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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. Physical modeling of liquid/liquid mass transfer in gas stirred ladles

    NASA Astrophysics Data System (ADS)

    Kim, Seon-Hyo; Fruehan, R. J.

    1987-06-01

    Several of the metallurgical reactions occurring in gas stirred steel ladles are controlled by liquid phase mass transfer between the metal and slag. In order to calculate the rate of these reactions, information about the two phase mass transfer parameter is necessary. The mass transfer between two immiscible liquids, oil and water simulating slag and steel, respectively, was measured in a scale model of a ladle. The mass transferred species was thymol which has an equilibrium partition ratio between oil and water similar to that for sulfur between slag and metal. The mass transfer rate was measured as a function of gas flow rate, tuyere position and size, method of injection, oil viscosity, and oil/water volume ratio. In addition, mixing times in the presence of the oil layer and mass transfer coefficient for the dissolution of solid benzoic acid rods were measured. The results show that there are three gas flow rate regimes in which the dependence of mass transfer on gas flow rate is different. At a critical gas flow rate, the oil layer breaks into droplets which are entrained into the water, resulting in an increase in the two phase interfacial area. This critical gas flow rate was found to be a function of tuyere position, oil volume, densities of two phases, and interfacial tension. Two phase mass transfer for a lance and a tuyere was found to be the same for the same stirring energy in low energy regions regardless of lance depth. Mass transfer is faster for a center tuyere as compared to an offcenter tuyere, but mixing times are smaller for the offcenter tuyere. From the results obtained, the optimum stirring conditions for metallurgical reactions are qualitatively discussed.

  3. 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

  4. Electron transfer kinetics at polarized nanoscopic liquid/liquid interfaces.

    PubMed

    Cai, Chenxin; Mirkin, Michael V

    2006-01-11

    Rapid kinetics of electron transfer (ET) reactions across the interface between water and 1,2-dichloroethane were measured by steady-state voltammetry at nanopipet electrodes (50- to 400-nm orifice radius). The origins of previously reported imperfect voltammetric responses of ET reactions at micropipets were investigated. Several new experimental systems were explored, and two of them yielded high-quality voltammograms suitable for kinetic experiments. The determined standard rate constants were compared to those measured previously at polarized and nonpolarized liquid/liquid interfaces. The effect of the interfacial dimensions on the magnitude of the apparent ET rate constant is discussed. A new approach to ET kinetic measurements based on the use of the scanning electrochemical microscope with a nanopipet tip and a metallic substrate has been developed and employed to check the validity of determined kinetic parameters. PMID:16390144

  5. Ion transfer battery: storing energy by transferring ions across liquid-liquid interfaces.

    PubMed

    Peljo, Pekka; Bichon, Marie; Girault, Hubert H

    2016-07-28

    A battery utilizing the Galvani potential difference between aqueous and organic phases is demonstrated. The battery consists of two organic redox electrolytes separated by an immiscible aqueous phase. The charge is stored by transferring a salt from the aqueous phase into organic phases in ion transfer coupled electron transfer reactions. PMID:27327108

  6. 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. PMID:25730302

  7. 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. PMID:26423626

  8. 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.

  9. 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…

  10. Photoinduced Electron Transfer of PAMAM Dendrimer-Zinc(II) Porphyrin Associates at Polarized Liquid|Liquid Interfaces.

    PubMed

    Nagatani, Hirohisa; Sakae, Hiroki; Torikai, Taishi; Sagara, Takamasa; Imura, Hisanori

    2015-06-01

    The heterogeneous photoinduced electron-transfer reaction of the ion associates between NH2-terminated polyamidoamine (PAMAM) dendrimers and 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrinato zinc(II) (ZnTPPS(4-)) was studied at the polarized water|1,2-dichloroethane (DCE) interface. The positive photocurrent arising from the photoreduction of ZnTPPS(4-) by a lipophilic quencher, decamethylferrocene, in the interfacial region was significantly enhanced by the ion association with the PAMAM dendrimers. The photocurrent response of the dendrimer-ZnTPPS(4-) associates was dependent on the pH condition and on the generation of dendrimer. A few cationic additives such as polyallylamine and n-octyltrimethyammonium were also examined as alternatives to the PAMAM dendrimer, but the magnitude of the photocurrent enhancement was rather small. The high photoreactivity of the dendrimer-ZnTPPS(4-) associates was interpreted mainly as a result of the high interfacial concentration of photoreactive porphyrin units associated stably with the dendrimer which was preferably adsorbed at the polarized water|DCE interface. The photochemical data observed in the second and fourth generation PAMAM dendrimer systems demonstrated that the higher generation dendrimer which can incorporate a porphyrin molecule more completely in the interior is less efficient for the photocurrent enhancement at the interface. These results indicated that the photoreactivity of ionic reactant at a polarized liquid|liquid interface can readily be modified via ion association with the charged dendrimer. PMID:25989445

  11. 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

  12. Application of dispersive liquid-liquid microextraction for the determination of phosphatidylethanol in blood by liquid chromatography tandem mass spectrometry.

    PubMed

    Cabarcos, Pamela; Ángel Cocho, José; Moreda, Antonio; Míguez, Martha; Jesús Tabernero, María; Fernández, Purificación; María Bermejo, Ana

    2013-07-15

    Phosphatidylethanol (PEth) is a phospholipid which requires for its metabolic formation the presence of relatively high ethanol levels. PEth is thus a promising marker to quentify ethanol abuse. Dispersive liquid-liquid microextraction has become a popular technique because it is fast, inexpensive, easy to operate and consumes low volume of organic solvent. In this method, the appropriate mixture of extraction solvent (230 μL dichloromethane) and disperser solvent (630 μL acetone) are injected into the sample by syringe, rapidly. The liquid chromatography method using a reversed phase-C8 column and a negative ion mode electrospray ionization tandem mass spectrometry detection instrument was developed for the determination of small amounts of PEth that might be present in blood samples, using phosphatidylbutanol (PBut) as an internal standard. The sensitivity of detection obtained with tandem MS was better than that of previous methods. Good linearity was obtained for a range of LOQ-10 μg/mL for PEth, whereas all of the deviations in precision and accuracy were less than 15% except for the LLOQ, where it should not exceed 20%. A set of 50 blood samples were analyzed by such method and whole blood concentrations of PEth 16:0/18:1 ranged from LLOQ to 1.71 μg/mL. PMID:23622544

  13. 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. PMID:25676868

  14. Determination of suvorexant in human plasma using 96-well liquid-liquid extraction and HPLC with tandem mass spectrometric detection.

    PubMed

    Breidinger, S A; Simpson, R C; Mangin, E; Woolf, E J

    2015-10-01

    A method, using liquid chromatography with tandem mass spectrometric detection (LC-MS/MS), was developed for the determination of suvorexant (MK-4305, Belsomra(®)), a selective dual orexin receptor antagonist for the treatment insomnia, in human plasma over the concentration range of 1-1000ng/mL. Stable isotope labeled (13)C(2)H3-suvorexant was used as an internal standard. The sample preparation procedure utilized liquid-liquid extraction, in the 96-well format, of a 100μL plasma sample with methyl t-butyl ether. The compounds were chromatographed under isocratic conditions on a Waters dC18 (50×2.1mm, 3μm) column with a mobile phase consisting of 30/70 (v/v %) 10mM ammonium formate, pH3/acetonitrile at a flow rate of 0.3mL/min. Multiple reaction monitoring of the precursor-to-product ion pairs for suvorexant (m/z 451→186) and (13)C(2)H3-suvorexant (m/z 455→190) on an Applied Biosystems API 4000 tandem mass spectrometer was used for quantitation. Intraday assay precision, assessed in six different lots of control plasma, was within 10% CV at all concentrations, while assay accuracy ranged from 95.6 to 105.0% of nominal. Quality control (QC) samples in plasma were stored at -20°C. Initial within day analysis of QCs after one freeze-thaw cycle showed accuracy within 9.5% of nominal with precision (CV) of 6.7% or less. The plasma QC samples were demonstrated to be stable for up to 25 months at -20°C. The method described has been used to support clinical studies during Phase I through III of clinical development. PMID:26343269

  15. 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%. PMID:24780255

  16. 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%. PMID:27016119

  17. Electrophoretic transport of biomolecules across liquid-liquid interfaces.

    PubMed

    Hahn, Thomas; Münchow, Götz; Hardt, Steffen

    2011-05-11

    The mass transfer resistance of a liquid-liquid interface in an aqueous two-phase system composed of poly(ethylene glycol) and dextran is investigated. Different types of proteins and DNA stained with fluorescent dyes serve as probes to study the transport processes close to the interface. A microfluidic device is employed to enable the electrophoretic transport of biomolecules from one phase to another. The results obtained for proteins can be explained solely via the different electrophoretic mobilities and different affinities of the molecules to the two phases, without any indications of a significant mass transfer resistance of the liquid-liquid interface. By contrast, DNA molecules adsorb to the interface and only desorb under an increased electric field strength. The desorption process carries the signature of a thermally activated escape from a metastable state, as reflected in the exponential decay of the fluorescence intensity at the interface as a function of time. PMID:21508474

  18. 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. PMID:25441341

  19. 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. PMID:26257251

  20. 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. PMID:24793850

  1. 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.

  2. Multicomponent mass transfer

    SciTech Connect

    Taylor, R.; Krishna, R.

    1993-01-01

    This is an important book on multicomponent mass transfer, meant for readers already acquainted with the theory of mass transfer and the fundamentals of transport phenomena. Part 1, entitled Molecular Diffusion, contains the following chapters: Preliminary Concepts; The Maxwell-Stefan Relations; Fick's Law; Estimation of Diffusion Coefficients; Solution of multicomponent Diffusion Problems: The Linearized Theory; and Solution of Multicomponent Diffusion Problems: Effective Diffusivity Methods. Part 2, entitled Interphase Transfer, contains the following chapters: Mass-Transfer Coefficients; Film Theory; Unsteady-State Mass-Transfer Models; Mass Transfer in Turbulent Flow; and Simultaneous Mass and Energy Transfer. Part 3, entitled Design, contains the following chapters: Multicomponent Distillation: Mass-Transfer Models; Multicomponent Distillation: Efficiency Models; Multicomponent Distillation: A Nonequilibrium Stage Model; and Condensation of Vapor Mixtures. Appendices are provided on matrix algebra, equation-solving and estimation of a thermodynamic derivative matrix. A computer diskette is provided with the book; the examples in Chapters 1--13 are solvable using this diskette and the commercial package Mathcad which the user must obtain. A separate software package, Chemsep, is needed for some of the exercises in Chapter 14.

  3. 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. PMID:25199442

  4. Screening and quantitative determination of twelve acidic and neutral pharmaceuticals in whole blood by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry.

