properties of acetate-degrading methanogenic granular sludge of different mean diameters were assessed at different up-flow velocities (V(up)). Using this approach, the influence of internal and external mass transfer could be estimated. First, the apparent Monod constant (K(S)) for each data set was calculated by means of a curve-fitting procedure. The experimental results revealed that variations in the V(up) did not affect the apparent K(S)-value, indicating that external mass-transport resistance normally can be neglected. With regard to the granule size, a clear increase in K(S) was found at increasing granule diameters. The experimental data were further used to validate a dynamic mathematical biofilm model. The biofilm model was able to describe reaction-diffusion kinetics in anaerobic granules, using a single value for the effective diffusion coefficient in the granules. This suggests that biogas formation did not influence the diffusion-rates in the granular biomass. Copyright 2001 John Wiley & Sons, Inc.

  7. Bio-inspired Murray materials for mass transfer and activity

    NASA Astrophysics Data System (ADS)

    Zheng, Xianfeng; Shen, Guofang; Wang, Chao; Li, Yu; Dunphy, Darren; Hasan, Tawfique; Brinker, C. Jeffrey; Su, Bao-Lian

    2017-04-01

    Both plants and animals possess analogous tissues containing hierarchical networks of pores, with pore size ratios that have evolved to maximize mass transport and rates of reactions. The underlying physical principles of this optimized hierarchical design are embodied in Murray's law. However, we are yet to realize the benefit of mimicking nature's Murray networks in synthetic materials due to the challenges in fabricating vascularized structures. Here we emulate optimum natural systems following Murray's law using a bottom-up approach. Such bio-inspired materials, whose pore sizes decrease across multiple scales and finally terminate in size-invariant units like plant stems, leaf veins and vascular and respiratory systems provide hierarchical branching and precise diameter ratios for connecting multi-scale pores from macro to micro levels. Our Murray material mimics enable highly enhanced mass exchange and transfer in liquid-solid, gas-solid and electrochemical reactions and exhibit enhanced performance in photocatalysis, gas sensing and as Li-ion battery electrodes.

  8. Bio-inspired Murray materials for mass transfer and activity

    PubMed Central

    Zheng, Xianfeng; Shen, Guofang; Wang, Chao; Li, Yu; Dunphy, Darren; Hasan, Tawfique; Brinker, C. Jeffrey; Su, Bao-Lian

    2017-01-01

    Both plants and animals possess analogous tissues containing hierarchical networks of pores, with pore size ratios that have evolved to maximize mass transport and rates of reactions. The underlying physical principles of this optimized hierarchical design are embodied in Murray's law. However, we are yet to realize the benefit of mimicking nature's Murray networks in synthetic materials due to the challenges in fabricating vascularized structures. Here we emulate optimum natural systems following Murray's law using a bottom-up approach. Such bio-inspired materials, whose pore sizes decrease across multiple scales and finally terminate in size-invariant units like plant stems, leaf veins and vascular and respiratory systems provide hierarchical branching and precise diameter ratios for connecting multi-scale pores from macro to micro levels. Our Murray material mimics enable highly enhanced mass exchange and transfer in liquid–solid, gas–solid and electrochemical reactions and exhibit enhanced performance in photocatalysis, gas sensing and as Li-ion battery electrodes. PMID:28382972

  9. Bio-inspired Murray materials for mass transfer and activity.

    PubMed

    Zheng, Xianfeng; Shen, Guofang; Wang, Chao; Li, Yu; Dunphy, Darren; Hasan, Tawfique; Brinker, C Jeffrey; Su, Bao-Lian

    2017-04-06

    Both plants and animals possess analogous tissues containing hierarchical networks of pores, with pore size ratios that have evolved to maximize mass transport and rates of reactions. The underlying physical principles of this optimized hierarchical design are embodied in Murray's law. However, we are yet to realize the benefit of mimicking nature's Murray networks in synthetic materials due to the challenges in fabricating vascularized structures. Here we emulate optimum natural systems following Murray's law using a bottom-up approach. Such bio-inspired materials, whose pore sizes decrease across multiple scales and finally terminate in size-invariant units like plant stems, leaf veins and vascular and respiratory systems provide hierarchical branching and precise diameter ratios for connecting multi-scale pores from macro to micro levels. Our Murray material mimics enable highly enhanced mass exchange and transfer in liquid-solid, gas-solid and electrochemical reactions and exhibit enhanced performance in photocatalysis, gas sensing and as Li-ion battery electrodes.