    PubMed

    Simonsen, Kirsten Wiese; Steentoft, Anni; Buck, Maike; Hansen, Lene; Linnet, Kristian

    2010-09-01

    We describe a multi-method for simultaneous identification and quantification of 12 acidic and neutral compounds in whole blood. The method involves a simple liquid-liquid extraction, and the identification and quantification are performed using liquid chromatography-tandem mass spectrometry. The method was fully validated for salicylic acid, paracetamol, phenobarbital, carisoprodol, meprobamate, topiramate, etodolac, chlorzoxazone, furosemide, ibuprofen, warfarin, and salicylamide. The method also tentatively includes thiopental, theophylline, piroxicam, naproxen, diclophenac, and modafinil, but these drugs were not included in the full validation program and are not described in detail here. Limit of quantitation was 1 mg/kg for the compounds with coefficients of variation of < 20%, except for furosemide, which had a coefficient of variation of 32% at limit of quantitation. The measuring interval was wide for most components. Extraction efficiencies were high, reflecting the high-yield capacity of the method. PMID:20822673

  5. Analysis of potential migrants from plastic materials in milk by liquid chromatography-mass spectrometry with liquid-liquid extraction and low-temperature purification.

    PubMed

    Bodai, Zsolt; Szabó, Bálint Sámuel; Novák, Márton; Hámori, Susanne; Nyiri, Zoltán; Rikker, Tamás; Eke, Zsuzsanna

    2014-10-15

    A simple and fast analytical method was developed for the determination of six UV stabilizers (Cyasorb UV-1164, Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 327, and Tinuvin 1577) and five antioxidants (Irgafos 168, Irganox 1010, Irganox 3114, Irganox 3790, and Irganox 565) in milk. For sample preparation liquid-liquid extraction with low-temperature purification combined with centrifugation was used to remove fats, proteins, and sugars. After the cleanup step, the sample was analyzed with high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). External standard and matrix calibrations were tested. External calibration proved to be acceptable for Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 327, Irganox 3114, and Irganox 3790. The method was successfully validated with matrix calibration for all compounds. Method detection limits were between 0.25 and 10 μg/kg. Accuracies ranged from 93 to 109%, and intraday precisions were <13%. PMID:25251884

  6. 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). PMID:26920309

  7. 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. PMID:25882424

  8. 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. PMID:21280211

  9. Probing Ion Transfer across Liquid-Liquid Interfaces by Monitoring Collisions of Single Femtoliter Oil Droplets on Ultramicroelectrodes.

    PubMed

    Deng, Haiqiang; Dick, Jeffrey E; Kummer, Sina; Kragl, Udo; Strauss, Steven H; Bard, Allen J

    2016-08-01

    We describe a method of observing collisions of single femtoliter (fL) oil (i.e., toluene) droplets that are dispersed in water on an ultramicroelectrode (UME) to probe the ion transfer across the oil/water interface. The oil-in-water emulsion was stabilized by an ionic liquid, in which the oil droplet trapped a highly hydrophobic redox probe, rubrene. The ionic liquid also functions as the supporting electrolyte in toluene. When the potential of the UME was biased such that rubrene oxidation would be possible when a droplet collided with the electrode, no current spikes were observed. This implies that the rubrene radical cation is not hydrophilic enough to transfer into the aqueous phase. We show that current spikes are observed when tetrabutylammonium trifluoromethanesulfonate or tetrahexylammonium hexafluorophosphate are introduced into the toluene phase and when tetrabutylammonium perchlorate is introduced into the water phase, implying that the ion transfer facilitates electron transfer in the droplet collisions. The current (i)-time (t) behavior was evaluated quantitatively, which indicated the ion transfer is fast and reversible. Furthermore, the size of these emulsion droplets can also be calculated from the electrochemical collision. We further investigated the potential dependence on the electrochemical collision response in the presence of tetrabutylammonium trifluoromethanesulfonate in toluene to obtain the formal ion transfer potential of tetrabutylammonium across the toluene/water interface, which was determined to be 0.754 V in the inner potential scale. The results yield new physical insights into the charge balance mechanism in emulsion droplet collisions and indicate that the electrochemical collision technique can be used to probe formal ion transfer potentials between water and solvents with very low (ε < 5) dielectric constants. PMID:27387789

  10. 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. PMID:25939092

  11. Determination of volatile nitrosamines in meat products by microwave-assisted extraction and dispersive liquid-liquid microextraction coupled to gas chromatography-mass spectrometry.

    PubMed

    Campillo, Natalia; Viñas, Pilar; Martínez-Castillo, Nelson; Hernández-Córdoba, Manuel

    2011-04-01

    Microwave-assisted extraction (MAE) and dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) were evaluated for use in the extraction and preconcentration of volatile nitrosamines in meat products. Parameters affecting MAE, such as the extraction solvent used, and DLLME, including the nature and volume of the extracting and disperser solvents, extraction time, salt addition and centrifugation time, were optimized. In the MAE method, 0.25g of sample mass was extracted in 10mL NaOH (0.05M) in a closed-vessel system. For DLLME, 1.5mL of methanol (disperser solvent) containing 20μL of carbon tetrachloride (extraction solvent) was rapidly injected by syringe into 5mL of the sample extract solution (previously adjusted to pH 6), thereby forming a cloudy solution. Phase separation was performed by centrifugation, and a volume of 3μL of the sedimented phase was analyzed by GC-MS. The enrichment factors provided by DLLME varied from 220 to 342 for N-nitrosodiethylamine and N-nitrosopiperidine, respectively. The matrix effect was evaluated for different samples, and it was concluded that sample quantification can be carried out by aqueous calibration. Under the optimized conditions, detection limits ranged from 0.003 to 0.014ngmL(-1) for NPIP and NMEA, respectively (0.12-0.56ngg(-1) in the meat products). PMID:21376329

  12. 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. PMID:25965876

  13. Sensitive liquid chromatography positive electrospray tandem mass spectrometry method for the quantitation of tegaserod in human plasma using liquid-liquid extraction.

    PubMed

    Nirogi, Ramakrishna; Kandikere, Vishwottam; Mudigonda, Koteshwara

    2009-02-01

    A sensitive and rapid high-performance liquid chromatography-positive ion electrospray tandem mass spectrometry method is developed and validated for the quantitation of tegaserod in human plasma. Following liquid-liquid extraction, the analytes are separated using an isocratic mobile phase on a reversed-phase column and analyzed by tandem mass spectrometry in the multiple reaction monitoring mode using the respective (M+H)+ ions, m/z 302 to 173 for tegaserod and m/z 409 to 228 for the internal standard. The assay exhibits a linear dynamic range of 100-10000 pg/mL for tegaserod in human plasma. The lower limit of quantitation is 100 pg/mL with a relative standard deviation of less than 7%. Acceptable precision and accuracy are obtained for concentrations over the standard curve range. A run time of 2.0 min for each sample makes it possible to analyze more than 250 human plasma samples per day. The validated method is successfully used to analyze human plasma samples for application in pharmacokinetic, bioavailability, or bioequivalence studies. PMID:19222925

  14. Determination of 2-ethylhexyl 4-(dimethylamino) benzoate using membrane-assisted liquid-liquid extraction and gas chromatography-mass spectrometric detection.

    PubMed

    March, J G; Genestar, C; Simonet, B M

    2009-06-01

    A flow-cell for micro-porous membrane liquid-liquid extraction with a sheet membrane was used to extract 2-ethylhexyl 4-(dimethylamino) benzoate (EDB) from urine of solar-cream users and spiked wine samples. The cell enabled the target analyte to be extracted from 7.9 mL of donor solution into 200 microL of acceptor solution (decane). After extraction, the acceptor solution was transferred to a micro-vial for GC-MS analysis without derivation. In this work, variables affecting the enrichment factor were also studied, such as organic solvent, extraction time, recirculation flow of the donor solution through the donor chamber, presence of potassium chloride and ethanol in the donor solution and pH. The method has been evaluated in terms of linearity, sensitivity, precision, limits of detection and quantification and extraction efficiency. Limits of quantification were 1 and 3 microg L(-1) EDB for urine and wine, respectively. Quantitative analysis has been carried out by applying the method of standard additions. Within- and between-day relative standard deviations were lower than 12% and 20%, respectively. EDB was found in the urine of users of cream containing EDB in the concentration interval 1.2-7.2 microg L(-1). Therefore, this provides evidence of EDB dermal absorption and subsequent excretion through the urinary tract. EDB was not found in the analysed wine samples. PMID:19347661

  15. 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. PMID:26592585

  16. 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. PMID:25618021

  17. 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). PMID:20652544

  18. 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. PMID:25952882

  19. 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. PMID:27063712

  20. Determination of immunosuppressive drugs in human urine and serum by surface-assisted laser desorption/ionization mass spectrometry with dispersive liquid-liquid microextraction.

    PubMed

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

    2016-01-01

    A rapid and sensitive method for the determination of immunosuppressive drugs through surface-assisted laser desorption/ionization mass spectrometric detection (SALDI/MS) was developed. Colloidal Pd and α-cyano-4-hydroxycinnamic acid (CHCA) were used as the SALDI co-matrix. To eliminate interference and enhance the sensitivity, dispersive liquid-liquid microextraction (DLLME) was employed to extract the immunosuppressive drugs from the aqueous solutions. Under optimal extraction and detection conditions, calibration curves for cyclosporine and everolimus in aqueous solutions were linear over a concentration range from 0.01 to 1.20 μM. For sirolimus, the linear concentration range of the calibration curve was from 0.05 to 2.00 μM. The limits of detection (LODs) were calculated to be 3, 3, and 14 nM for cyclosporine, everolimus, and sirolimus, respectively. The enrichment factors of DLLME were calculated to be 108, 122, and 101 for cyclosporine, everolimus, and sirolimus, respectively. This novel method was successfully applied for the determination of immunosuppressive drugs in human urine and serum samples. PMID:26521180

  1. Rapid Monitoring and Determination of Class 1 Residual Solvents in Pharmaceuticals Using Dispersive Liquid-Liquid Microextraction and Gas Chromatography-Mass Spectrometry.

    PubMed

    Heydari, Rouhollah; Azizi, Saber

    2015-07-01

    A simple and rapid dispersive liquid-liquid microextraction (DLLME) method coupled with gas chromatography-mass spectrometry (GC-MS) for monitoring and determination of class 1 residual solvents, benzene (Bz), carbon tetrachloride (CT), 1,2-dichloroethane (1,2-DCE), 1,1-dichloroethene (1,1-DCE), 1,1,1-trichloroethane (1,1,1-TCE), in pharmaceuticals was developed and evaluated. The parameters affecting the extraction efficiency of analytes such as type and volume of extraction solvent, type and volume of dispersive solvent and ionic strength were investigated and optimized. 1-Octanol and methanol proved to be the most suitable extraction and dispersive solvents, respectively. The method showed linearity for 1,1-DCE, 1,1,1-TCE, CT, Bz and 1,2-DCE in the ranges of 0.001-80, 0.005-80, 0.002-80, 0.0001-40 and 0.001-80 µg/mL, respectively. The relative recoveries were in the range of 84-92, 87-98, 83-94, 89-98 and 87-96% for 1,1-DCE, 1,1,1-TCE, CT, Bz and 1,2-DCE, respectively. The obtained results showed that the proposed method can be used to monitor and determine class 1 residual solvents in pharmaceuticals. PMID:25398952

  2. 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. PMID:27317004

  3. 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.

  4. An in situ derivatization - dispersive liquid-liquid microextraction combined with gas-chromatography - mass spectrometry for determining biogenic amines in home-made fermented alcoholic drinks.

    PubMed

    Płotka-Wasylka, Justyna; Simeonov, Vasil; Namieśnik, Jacek

    2016-07-01

    A novel dispersive liquid-liquid microextraction (DLLME) gas chromatography mass-spectrometry (GC-MS) method was developed for the determination of 13 biogenic amines in home-made wine samples. The method allows to simultaneous extraction and derivatization of the amines providing a simple and fast mode of extract enrichment. During the study, two different procedures were examined. Statistical analysis was performed to choose better procedure, as well as the conditions of derivatization reaction. At least, a mixture of methanol (dispersive solvent; 215μL), chloroform (extractive solvent; 400μL), and isobutyl choloroformate (derivatizing reagent; 90μL) was used as extractive/derivatizing reagent, added to 5mL of sample. The addition of mixture of pyridine and HCl was necessary to eliminate the by-products. The proposed method showed good linearity (correlation coefficients >0.9961), good recoveries (from 77 to 105%), and good intra-day precision (below 13%) and inter-day precision (below 10%). Moreover, detection limits were never over 4.1μg/L. The developed method was successfully applied to the analysis of 17 home-made wine samples not regulated by law. All of the biogenic amines analyzed were found in most of the wines. PMID:27237593

  5. 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%. PMID:25841611

  6. 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

  7. 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.

  8. 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. PMID:27302585

  9. 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

    2015-01-01

    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. PMID:25537172

  10. 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. PMID:24054273

  11. 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. PMID:24468359

  12. [Determination of capsaicinoids and eugenol in waste-edible-oil by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry].

    PubMed

    Zhang, Zhong; Ren, Fei; Zhang, Pan

    2012-11-01

    A method was developed for the determination of capsaicinoids (capsaicin, dihydrocapsaicin and synthetic capsaicin) and eugenol in waste-edible-oil extracted by liquid-liquid extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS). The capsaicinoids and eugenol in waste-edible-oil were extracted by methanol, and then separated by a SUPEL COSIL ABZ + Plus dC18 column (150 mm x4.6 mm, 5 microm). The analysis was performed by MS/MS with electrospray ionization in positive and negative ion modes with multiple reaction monitoring (MRM). The limits of detection for capsaicin, dihydrocapsaicin, synthetic capsaicin and eugenol were 0.02, 0.03, 0.03 and 0.6 microg/L, respectively. The good linear relationships were obtained in certain concentration ranges of capsaicinoids and eugenol. The relative standard deviations (RSDs, n=5) of same-worker and different-worker were less than 5%. The method is exclusive, sensitive and accurate, and can be used in waste-edible-oil determination. PMID:23451511

  13. Salting-out-assisted liquid-liquid extraction with acetonitrile for the determination of trimetazidine in rat plasma using liquid chromatography-mass spectrometry.

    PubMed

    Xiong, Xin; Yang, Li

    2015-02-01

    A high-throughout bioanalytical method based on salting-out-assisted liquid/liquid extraction (SALLE) method with acetonitrile and mass spectrometry-compatible salts followed by LC-MS/MS analysis of trimetazidine in rat plasma is presented. It required only 50 μL of plasma and allows the use of minimal volumes of organic solvents. The seamless interface of SALLE and LC-MS eliminated the drying-down step and the extract was diluted and injected into an LC-MS/MS system with a cycle time of 2.5 min/sample. The retention times of trimetazidine and IS were approximately 1.1 and 1.7 min, respectively. Calibration curves were linear over the concentration range of 0.1-100 ng/mL, which can be extended to 500 ng/mL by dilution. The intra- and inter-batch precision, accuracy and the relative standard deviation were all <15%. This method was successfully applied to determine trimetazidine concentrations in rat plasma. PMID:24954771

  14. Determination of synthetic polycyclic musks in aqueous samples by ultrasound-assisted dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry.

    PubMed

    Yang, Ching-Ya; Ding, Wang-Hsien

    2012-02-01

    A simple and solvent-minimized procedure for the determination of six commonly found synthetic polycyclic musks in aqueous samples using ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) is described. The parameters affecting the extraction efficiency of analytes from water samples were systematically investigated. The best extraction conditions involved the rapid injection of a mixture of 1.0 mL of isopropyl alcohol (as a dispersant) and 10 μL of carbon tetrachloride (as an extractant) into 10 mL of water containing 0.5 g of sodium chloride in a conical-bottom glass tube. After ultrasonication for 1.0 min and centrifugation at 5,000 rpm (10 min), the sedimented phase 1.0 μL was directly injected into the GC-MS system. The limits of quantitation (LOQs) were less than 0.6 ng/L. The precision for these analytes, as indicated by relative standard deviations (RSDs), was less than 11% for both intra- and interday analysis. Accuracy, expressed as the mean extraction recovery, was between 71 and 104%. Their total concentrations were determined in the range from 8.3 to 63.9 ng/L in various environmental samples by using a standard addition method. PMID:22139524

  15. 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. PMID:26893021

  16. Evaluation of dispersive liquid-liquid microextraction for the simultaneous determination of chlorophenols and haloanisoles in wines and cork stoppers using gas chromatography-mass spectrometry.

    PubMed

    Campillo, Natalia; Viñas, Pilar; Cacho, Juan I; Peñalver, Rosa; Hernández-Córdoba, Manuel

    2010-11-19

    Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) was evaluated for the simultaneous determination of five chlorophenols and seven haloanisoles in wines and cork stoppers. Parameters, such as the nature and volume of the extracting and disperser solvents, extraction time, salt addition, centrifugation time and sample volume or mass, affecting the DLLME were carefully optimized to extract and preconcentrate chlorophenols, in the form of their acetylated derivatives, and haloanisoles. In this extraction method, 1mL of acetone (disperser solvent) containing 30μL of carbon tetrachloride (extraction solvent) was rapidly injected by a syringe into 5mL of sample solution containing 200μL of acetic anhydride (derivatizing reagent) and 0.5mL of phosphate buffer solution, thereby forming a cloudy solution. After extraction, phase separation was performed by centrifugation, and a volume of 4μL of the sedimented phase was analyzed by GC-MS. The wine samples were directly used for the DLLME extraction (red wines required a 1:1 dilution with water). For cork samples, the target analytes were first extracted with pentane, the solvent was evaporated and the residue reconstituted with acetone before DLLME. The use of an internal standard (2,4-dibromoanisole) notably improved the repeatability of the procedure. Under the optimized conditions, detection limits ranged from 0.004 to 0.108ngmL(-1) in wine samples (24-220pgg(-1) in corks), depending on the compound and the sample analyzed. The enrichment factors for haloanisoles were in the 380-700-fold range. PMID:20956005

  17. Determination of lewisite metabolite 2-chlorovinylarsonous acid in urine by use of dispersive derivatization liquid-liquid microextraction followed by gas chromatography-mass spectrometry.

    PubMed

    Naseri, Mohammad Taghi; Shamsipur, Mojtaba; Babri, Mehran; Saeidian, Hamid; Sarabadani, Mansour; Ashrafi, Davood; Taghizadeh, Naser

    2014-08-01

    The purpose of this study was to develop a sensitive and simple method, based on dispersive derivatization liquid-liquid microextraction-gas chromatography-mass spectrometry (DDLLME-GC-MS) in scanning and selected-ion-monitoring (SIM) modes, for detection of 2-chlorovinylarsonous acid (CVAA) as a hydrolysis product and urinary metabolite of lewisite in urine samples. Chloroform (65 μL), methanol (500 μL), and ethanedithiol (10 μL) were used as extraction solvent, dispersive solvent, and derivatizing reagent, respectively. Critical conditions of the proposed method were optimized. The nucleophilic reactions of dithiol and monothiol compounds with CVAA were also studied using a competitive method. In view of the high affinity of trivalent arsenic for sulfhydryl groups, the interaction between CVAA and bis(2-chlorovinyl)arsonous acid (BCVAA) and free cysteine (Cys) was also investigated using liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS). The interference of Cys, present in human urine, with the detection of CVAA was evaluated using dithiol and monothiol chemicals as derivatization agents. The developed method provided a preconcentration factor of 250, and limits of detection of 0.015 and 0.30 μg L(-1) in SIM and scanning modes, respectively. The calibration curves were linear over the concentration range of 1-400 μg L(-1) in full-scan mode. The relative standard deviation (RSD) values were calculated to be 5.5 and 3.2% at concentrations of 20 and 100 μg L(-1), respectively. Collision-induced dissociation studies of the major electron-impact (EI) ions were performed to confirm the proposed fragment structure of CVAA-dithiols derivatives. Results indicated that the developed method for analysis of CVAA is suitable not only for verification of human exposure to lewisite, but also for quantification of CVAA in urine samples. PMID:24677032

  18. 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.

  19. Geochemical Speciation Mass Transfer

    Energy Science and Technology Software Center (ESTSC)

    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 mineralmore » 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.« less

  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. PMID:22717553

  1. 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

    2011-01-01

    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. PMID:21112591

  2. 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

    2016-02-01

    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. PMID:26653427

  3. Ultra sound assisted one step rapid derivatization and dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometric determination of amino acids in complex matrices.