  10. Numerical simulations of heat and mass transfer at ablating surface in hypersonic flow

    NASA Astrophysics Data System (ADS)

    Bocharov, A. N.; Golovin, N. N.; Petrovskiy, V. P.; Teplyakov, I. O.

    2015-11-01

    The numerical technique was developed to solve heat and mass transfer problem in 3D hypersonic flow taking into account destruction of thermal protection system. Described technique was applied for calculation of heat and mass transfer in sphere-cone shaped body. The data on temperature, heat flux and mass flux were obtained.

  11. Coarse-Graining the Liquid-Liquid Interfaces with the MARTINI Force Field: How Is the Interfacial Tension Reproduced?

    PubMed

    Ndao, Makha; Devémy, Julien; Ghoufi, Aziz; Malfreyt, Patrice

    2015-08-11

    We report two-phase coarse-grained (CG) simulations of organic-water liquid-liquid interfaces with the MARTINI force field. We discuss the ability of the CG force field to predict quantitatively the interfacial tension of alkanes-water, benzene-water, chloroform-water, and alcohol-water systems. The performance of the prediction of the interfacial tension is evaluated through its dependence on temperature and alkane length. This study contributes to the challenging discussion about the robustness and the transferability of the MARTINI force field to interfacial properties. We have also used the distributions of the molecules along the direction normal to the interface to investigate the composition of the interfacial region and to compare the simulated densities of the coexisting phases with experiments.

  12. Liquid-liquid phase transitions in supercooled water studied by computer simulations of various water models.

    PubMed

    Brovchenko, Ivan; Geiger, Alfons; Oleinikova, Alla

    2005-07-22

    Liquid-liquid and liquid-vapor coexistence regions of various water models were determined by Monte Carlo (MC) simulations of isotherms of density fluctuation-restricted systems and by Gibbs ensemble MC simulations. All studied water models show multiple liquid-liquid phase transitions in the supercooled region: we observe two transitions of the TIP4P, TIP5P, and SPCE models and three transitions of the ST2 model. The location of these phase transitions with respect to the liquid-vapor coexistence curve and the glass temperature is highly sensitive to the water model and its implementation. We suggest that the apparent thermodynamic singularity of real liquid water in the supercooled region at about 228 K is caused by an approach to the spinodal of the first (lowest density) liquid-liquid phase transition. The well-known density maximum of liquid water at 277 K is related to the second liquid-liquid phase transition, which is located at positive pressures with a critical point close to the maximum. A possible order parameter and the universality class of liquid-liquid phase transitions in one-component fluids are discussed.

  13. Effectiveness of Liquid-Liquid Extraction, Solid Phase Extraction, and Headspace Technique for Determination of Some Volatile Water-Soluble Compounds of Rose Aromatic Water.

    PubMed

    Canbay, Hale Seçilmiş

    2017-01-01

    Steam distillation is used to isolate scent of rose flowers. Rose aromatic water is commonly used in European cuisine and aromatherapy besides its use in cosmetic industry for its lovely scent. In this study, three different sampling techniques, liquid-liquid extraction (LLE), headspace technique (HS), and solid phase extraction (SPE), were compared for the analysis of volatile water-soluble compounds in commercial rose aromatic water. Some volatile water-soluble compounds of rose aromatic water were also analyzed by gas chromatography mass spectrometry (GCMS). In any case, it was concluded that one of the solid phase extraction methods led to higher recoveries for 2-phenylethyl alcohol (PEA) in the rose aromatic water than the liquid-liquid extraction and headspace technique. Liquid-liquid extraction method provided higher recovery ratios for citronellol, nerol, and geraniol than others. Ideal linear correlation coefficient values were observed by GCMS for quantitative analysis of volatile compounds (r(2) ≥ 0.999). Optimized methods showed acceptable repeatability (RSDs < 5%) and excellent recovery (>95%). For compounds such as α-pinene, linalool, β-caryophyllene, α-humulene, methyl eugenol, and eugenol, the best recovery values were obtained with LLE and SPE.

  14. Determination of 19 sulfonamides residues in pork samples by combining QuEChERS with dispersive liquid-liquid microextraction followed by UHPLC-MS/MS.