    PubMed

    Mudiam, Mohana Krishna Reddy; Ratnasekhar, Ch

    2013-05-24

    A rapid and economical method for the simultaneous determination of 20 amino acids in complex biological and food matrices (hair, urine and soybean seed samples) has been developed using ultrasound assisted dispersive liquid-liquid micro extraction (UA-DLLME). The method involves simultaneous derivatization and extraction followed by gas chromatography-mass spectrometric (GC-MS) analysis of amino acids. The parameters of UA-DLLME were optimized with the aid of design of experiments approach. The procedure involves the rapid injection of mixture of acetonitrile (disperser solvent), trichloroethylene (TCE) (extraction solvent) and ethylchloroformate (derivatization reagent) into the aqueous phase of sample extract containing pyridine. The Plackett-Burman design has indicated that, the factors such as volume of disperser and extraction solvents and pH were found to be significantly affects the extraction efficiency of the method. The optimum conditions of these factors based on central composite design were found to be 250μL of acetonitrile, 80μL of TCE and pH of 10. The limit of detection and limit of quantification were found to be in the range of 0.36-3.68μgL(-1) and 1.26-12.01μgL(-1) respectively. This is the first application of DLLME for the analysis of amino acids in any matrices. The advantages like (i) in situ derivatization and extraction of amino acids without any prior lyophilization and cleanup of sample, (ii) low consumption of extraction solvent, (iii) fast and simple, (iv) cost-effective and (iv) good repeatability make the method amenable for the routine analysis of amino acids in clinical, toxicological, nutritional and quality control laboratories. PMID:23602642

  4. 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.

  5. Determination of aqueous fullerene aggregates in water by ultrasound-assisted dispersive liquid-liquid microextraction with liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry.

    PubMed

    Chen, Hsin-Chang; Ding, Wang-Hsien

    2012-02-01

    A simple and solvent-minimized method for the determination of three aqueous fullerene aggregates (nC₆₀, nC₇₀, and aqueous [6,6]-phenyl C₆₁ butyric acid methyl ester (nPCBM)) in water samples is described. The method involves the use of ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) coupled liquid chromatography-tandem mass spectrometry with atmospheric pressure photoionization (LC-APPI-MS/MS). The parameters affecting the extraction efficiency of the analytes from water samples were systematically investigated and the conditions optimized. The best extraction conditions involved the rapid injection of a mixture of 1.0 mL of 2-propanol (as a disperser solvent) and 10 μL of benzyl bromide (as an extraction solvent) into 10 mL of an aqueous solution (pH 10.0) containing 1% sodium chloride in a conical bottom glass tube. After ultrasonication for 1.0 min and centrifugation at 5000 pm (10 min), the sedimented phase 5.0 μL was directly injected into the LC-APPI-MS/MS system. The limits of quantification (LOQs) were 150, 60 and 8 ng L⁻¹ for nPCBM, nC₆₀ and nC₇₀, respectively. The precision for these analytes, as indicated by relative standard deviations (RSDs), were less than 12% for both intra- and inter-day analysis. Accuracy, expressed as the mean extraction recovery, was between 70 and 86%. A standard addition method was used to quantitate three aqueous fullerene aggregates, and the concentrations of these aqueous fullerene aggregates were determined to be in the range from n.d. to 130 ng L⁻¹ in various environmental samples including municipal influent and effluent samples, industrial wastewater samples, and surface water samples. PMID:22209304

  6. Rapid analysis of aflatoxin M1 in milk using dispersive liquid-liquid microextraction coupled with ultrahigh pressure liquid chromatography tandem mass spectrometry.

    PubMed

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

    2013-10-01

    A simple, rapid, and sensitive method based on simultaneous protein precipitation and extraction of aflatoxin M1 (AFM1) followed by dispersive liquid-liquid microextraction (DLLME) and ultrahigh pressure liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis was developed for the determination of AFM1 in milk samples. In order to precipitate the proteins and extract AFM1 from milk, a sample pretreatment using acetonitrile and NaCl as the extraction/denaturant solvent and salting-out agent, respectively, was optimised. Subsequently, the acetonitrile (upper) phase, containing AFM1, was used as the disperser solvent in DLLME, and extractant (chloroform) and water were added in turn to the extract to perform the DLLME process. The main parameters affecting the extraction efficiency of the whole analytical procedure, such as acetonitrile volume, amount of salt, type and volume of extractant and water volume, were carefully optimised by experimental design. Under optimum conditions, the developed method provides an enrichment factor of 33 and detection and quantification limits (0.6 and 2.0 ng kg(-1), respectively) below the maximum levels imposed by current regulations for AFM1 in milk and infant milk formulae. Recoveries (61.3-75.3%) and repeatability (RSD < 10, n = 3), tested in different types of milk at four AFM1 levels, met the performance criteria required by EC Regulation No. 401/2006. Moreover, the matrix effect on the signal intensity of the analyte was negligible. The proposed method provides a rapid extraction and an accurate determination of AFM1 in milk and formula milk using a simple and inexpensive sample preparation procedure. PMID:23942569

  7. 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)

  8. 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. PMID:26304788

  9. 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

  10. 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

    2013-12-01

    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

  11. 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. PMID:26003714

  12. 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. PMID:24070627

  13. Microwave-assisted extraction and dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry for isolation and determination of polycyclic aromatic hydrocarbons in smoked fish.

    PubMed

    Ghasemzadeh-Mohammadi, Vahid; Mohammadi, Abdorreza; Hashemi, Maryam; Khaksar, Ramin; Haratian, Parivash

    2012-05-11

    A simple and efficient method was developed using microwave-assisted extraction (MAE) and dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) for the extraction and quantification of 16 polycyclic aromatic hydrocarbons (PAHs) in smoked fish. Benzo[a]pyrene, chrysene and pyrene were employed as model compounds and spiked to smoked fish to assess the extraction procedure. Several parameters, including the nature and volume of hydrolysis, extracting and disperser solvents, microwave time and pH, were optimized. In the optimum condition for MAE, 1g of fish sample was extracted in 12 mL KOH (2M) and ethanol with a 50:50 ratio in a closed-vessel system. For DLLME, 500 μL of acetone (disperser solvent) containing 100 μL of ethylene tetrachloride (extraction solvent) was rapidly injected by syringe into 12 mL of the sample extract solution (previously adjusted to pH 6.5), thereby forming a cloudy solution. Phase separation was performed by centrifugation and a volume of 1.5 μL of the sedimented phase was analyzed by GC-MS in select ion monitoring (SIM) mode. Satisfactory results were achieved when this method was applied to analyze the PAHs in smoked fish samples. The MAE-DLLME method coupled with GC-MS provided excellent enrichment factors (in the range of 244-373 for 16 PAHs) and good repeatability (with a relative standard deviation between 2.8 and 9%) for spiked smoked fish. The calibration graphs were linear in the range of 1-200 ng g(-1), with the square of the correlation coefficient (R(2))>0.981 and detection limits between 0.11 and 0.43 ng g(-1). The recoveries of those compounds in smoked fish were from 82.1% to 105.5%. A comparison of this method with previous methods demonstrated that the proposed method is an accurate, rapid and reliable sample-pretreatment method that gives very good enrichment factors and detection limits for extracting and determining PAHs from smoked fish. PMID:22483095

  14. Mathematical Modeling of Mass Transfer in Laminar Motion of a Droplet in a Liquid Medium

    NASA Astrophysics Data System (ADS)

    Elizarov, D. V.; Elizarov, V. V.; Kamaliev, T. S.; D‧yakonov, S. G.

    2016-03-01

    Consideration is given to mathematical modeling of the process of nonstationary liquid-liquid extraction in apparatuses with free motion of a dispersed phase. Solutions of nonstationary equations of transfer of momentum and mass in the boundary layer on the droplet and inside the droplet near the phase boundary are given. Equations for calculation of the coefficients of mass transfer and concentration of the extracted component are obtained. A comparison is made of the calculated data and experimental results in extracting various liquid mixtures.

  15. 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. PMID:24993054

  16. Dispersive liquid-liquid microextraction for the determination of macrocyclic lactones in milk by liquid chromatography with diode array detection and atmospheric pressure chemical ionization ion-trap tandem mass spectrometry.

    PubMed

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

    2013-03-22

    Eprinomectin (EPRI), abamectin (ABA), doramectin (DOR), moxidectin (MOX) and ivermectin (IVM) were determined in milk samples using dispersive liquid-liquid microextraction (DLLME) and liquid chromatography with diode array detection (LC-DAD) coupled to atmospheric pressure chemical ionization in negative ion mode ion-trap tandem mass spectrometry (APCI-IT-MS/MS). Milk proteins were removed by precipitation with trichloroacetic acid and the analytes were preconcentrated using 2mL of acetonitrile containing 200μL of chloroform as extraction mixture. The effect of several parameters for the liquid-liquid microextraction efficiency was evaluated. Standard additions method was used for quantification purposes, the correlation coefficients were better than 0.9970 in all cases and the quantification limits ranged from 1.0 to 4.7ngg(-1) and from 0.1 to 2.4ngg(-1) when using DAD and MS, respectively. The DLLME-LC-APCI-IT-MS/MS optimized method was successfully applied to different milk samples and none of the studied analytes was detected in the samples studied. The recoveries for milk samples spiked at concentration levels ranging between 0.5 and 50ngg(-1), depending on the compound, were between 89.5 and 105%, with relative standard deviations lower than 9% (n=135). Simplicity, rapidity and reliability are important advantages of the proposed method, while the sample preparation step can be regarded as environmentally friendly. PMID:23415139

  17. 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. PMID:26823154

  18. 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. PMID:23622535

  19. 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. PMID:25732691

  20. 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. PMID:26780712

  1. 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.

  2. 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. PMID:26877173

  3. 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. PMID:25622579

  4. 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...

  5. 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.

  6. 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.

  7. 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. PMID:26695317

  8. 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. PMID:27144480

  9. 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

  10. Development and application of salting-out assisted liquid/liquid extraction for multi-mycotoxin biomarkers analysis in pig urine with high performance liquid chromatography/tandem mass spectrometry.

    PubMed

    Song, Suquan; Ediage, Emmanuel Njumbe; Wu, Aibo; De Saeger, Sarah

    2013-05-31

    Direct determination of urinary mycotoxins is a better approach to assess individual's exposure than the indirect estimation from average dietary intakes. In this study, a new analytical method was developed and validated for simultaneous analysis of aflatoxin B1, deoxynivalenol, fumonisin B1, ochratoxin A, zearalenone and T2 toxin and their metabolites in pig urine. In total 12 analytes were selected. A salting-out assisted liquid-liquid extraction procedure was used for sample preparation. High performance liquid chromatography/tandem mass spectrometry was used for the separation and detection of all the analytes. The extraction recoveries were in a range of 70-108%, with the intra-day relative standard deviation and inter-day relative standard deviation lower than 25% for most of the compounds at 3 different concentration levels. Meanwhile the method bias for all the analytes did not exceed 20%. The limits of quantification ranged from 0.07ngmL(-1) for ochratoxin A to 3.3ngmL(-1) for deoxynivalenol. Matrix effect was evaluated in this study and matrix-matched calibration was used for quantification. The developed method was also validated for human urine as an extension of its application. Finally, the developed method was applied in a pilot study to analyze 28 pig urine samples. Deoxynivalenol, aflatoxin B1, fumonisin B1 and ochratoxin A were detected in these samples. PMID:23177157

  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. PMID:24401436

  12. Determination of nine sensitizing disperse dyes in activated sludge by ultrasound-assisted liquid-liquid extraction-ultra-performance liquid chromatography-electrospray ionization-tandem mass spectrometry.

    PubMed

    Zhou, Linjun; Shi, Lili; Liu, Jining; Lv, Fenglan; Xu, Yanhua

    2016-01-01

    A method was developed on the basis of ultrasound-assisted liquid-liquid extraction ultra-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (ULLE-UPLC-ESI-MS/MS) to determine nine sensitizing disperse dyes in activated sludge. The samples were extracted using ULLE and separated through UPLC on an ACQUITY UPLCTM BEH C18 column with a gradient elution program of acetonitrile and acidified water (containing 2% acetonitrile, 0.2% formic acid, and 0.005 mol/L ammonium; pH 2.7) as the mobile phase. The samples were then identified and quantified through UPLC-ESI-MS/MS in a positive mode and multiple reaction monitoring. Results showed good linearity (10-1000 μg/L, 0.9934-0.9998), detection limit (0.08-2.17 μg/L), and quantification limit (0.27-7.38 μg/L) for the nine sensitizing disperse dyes, with recoveries ranging from 65.0 to 111.3%. The proposed method was applied to detect and determine the concentration of sensitizing disperse dyes in sludge samples obtained from various sewage treatment plants (six dyeing enterprises and one dye manufacturer). Three sensitizing disperse dyes were identified, and the lowest concentration detected was 10 μg/kg. PMID:26521175

  13. [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. PMID:26182473

  14. 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. PMID:26773891

  15. 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. PMID:26452878

  16. Determination of alkylphenols and bisphenol A in seawater samples by dispersive liquid-liquid microextraction and liquid chromatography tandem mass spectrometry for compliance with environmental quality standards (Directive 2008/105/EC).

    PubMed

    Salgueiro-González, N; Concha-Graña, E; Turnes-Carou, I; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

    2012-02-01

    A fast, simple, sensitive and green analytical chemistry method for the simultaneous determination of alkylphenols (4-tert-octylphenol, 4-octylphenol, 4-n-nonylphenol, nonylphenol) and bisphenol A in seawater was developed and validated. The procedure was based on a dispersive liquid-liquid microextraction (DLLME) of a small volume of seawater sample (30 mL) using only 100 μL of 1-octanol, combined with liquid chromatography-electrospray ionization tandem mass spectrometry in negative mode (LC-ESI-MS/MS). The matrix effect was studied and compensated using deuterated labelled standards as surrogate standards for the quantitation of target compounds. The analytical features of the proposed method were satisfactory: repeatability and intermediate precision were <10% and recoveries were around 84-104% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) ranged between 0.005 and 0.03 μg L⁻¹, therefore the levels established in the Directive 2008/105/EC were achieved. The applicability of the proposed method was demonstrated analyzing seawater samples from different sites of A Coruña (Northwest of Spain). The analyses showed the presence of all compounds at levels between 0.035 (bisphenol A) and 0.14 μg L⁻¹ (nonylphenol). PMID:22227360

  17. 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.

  18. [Determination of L-dopa and dopamine in rat brain microdialysate by ultra high performance liquid chromatography-tandem mass spectrometry using stable isotope-coded derivatization coupled with dispersive liquid-liquid microextraction].

    PubMed

    Qi, Weimei; Zhao, Xian-en; Qi, Yong; Sun, Zhiwei; Chen, Guang; You, Jinmao; Suo, Yourui

    2015-09-01

    The sensitive detection method of levodopa (L-DOPA) and dopamine (DA) in rat brain microdialysate of Parkinson's disease (PD) is an essential tool for the clinical study and attenuated synergistic drug screening for L-DOPA from traditional Chinese medicines. Using d0/d3-10-methyl-acridone-2-sulfonyl chloride (d0/d3-MASC) as stable isotope derivatization reagent, a novel ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated for L-DOPA and DA by stable isotope- coded derivatization coupled with ultrasonic-assisted dispersive liquid-liquid microextraction (UA-DLLME). d3-MASC (light) and d3-MASC (heavy) were used as derivatization reagents for microdialysate samples and standards, respectively. Mixtures of the two solutions were prepared by UA-DLLME for UHPLC-MS/MS analysis with multiple reaction monitoring (MRM) mode. With d3-MASC heavy derivatives as internal standards for corresponding light derivatives from samples, the stable isotope internal standard quantification for L-DOPA and DA was carried out. The stable derivatives were obtained in aqueous acetonitrile (pH 10.8 sodium carbonate-sodium bicarbonate buffer) at 37 °C for 3.0 min, and then were separated within 2.0 min using gradient elution. Linear range was 0.20-1500.0 nmol/L (R > 0.994). LODs were 0.005 and 0.009 nmol/L for DA and L-DOPA (S/N = 3), respectively. This method was validated, and it showed obvious advantages in comparing with the reported methods in terms of sensitivity, analysis speed and anti-matrix interference. This method has been successfully applied to the study of effect of Shouwu Fang on L-DOPA and DA concentration fluctuations in PD rat brain microdialysate. PMID:26753287

  19. 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. PMID:22995997

  20. 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. PMID:23895920

  1. 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. PMID:25801996

  2. Ultrasound leaching-dispersive liquid-liquid microextraction based on solidification of floating organic droplet for determination of polybrominated diphenyl ethers in sediment samples by gas chromatography-tandem mass spectrometry.

    PubMed

    Lana, Nerina B; Berton, Paula; Covaci, Adrian; Atencio, Adrián G; Ciocco, Néstor F; Altamirano, Jorgelina C

    2013-04-12

    Ultrasound leaching-dispersive liquid-liquid microextraction using solidification of floating organic droplet (USL-DLLME-SFO) technique is proposed for extraction and isolation of polybrominated diphenyl ethers (PBDEs) from sediment and further determination by gas chromatography-tandem mass spectrometry (GC-MS/MS). Parameters that affect the efficiency of the procedure were investigated by a full factorial (2(k)) screening design. Variables showing significant effects on the analytical responses were considered within a further central composite design (CCD). The optimization assays have led to following protocol: ultrasound assisted lixiviation of 1g sediment was carried out by using 1.2 mL MeOH. Further, the analytes were isolated from 0.4 mL of the extract using the DLLME-SFO technique. The microextraction was performed using 0.1 mL MeOH, 22 mg 1-dodecanol, 1 mL NaCl solution 6.15M and 4.4 mL ultrapure water as dispersive and extracting solvents, medium ionic strength and dispersant bulk, respectively. Under optimum conditions, the method exhibits good performance in terms of linearity and precision (RSD<9.2%), with recoveries above 71% and limits of detection (LODs) within the range 0.5-1.8 pgg(-1) dry weight (d.w.). Method validation was demonstrated through the analysis of environmental sediment samples in which PBDEs were detected and quantified. The presence of BDE-47, -100, -99 and -153 was reported within the concentration range of

  3. 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

    2015-10-01

    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. PMID:26341596

  4. Dispersive liquid-liquid microextraction for the determination of vitamins D and K in foods by liquid chromatography with diode-array and atmospheric pressure chemical ionization-mass spectrometry detection.

    PubMed

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

    2013-10-15

    A simple and rapid method was developed using reversed-phase liquid chromatography (LC) with both diode array (DAD) and atmospheric pressure chemical ionization mass spectrometric (APCI-MS) detection, for the simultaneous analysis of the vitamins ergocalciferol (D2), cholecalciferol (D3), phylloquinone (K1), menaquinone-4 (K2) and a synthetic form of vitamin K, menadione (K3). The Taguchi experimental method, an orthogonal array design (OAD), was used to optimize an efficient and clean preconcentration step based on dispersive liquid-liquid microextraction (DLLME). A factorial design was applied with six factors and three levels for each factor, namely, carbon tetrachloride volume, methanol volume, aqueous sample volume, pH of sample, sodium chloride concentration and time of the centrifugation step. The DLLME optimized procedure consisted of rapidly injecting 3 mL of acetonitrile (disperser solvent) containing 150 µL carbon tetrachloride (extraction solvent) into the aqueous sample, thereby forming a cloudy solution. Phase separation was performed by centrifugation, and the sedimented phase was evaporated with nitrogen, reconstituted with 50 µL of acetonitrile, and injected. The LC analyses were carried out using a mobile phase composed of acetonitrile, 2-propanol and water, under gradient elution. Quantification was carried out by the standard additions method. The APCI-MS spectra, in combination with UV spectra, permitted the correct identification of compounds in the food samples. The method was validated according to international guidelines and using a certified reference material. The validated method was applied for the analysis of vitamins D and K in infant foods and several green vegetables. There was little variability in the forms of vitamin K present in vegetables, with the most abundant vitamer in all the samples being phylloquinone, while menadione could not be detected. Conversely, cholecalciferol, which is present in food of animal origin, was

  5. 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. PMID:23290361

  6. Calculation of mass transfer in multiphase flow

    SciTech Connect

    Wang, L.; Gopal, M.

    1998-12-31

    This paper summarizes the results of mass transfer mechanisms under disturbed liquid-gas flow in 10 cm diameter pipe using electrochemical limiting current density and potentiostatic noise technique. The solution used is potassium ferro/ferricyanide dissolve in 1.3 N sodium hydroxide system. Mass transfer coefficients in full pipe flow and slug flow are obtained. The relationship between mass transfer coefficient with full pipe flow velocities and with slug flow Froude numbers are studied. The impact of bubbles in slugs on the mass transfer coefficient is revealed, The impact of flow disturbance, including weld beads and pits, are discussed for both full pipe flow and slug flow.

  7. Detection of food additives by voltammetry at the liquid-liquid interface.

    PubMed

    Herzog, Grégoire; Kam, Victor; Berduque, Alfonso; Arrigan, Damien W M

    2008-06-25

    Electrochemistry at the liquid-liquid interface enables the detection of nonredoxactive species with electroanalytical techniques. In this work, the electrochemical behavior of two food additives, aspartame and acesulfame K, was investigated. Both ions were found to undergo ion-transfer voltammetry at the liquid-liquid interface. Differential pulse voltammetry was used for the preparation of calibration curves over the concentration range of 30-350 microM with a detection limit of 30 microM. The standard addition method was applied to the determination of their concentrations in food and beverage samples such as sweeteners and sugar-free beverages. Selective electrochemically modulated liquid-liquid extraction of these species in both laboratory solutions and in beverage samples was also demonstrated. These results indicate the suitability of liquid-liquid electrochemistry as an analytical approach in food analysis. PMID:18512937

  8. 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.