    PubMed

    Li, Xiaojing; Yu, Hong; Peng, Rongfei; Gan, Pingsheng

    2017-03-01

    A new simple and rapid pretreatment method for simultaneous determination of 19 sulfonamides in pork samples was developed through combining the QuEChERS method with dispersive liquid-liquid microextraction followed by ultra-high performance liquid chromatography with tandem mass spectrometry. The sample preparation involves extraction/partitioning with QuEChERS method followed by dispersive liquid-liquid microextraction using tetrachloroethane as extractive solvent and the acetonitrile extract as dispersive solvent that obtained by QuEChERS. The enriched tetrachloroethane organic phase by dispersive liquid-liquid microextraction was evaporated, reconstituted with 100 μL acetonitrile/water (1:9 v/v) and injected into an ultra-high performance liquid chromatography with a mobile phase composed of acetonitrile and 0.1% v/v formic acid under gradient elution and separated using a BHE C18 column. Various parameters affecting the extraction efficiency were investigated. Matrix-matched calibration curves were established. Good linear relationships were obtained for all analytes in a range of 2.0-100 μg/kg and the limits of detection were 0.04-0.49 μg/kg. Average recoveries at three spiking levels were in the range of 78.3-106.1% with relative standard deviations less than 12.7% (n = 6). The developed method was successfully applied to determine sulfonamide residues in pork samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Effectiveness of Liquid-Liquid Extraction, Solid Phase Extraction, and Headspace Technique for Determination of Some Volatile Water-Soluble Compounds of Rose Aromatic Water

    PubMed Central

    2017-01-01

    Steam distillation is used to isolate scent of rose flowers. Rose aromatic water is commonly used in European cuisine and aromatherapy besides its use in cosmetic industry for its lovely scent. In this study, three different sampling techniques, liquid-liquid extraction (LLE), headspace technique (HS), and solid phase extraction (SPE), were compared for the analysis of volatile water-soluble compounds in commercial rose aromatic water. Some volatile water-soluble compounds of rose aromatic water were also analyzed by gas chromatography mass spectrometry (GCMS). In any case, it was concluded that one of the solid phase extraction methods led to higher recoveries for 2-phenylethyl alcohol (PEA) in the rose aromatic water than the liquid-liquid extraction and headspace technique. Liquid-liquid extraction method provided higher recovery ratios for citronellol, nerol, and geraniol than others. Ideal linear correlation coefficient values were observed by GCMS for quantitative analysis of volatile compounds (r2 ≥ 0.999). Optimized methods showed acceptable repeatability (RSDs < 5%) and excellent recovery (>95%). For compounds such as α-pinene, linalool, β-caryophyllene, α-humulene, methyl eugenol, and eugenol, the best recovery values were obtained with LLE and SPE. PMID:28791049

  16. Theoretical approach for enhanced mass transfer effects in-duct flue gas desulfurization processes

    SciTech Connect

    1989-08-21

    Mass transfer investigation experiments were performed to determine the controlling physical and chemical processes that limit Ca(OH){sub 2} sorbent utilization in flue gas desulfurization. A computer model has been established to estimate the relative contribution of gas- and liquid-phase mass transfer and inherent sorbent reactivity. Currently, the mass transfer investigation tests are on schedule and will be continued next year. More pilot-plant tests are planned to support field tests and mass transfer enhancement evaluations. 48 figs., 7 tabs.

  17. Direct Geoelectrical Evidence of Mass Transfer at the Lab scale

    NASA Astrophysics Data System (ADS)

    Swanson, R. D.; Singha, K.; Day-Lewis, F. D.; Keating, K.; Binley, A.; Clifford, J.; Haggerty, R.

    2011-12-01

    At many field sites, anomalous tailing behavior-- a long, slow decrease of solute concentration in time-- is observed yet cannot be explained with the advection-dispersion model. One explanation for this commonly observed behavior is the exchange of solute between mobile and immobile domains; however, direct experimental observations of this controlling process remain elusive. Circumstantial evidence for a less-mobile phase is typically inferred from tailing behavior observed in fluid samples of the mobile phase. Electrical methods provide a measure of the total solutes in both the immobile and mobile domain and therefore have been hypothesized to provide, in combination with fluid sampling, direct experimental evidence for a less-mobile and mobile model, yet experimental evidence is needed to support this claim. Here, we conduct column solute tracer tests and measure both electrical resistivity and fluid conductivity on unconsolidated, well-sorted sand in addition to fine and coarse fractions of the porous zeolite clinoptilolite. We examine nearly co-located time-lapse standard fluid conductivity and bulk apparent resistivity measurements to identify solute exchange between multiple domains at the lab scale. Our results show extensive tailing behavior in both fluid and bulk electrical conductivity measurements in the zeolite but not in sand, providing evidence for a mobile-immobile framework. Transport parameters are estimated by minimizing the root-mean-square error between the observed and simulated fluid conductivity in COMSOL Multiphysics. These best-fit parameters support our claims of mass transfer occurring in the zeolite columns and provide the first direct electrical evidence of dual-domain mass