  9. Transport of microspheres across liquid-liquid interfaces

    NASA Astrophysics Data System (ADS)

    Hardt, Steffen; Sinha, Ashok; Mollah, Amlan; Ganguly, Ranjan

    2013-11-01

    Experiments with magnetic microspheres crossing the interface between two immiscible polymer solutions under the influence of a magnetic field are reported. The liquids form a bilaminated configuration in a microchannel, allowing a detailed inspection of the liquid-liquid interface. The trajectories of the particles close to the interface are examined using bright-field microscopy and a high-speed camera. During the interaction phase the interface gets deformed and the particles ``snap in,'' indicating that a three-phase contact line is formed. The dependence of the particle-interface interaction on the size of the microspheres is studied, showing that via transfer across a liquid-liquid interface a size separation of particles can be achieved. Comparing the results for 1.29 micron diameter spheres with those for 4.69 micron spheres, it is found that the small particles are able to cross the interface more easily than what is expected from a simple scaling analysis taking into account the balance between magnetic and interfacial forces on the particles. The most likely explanation for this phenomenon involves the line tension that destabilizes smaller particles adsorbed to a liquid-liquid interface more than larger particles.

  10. 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.

  11. 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…

  12. Automated Agitation-Assisted Demulsification Dispersive Liquid-Liquid Microextraction.

    PubMed

    Guo, Liang; Chia, Shao Hua; Lee, Hian Kee

    2016-03-01

    Dispersive liquid-liquid microextraction (DLLME) is an extremely fast and efficient sample preparation procedure. For its capability and applicability to be fully exploited, full automation of its operations seamlessly integrated with analysis is necessary. In this work, for the first time, fully automated agitation-assisted demulsification (AAD)-DLLME integrated with gas chromatography/mass spectrometry was developed for the convenient and efficient determination of polycyclic aromatic hydrocarbons in environmental water samples. The use of a commercially available multipurpose autosampler equipped with two microsyringes of different capacities allowed elimination or significant reduction of manpower, labor, and time with the large-volume microsyringe used for liquid transfers and the small-volume microsyringe for extract collection and injection for analysis. Apart from enhancing accessibility of DLLME, the procedure was characterized by the application of agitation after extraction to break up the emulsion (that otherwise would need centrifugation or a demulsification solvent), further improving overall operational efficiency and flexibility. Additionally, the application of low-density solvent as extractant facilitated the easy collection of extract as the upper layer over water. Some parameters affecting the automated AAD-DDLME procedure were investigated. Under the optimized conditions, the procedure provided good linearity (ranging from a minimum of 0.1-0.5 μg/L to a maximum of 50 μg/L), low limits of detection (0.010-0.058 μg/L), and good repeatability of the extractions (relative standard deviations, below 5.3%, n = 6). The proposed method was applied to analyze PAHs in real river water samples. PMID:26818217

  13. 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

    2016-08-01

    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

  14. 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

  15. Ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction coupled with liquid chromatography-quadrupole-linear ion trap-mass spectrometry for simultaneous analysis of pharmaceuticals in wastewaters.

    PubMed

    Parrilla Vázquez, M M; Parrilla Vázquez, P; Martínez Galera, M; Gil García, M D; Uclés, A

    2013-05-24

    A simple, rapid, low environmental toxicity and sensitive ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of nine pharmaceuticals (paracetamol, metoprolol, bisoprolol, betaxolol, ketoprofen, naproxen, ibuprofen, flufenamic acid and tolfenamic acid) in wastewater, and their determination using high-performance liquid chromatography with a hybrid triple quadrupole-linear ion trap-mass spectrometer (LC-QqLIT-MS). The IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) and acetonitrile (ACN) were used as extraction and disperser solvent, respectively, for the DLLME procedure, instead of using toxic chlorinated solvent. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, type and volume of disperser solvent, cooling in ice-water, sonication time, centrifuging time, sample pH and ionic strength, were optimized. The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.5mL of acetonitrile), which increased the extraction efficiency and reduced the equilibrium time. A slight increase in the recoveries of pharmaceuticals was observed when an ice-water bath extraction step was included in the analytical procedure. In this way, enrichment factors between 255 and 340 were obtained. Data acquisition in selected reaction monitoring mode (SRM), allowed the simultaneous identification and quantification of the analytes using two transitions (SRM1 and SRM2). Additionally, the information dependent acquisition (IDA) scan was performed to carry out the identification of those analytes whose second transition was absent or was present at low intensity, also providing extra confirmation for the other analytes. The optimized US-IL-DLLME-LC-QqLIT-MS method showed a good precision level, with relative standard deviation values between 1.1% and 11.3%. Limits of

  16. 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. PMID:24997113

  17. Mass transfer in electromembrane extraction--The link between theory and experiments.

    PubMed

    Huang, Chuixiu; Jensen, Henrik; Seip, Knut Fredrik; Gjelstad, Astrid; Pedersen-Bjergaard, Stig

    2016-01-01

    Electromembrane extraction was introduced in 2006 as a totally new sample preparation concept for the extraction of charged analytes present in aqueous samples. Electromembrane extraction is based on electrokinetic migration of the analytes through a supported liquid membrane and into a μL-volume of acceptor solution under the influence of an external electrical field. To date, electromembrane extraction has mostly been used for the extraction of drug substances, amino acids, and peptides from biological fluids, and for organic micropollutants from environmental samples. Electromembrane extraction has typically been combined with chromatography, mass spectrometry, and electrophoresis for analyte separation and detection. At the moment, close to 125 research papers have been published with focus on electromembrane extraction. Electromembrane extraction is a hybrid technique between electrophoresis and liquid-liquid extraction, and the fundamental principles for mass transfer have only partly been investigated. Thus, although there is great interest in electromembrane extraction, the fundamental principle for mass transfer has to be described in more detail for the scientific acceptance of the concept. This review summarizes recent efforts to describe the fundamentals of mass transfer in electromembrane extraction, and aim to give an up-to-date understanding of the processes involved. PMID:26420509

  18. Direct determination of chlorophenols in water samples through ultrasound-assisted hollow fiber liquid-liquid-liquid microextraction on-line coupled with high-performance liquid chromatography.

    PubMed

    Chao, Yu-Ying; Tu, Yi-Ming; Jian, Zhi-Xuan; Wang, Hsaio-Wen; Huang, Yeou-Lih

    2013-01-01

    In this study we on-line coupled hollow fiber liquid-liquid-liquid microextraction (HF-LLLME), assisted by an ultrasonic probe, with high-performance liquid chromatography (HPLC). In this approach, the target analytes - 2-chlorophenol (2-CP), 3-chlorophenol (3-CP), 2,6-dichlorophenol (2,6-DCP), and 3,4-dichlorophenol (3,4-DCP) - were extracted into a hollow fiber (HF) supported liquid membrane (SLM) and then back-extracted into the acceptor solution in the lumen of the HF. Next, the acceptor solution was withdrawn on-line into the HPLC sample loop connected to the HF and then injected directly into the HPLC system for analysis. We found that the chlorophenols (CPs) could diffuse quickly through two sequential extraction interfaces - the donor phase - SLM and the SLM - acceptor phase - under the assistance of an ultrasonic probe. Ultrasonication provided effective mixing of the extracted boundary layers with the bulk of the sample and it increased the driving forces for mass transfer, thereby enhancing the extraction kinetics and leading to rapid enrichment of the target analytes. We studied the effects of various parameters on the extraction efficiency, viz. the nature of the SLM and acceptor phase, the compositions of the donor and acceptor phases, the fiber length, the stirring rate, the ion strength, the sample temperature, the sonication conditions, and the perfusion flow rate. This on-line extraction method exhibited linearity (r(2)≥0.998), sensitivity (limits of detection: 0.03-0.05 μg L(-1)), and precision (RSD%≤4.8), allowing the sensitive, simple, and rapid determination of CPs in aqueous solutions and water samples with a sampling time of just 2 min. PMID:23237709

  19. 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.

  20. Gas mass transfer for stratified flows

    SciTech Connect

    Duffey, R.B.; Hughes, E.D.

    1995-07-01

    We analyzed gas absorption and release in water bodies using existing surface renewal theory. We show a new relation between turbulent momentum and mass transfer from gas to water, including the effects of waves and wave roughness, by evaluating the equilibrum integral turbulent dissipation due to energy transfer to the water from the wind. Using Kolmogoroff turbulence arguments the gas transfer velocity, or mass transfer coefficient, is then naturally and straightforwardly obtained as a non-linear function of the wind speed drag coefficient and the square root of the molecular diffusion coefficient. In dimensionless form, the theory predicts the turbulent Sherwood number to be Sh{sub t} = (2/{radical}{pi}) Sc{sup 1/2}, where Sh{sub t} is based on an integral dissipation length scale in the air. The theory confirms the observed nonlinear variation of the mass transfer coefficient as a function of the wind speed; gives the correct transition with turbulence-centered models for smooth surfaces at low speeds; and predicts experimental data from both laboratory and environmental measurements within the data scatter. The differences between the available laboratory and field data measurements are due to the large differences in the drag coefficient between wind tunnels and oceans. The results also imply that the effect of direct aeration due to bubble entrainment at wave breaking is no more than a 20% increase in the mass transfer for the highest speeds. The theory has importance to mass transfer in both the geophysical and chemical engineering literature.

  1. Gas mass transfer for stratified flows

    SciTech Connect

    Duffey, R.B.; Hughes, E.D.

    1995-06-01

    We analyzed gas absorption and release in water bodies using existing surface renewal theory. We show a new relation between turbulent momentum and mass transfer from gas to water, including the effects of waves and wave roughness, by evaluating the equilibrium integral turbulent dissipation due to energy transfer to the water from the wind. Using Kolmogoroff turbulence arguments the gas transfer velocity, or mass transfer coefficient, is then naturally and straightforwardly obtained as a non-linear function of the wind speed drag coefficient and the square root of the molecular diffusion coefficient. In dimensionless form, the theory predicts the turbulent Sherwood number to be Sh{sub t} = (2/{radical}{pi})Sc{sup 1/2}, where Sh{sub t} is based on an integral dissipation length scale in the air. The theory confirms the observed nonlinear variation of the mass transfer coefficient as a function of the wind speed; gives the correct transition with turbulence-centered models for smooth surfaces at low speeds; and predicts experimental data from both laboratory and environmental measurements within the data scatter. The differences between the available laboratory and field data measurements are due to the large differences in the drag coefficient between wind tunnels and oceans. The results also imply that the effect of direct aeration due to bubble entrainment at wave breaking is no more than a 20% increase in the mass transfer for the highest speeds. The theory has importance to mass transfer in both the geo-physical and chemical engineering literature.

  2. 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.

  3. Mass transfer effects in a gasification riser

    SciTech Connect

    Breault, Ronald W; Li, Tingwen; Nicoletti, Phillip

    2013-01-01

    In the development of multiphase reacting computational fluid dynamics (CFD) codes, a number of simplifications were incorporated into the codes and models. One of these simplifications was the use of a simplistic mass transfer correlation for the faster reactions and omission of mass transfer effects completely on the moderate speed and slow speed reactions such as those in a fluidized bed gasifier. Another problem that has propagated is that the mass transfer correlation used in the codes is not universal and is being used far from its developed bubbling fluidized bed regime when applied to circulating fluidized bed (CFB) riser reactors. These problems are true for the major CFD codes. To alleviate this problem, a mechanistic based mass transfer coefficient algorithm has been developed based upon an earlier work by Breault et al. This fundamental approach uses the local hydrodynamics to predict a local, time varying mass transfer coefficient. The predicted mass transfer coefficients and the corresponding Sherwood numbers agree well with literature data and are typically about an order of magnitude lower than the correlation noted above. The incorporation of the new mass transfer model gives the expected behavior for all the gasification reactions evaluated in the paper. At the expected and typical design values for the solid flow rate in a CFB riser gasifier an ANOVA analysis has shown the predictions from the new code to be significantly different from the original code predictions. The new algorithm should be used such that the conversions are not over predicted. Additionally, its behaviors with changes in solid flow rate are consistent with the changes in the hydrodynamics.

  4. 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.

  5. 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

  6. Mass transfer in composite catalytic membranes

    SciTech Connect

    Langhendries, G.; Claessens, R.; Baron, G.V.

    1996-12-31

    The partial oxidation of cyclohexane was studied in a composite polymer-zeolite catalytic membrane reactor. In a first step the equilibrium and mass transfer properties (swelling, diffusion and sorption) of dense composite membranes were examined. The swelling behavior of the crosslinked poly(dimethylsiloxane) network was determined for several solvents and related to the differences between the Hildebrand solubility parameters of solvent and polymer. Time lag experiments, which enable us to measure simultaneously diffusion and partition coefficients, were carried out on a dense poly(dimethylsiloxane) membrane. A mathematical model describing the mass transfer behavior of these catalytic membranes was derived and validated with experimental data. Mass transfer through composite catalytic membranes can be predicted using the properties of pure catalyst and polymer material, and a single tortuosity factor. 9 refs., 5 figs., 4 tabs.

  7. 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.

  8. An innovative arrangement for in-vial membrane-assisted liquid-liquid microextraction: application to the determination of esters of phthalic acid in alcoholic beverages by gas chromatography-mass spectrometry.

    PubMed

    March, Juan Gabriel; Cerdà, Victor

    2015-05-01

    A new arrangement for membrane-assisted liquid-liquid microextraction is presented. The extracting organic solvent was placed into a chromatographic microvial, compatible with the chromatograph autosampler, whose septum was replaced by a disc of porous hydrophobic membrane. This extraction device was completely immersed into the analytical sample contained in a cylindrical container subjected to rotary and basculant movement. Then, the extraction of analytes took place from the sample to the organic solvent contained in the vial through the membrane. Esters of the phthalic acid have been selected as model analytes to determine the performance characteristics of the extraction system. The limits of detection, limits of quantification and relative standard deviations (%) were in the range 0.1-0.4, 0.3-1 and 4-7, respectively. Esters of phthalic acid have been successfully analysed in alcoholic beverages. The main operational advantages of this arrangement consisted of minimal required handling, minimal risk of cross contamination and its simplicity. PMID:25876533

  9. Liquid liquid phase transition in Stillinger Weber silicon

    NASA Astrophysics Data System (ADS)

    Beaucage, Philippe; Mousseau, Normand

    2005-04-01

    It was recently demonstrated that Stillinger-Weber silicon undergoes a liquid-liquid first-order phase transition deep into the supercooled region (Sastry and Angell 2003 Nat. Mater. 2 739). Here we study the effects of perturbations on this phase transition. We show that the order of the liquid-liquid transition changes with negative pressure. We also find that the liquid-liquid transition disappears when the three-body term of the potential is strengthened by as little as 5%. This implies that the details of the potential could affect strongly the nature and even the existence of the liquid-liquid phase.

  10. Non-conservative mass transfers in Algols

    NASA Astrophysics Data System (ADS)

    Erdem, A.; Öztürk, O.

    2014-06-01

    We applied a revised model for non-conservative mass transfer in semi-detached binaries to 18 Algol-type binaries showing orbital period increase or decrease in their parabolic O-C diagrams. The combined effect of mass transfer and magnetic braking due to stellar wind was considered when interpreting the orbital period changes of these 18 Algols. Mass transfer was found to be the dominant mechanism for the increase in orbital period of 10 Algols (AM Aur, RX Cas, DK Peg, RV Per, WX Sgr, RZ Sct, BS Sct, W Ser, BD Vir, XZ Vul) while magnetic braking appears to be the responsible mechanism for the decrease in that of 8 Algols (FK Aql, S Cnc, RU Cnc, TU Cnc, SX Cas, TW Cas, V548 Cyg, RY Gem). The peculiar behaviour of orbital period changes in three W Ser-type binary systems (W Ser, itself a prototype, RX Cas and SX Cas) is discussed. The empirical linear relation between orbital period (P) and its rate of change (dP/dt) was also revised.

  11. 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

  12. 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. PMID:25543304

  13. 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. PMID:25394185

  14. 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. PMID:23727731

  15. Heat and mass transfer in materials processing

    NASA Astrophysics Data System (ADS)

    Tanasawa, Ichiro; Lior, Noam

    Various papers on heat and mass transfer in materials processing are presented. The topics addressed include: heat transfer in plasma spraying, structure of ultrashort pulse plasma for CVD processing, heat flow and thermal contraction during plasma spray deposition, metal melting process by laser heating, improved electron beam weld design and control with beam current profile measurements, transport phenomena in laser materials processing, perspectives on integrated modeling of transport processes in semiconductor crystal growth, numerical simulation of natural convection in crystal growth in space and on the earth, conjugate heat transfer in crystal growth, effects of convection on the solidification of binary mixtures. Also discussed are: heat transfer in in-rotating-liquid-spinning process, thermal oscillations in materials processing, modeling and simulation of manufacturing processes of advanced composite materials, reaction engineering principles of combustion synthesis of advanced materials, numerical evaluation of the physical properties of magnetic fluids suitable for heat transfer control, and measurement techniques of thermophysical properties of high temperature melts. (For individual items see A93-10827 to A93-10843)

  16. 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. PMID:27294533

  17. 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%. PMID:23483741

  18. 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. PMID:24939087

  19. 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

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. [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. PMID:24558843

  5. 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.

  6. 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.

  7. 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.

  8. USINT. Heat and Mass Transfer In Concrete

    SciTech Connect

    Eyberger, L.R.

    1989-12-01

    USINT was developed to model the thermal response of concrete to very high heating rates such as might occur from sodium spills on concrete surfaces in a breeder reactor. The major phenomena treated are conductive energy transport; chemical decomposition of concrete; and two-phase, three-component heat and mass transfer of the decomposition products: steam, liquid water, and carbon dioxide. The USINT model provides for porosity to increase as water and carbon-dioxide are formed from the concrete. The concrete is treated generally as divided into two basic regions, wet and dry. In the wet region, steam, carbon-dioxide, and liquid water may co-exist, but in the dry region, there is no liquid water. There is also the possibility of a third region in which there is only liquid water and no gases.

  9. USINT. Heat and Mass Transfer in Concrete

    SciTech Connect

    Beck, J.V.; Knight, R.L.

    1989-12-01

    USINT was developed to model the thermal response of concrete to very high heating rates such as might occur from sodium spills on concrete surfaces in a breeder reactor. The major phenomena treated are conductive energy transport; chemical decomposition of concrete; and two-phase, three-component heat and mass transfer of the decomposition products: steam, liquid water, and carbon dioxide. The USINT model provides for porosity to increase as water and carbon-dioxide are formed from the concrete. The concrete is treated generally as divided into two basic regions, wet and dry. In the wet region, steam, carbon-dioxide, and liquid water may co-exist, but in the dry region, there is no liquid water. There is also the possibility of a third region in which there is only liquid water and no gases.

  10. 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. PMID:24582396

  11. Fundamental mass transfer models for indoor air pollution sources

    SciTech Connect

    Tichenor, B.A.; Guo, Z.; Sparks, L.E.

    1993-01-01

    The paper discusses a simple, fundamental mass transfer model, based on Fick's Law of Diffusion, for indoor air pollution wet sorbent-based sources. (Note: Models are needed to predict emissions from indoor sources. While empirical approaches based on dynamic chamber data are useful, a more fundamental approach is needed to fully elucidate the relevant mass transfer processes). In the model, the mass transfer rate is assumed to be gas-phase limited and controlled by the boundary layer mass transfer coefficient, the saturation vapor pressure of the material being emitted, and the mass of volatile material remaining. Results of static and dynamic chamber tests, as well as test house studies, are presented.

  12. Numerical modeling of liquid-liquid bi-propellant droplet/gas reacting flows

    NASA Astrophysics Data System (ADS)

    Tang, Yupai L.; Schuman, M. D.

    1992-01-01

    A liquid-liquid bipropellant capability for numerically simulating droplets and gas two-phase flows for impinging type rocket injectors was developed through modification of the KIVA-II computer program. This added feature of liquid-liquid bipropellant sprays makes it possible to analyze the impinging type injectors through prescribed drop size and velocity distributions near the point of impingement. Two sample cases for LOX/liquid propane were run at mixture ratios of 3.06 and 2.72 respectively for a 3.4-inch diameter rocket engine with a contraction ratio of four and an expansion ratio of two. The predicted performance as well as the chamber heat transfer were found to be in reasonable agreement with the experimental data.

  13. Spontaneous liquid-liquid phase separation of water.

    PubMed

    Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

    2014-02-01

    We report a molecular dynamics simulation demonstrating a fast spontaneous liquid-liquid phase separation of water and a subsequent slow crystallization to ice. It is found that supercooled water separates rapidly into low- and high-density domains so as to reduce the surface energy in the rectangular simulation cell at certain thermodynamic states. The liquid-liquid phase separation, which is about two orders of magnitude faster than the crystallization, suggests a possibility to observe this phenomenon experimentally. PMID:25353404

  14. Behavior of the mass transfer zone in a biosorption column.

    PubMed

    Naja, Ghinwa; Volesky, Bohumil

    2006-06-15

    Modeling of the mass transfer zone behavior under variable conditions in a flow-through fixed-bed sorption column enabled the prediction of breakthrough curves for Cu2+ and Ca-preloaded Sargassum fluitans biomass. The mass transfer resistance, particle diffusion, and the axial dispersion were incorporated in the model. The dynamics of the mass transfer zone was described under variable sorption column operating conditions including different column lengths and fluid flow rates. Accurate estimation of the behavior of the mass transfer zone as it progressed through the column, reflected eventually in the breakthrough curve, assisted in its relevant interpretations. Furthermore, the proposed mathematical model of the biosorption process was capable of demonstrating the expanding and broadening of the mass transfer zone linked to the equilibrium sorption isotherm. The fundamental understanding of the mass transfer zone dynamics is particularly important for process scale-up where maintaining the process efficiency is critical. PMID:16830573

  15. Enhancement of heat and mass transfer by cavitation

    NASA Astrophysics Data System (ADS)

    Zhang, Y. N.; Zhang, Y. N.; Du, X. Z.; Xian, H. Z.

    2015-01-01

    In this paper, a brief summary of effects of cavitation on the heat and mass transfer are given. The fundamental studies of cavitation bubbles, including its nonlinearity, rectified heat and mass diffusion, are initially introduced. Then selected topics of cavitation enhanced heat and mass transfer were discussed in details including whales stranding caused by active sonar activity, pool boiling heat transfer, oscillating heat pipe and high intensity focused ultrasound treatment.

  16. 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.

  17. 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. PMID:25155655

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

    PubMed

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

    2016-07-01

    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. PMID:27327198

  19. Novel Detection Method of Liquid-Liquid Phase Separation

    NASA Astrophysics Data System (ADS)

    Kato, Hitoshi; Katayanagi, Hideki; Koga, Yoshikata; Nishikawa, Keiko

    2004-12-01

    A novel method of determining a liquid-liquid phase boundary was developed. This method is based on our discovery that a nascent low-density phase is attracted to the center of a Rankine vortex at the onset of phase separation. Thus a liquid-liquid phase boundary is detected easily, rapidly, and accurately. The phase diagrams of the ternary systems NaCl-H2O-1-propanol and NaCl-H2O-1-butanol were obtained by this method. The results matched well with literature values.

  20. 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

    2009-08-01

    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. PMID:19576591

  1. Electron Transfer Dissociation Mass Spectrometry of Hemoglobin on Clinical Samples

    NASA Astrophysics Data System (ADS)

    Coelho Graça, Didia; Lescuyer, Pierre; Clerici, Lorella; Tsybin, Yury O.; Hartmer, Ralf; Meyer, Markus; Samii, Kaveh; Hochstrasser, Denis F.; Scherl, Alexander

    2012-10-01

    A mass spectrometry-based assay combining the specificity of selected reaction monitoring and the protein ion activation capabilities of electron transfer dissociation was developed and employed for the rapid identification of hemoglobin variants from whole blood without previous proteolytic cleavage. The analysis was performed in a robust ion trap mass spectrometer operating at nominal mass accuracy and resolution. Subtle differences in globin sequences, resulting with mass shifts of about one Da, can be unambiguously identified. These results suggest that mass spectrometry analysis of entire proteins using electron transfer dissociation can be employed on clinical samples in a workflow compatible with diagnostic applications.

  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. 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.

  4. Enhanced flavour extraction in continuous liquid-liquid extractors.

    PubMed

    Apps, Peter; Tock, Margaux Lim Ah

    2005-08-12

    Continuous liquid-liquid extraction is a versatile, reliable and robust sample preparation technique, but there is a tendency for the solvent to make channels through the sample, causing uneven and incomplete extraction. A simple, cheap magnetic stirrer that prevents channelling improves extraction efficiency by between 2.8 and 17.6 times. PMID:16078710

  5. 13 CFR 307.20 - Partial liquidation; liquidation upon termination.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 13 Business Credit and Assistance 1 2012-01-01 2012-01-01 false Partial liquidation; liquidation upon termination. 307.20 Section 307.20 Business Credit and Assistance ECONOMIC DEVELOPMENT ADMINISTRATION, DEPARTMENT OF COMMERCE ECONOMIC ADJUSTMENT ASSISTANCE INVESTMENTS Special Requirements...

  6. 13 CFR 307.20 - Partial liquidation; liquidation upon termination.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 13 Business Credit and Assistance 1 2010-01-01 2010-01-01 false Partial liquidation; liquidation upon termination. 307.20 Section 307.20 Business Credit and Assistance ECONOMIC DEVELOPMENT ADMINISTRATION, DEPARTMENT OF COMMERCE ECONOMIC ADJUSTMENT ASSISTANCE INVESTMENTS Special Requirements...

  7. 13 CFR 307.20 - Partial liquidation; liquidation upon termination.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 13 Business Credit and Assistance 1 2011-01-01 2011-01-01 false Partial liquidation; liquidation upon termination. 307.20 Section 307.20 Business Credit and Assistance ECONOMIC DEVELOPMENT ADMINISTRATION, DEPARTMENT OF COMMERCE ECONOMIC ADJUSTMENT ASSISTANCE INVESTMENTS Special Requirements...

  8. 13 CFR 307.20 - Partial liquidation; liquidation upon termination.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 13 Business Credit and Assistance 1 2013-01-01 2013-01-01 false Partial liquidation; liquidation upon termination. 307.20 Section 307.20 Business Credit and Assistance ECONOMIC DEVELOPMENT ADMINISTRATION, DEPARTMENT OF COMMERCE ECONOMIC ADJUSTMENT ASSISTANCE INVESTMENTS Special Requirements...

  9. 13 CFR 307.20 - Partial liquidation; liquidation upon termination.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 13 Business Credit and Assistance 1 2014-01-01 2014-01-01 false Partial liquidation; liquidation upon termination. 307.20 Section 307.20 Business Credit and Assistance ECONOMIC DEVELOPMENT ADMINISTRATION, DEPARTMENT OF COMMERCE ECONOMIC ADJUSTMENT ASSISTANCE INVESTMENTS Special Requirements...

  10. Polymers at liquid-liquid interfaces: Photophysics and photoredox chemistry

    SciTech Connect

    Webber, S.E.

    1990-11-01

    Research continued on polymers at liquid-liquid interfaces. This quarter, work concentrated on: preparation of poly(styrene-alt-maleic acid-co-chromophore) polymers; studies of vinylnapthalene-maleic acid polymers as emulsifying agents for water-octane; and assembly of optical fiber reticon-based transient absorption system. 3 refs., 1 fig. (CBS)

  11. 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

  12. Probing the Mass-Transfer Stability Limit in Close Binaries

    NASA Astrophysics Data System (ADS)

    D'Souza, M. C. R.; Motl, P. M.; Tohline, J. E.; Frank, J.

    2004-12-01

    We present results from numerical simulations that follow the nonlinear development of mass-transfer instabilities in close binary star systems. A self-consistent-field (SCF) technique is used to construct initial equilibrium models, which are synchronously rotating, semi-detached, polytropic stars on circular orbits. These models are evolved with an Eulerian, finite-difference hydrodynamics code in a fully self-consistent manner. Results are presented for binary systems having a wide range of initial conditions; emphasis is placed on systems in which the mass-transfer stream directly impacts the surface of the accreting star. Some systems are dynamically unstable and result in a merger; others approach a long-term, stable phase of mass transfer. The time-evolutionary behavior of the binary separation, mass transfer rate, spin angular momentum of the accretor, and gravitational wave strain are presented.

  13. Nonstationary Mass Transfer Near the Surface of a Cylindrical Body

    NASA Astrophysics Data System (ADS)

    Rudobashta, S. P.; Kosheleva, M. K.; Kartashov, É. M.

    2015-11-01

    The problem of nonstationary diffusion of the target component to a phase that is external relative to the surface of a cylindrical body has been formulated and solved analytically. From the found solution the dependences have been obtained for calculating the instantaneous mass transfer coefficient and the phase-contact-time mean mass transfer coefficient, on the basis of which the process of extraction of technological pollutants from fibrous materials has been analyzed.

  14. Heat and mass transfer in materials processing

    SciTech Connect

    Tanasawa, I. . Inst. of Industrial Science); Lior, N. . Dept. of Mechanical Engineering and Applied Mechanics)

    1992-01-01

    This book contains forty papers presented at the seminar. The papers are representative of the seminar's scope, and include plasma spraying, laser and electron beam processing, crystal growth, solidification, steel processing, casting and molding, and papermaking, as well as fundamental heat transfer issues and physical properties underlying all of the above. The seminar emphasized thorough discussion of the presentations and of the subfields. Brief summaries of the discussions are presented in the rapporteurs' reports.

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

    DOE PAGESBeta

    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

  16. Oscillatory flow through submerged canopies: 2. Canopy mass transfer

    NASA Astrophysics Data System (ADS)

    Lowe, Ryan J.; Koseff, Jeffrey R.; Monismith, Stephen G.; Falter, James L.

    2005-10-01

    Mass transfer rates from submerged canopies constructed from arrays of vertical cylinders were investigated for a range of different cylinder spacings under both unidirectional and oscillatory flow. Individual canopy elements made from gypsum were dissolved in fresh water to simulate the mass transfer of dissolved metabolites to and from canopies of living benthic organisms. Mass transfer rates under oscillatory flow were up to three times higher than values measured for a comparable unidirectional current. This enhancement was shown to be a strong function of the canopy element spacing. A model was developed to predict canopy mass transfer rates on the basis of the in-canopy flow speed and was generalized to incorporate either unidirectional or oscillatory flow. Agreement between the modeled and experimentally measured mass transfer rates indicate that enhanced mass transfer to/from living benthic canopies under oscillatory flow is driven primarily by the higher in-canopy water motion generated by the oscillatory flow, as detailed in the companion paper (Lowe et al., 2005).

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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 packed bed. A numerical simulation helps to understand the phenomena of heat and mass transfer in the bed. Overall transfer coefficients of them as properties for the simulation were estimated by performing both experiment and calculation. It was clarified that the transient overall equivalent heat and mass transfer does not strongly depend on the air flow rate through the packed bed, the averaged equivalent mass transfer is governed by surface and pore diffusion in a particle of adsorbent at low flow rate. Moreover, the coefficient during the adsorption process is slightly larger than desorption. An equation of the overall mass transfer coefficient is derived. It shows five times as large as the value estimated by experiment. Therefore, the correlation and fitting parameters are presented for prediction of the overall heat and mass transfer coefficients. The estimation accuracy was improved.

  2. Bubble departure in the direct-contact boiling field with a continuous liquid-liquid interface

    SciTech Connect

    Kadoguchi, Katsuhiko

    2007-01-15

    Behavior of vapor bubbles was experimentally investigated in the boiling field where a volatile liquid layer of per-fluorocarbon PF5050 (boiling point 306K) was directly in contact with an immiscible hot liquid layer of water above it. Heat was supplied to the continuous liquid-liquid interface by the impingement of the downward hot water jet. Vapor bubbles were generated not only from this continuous interface but from a large number of PF5050 droplets floating on it. According to precise observation, incipience of boiling did not occur at the liquid-liquid interface but in the PF5050 liquid close to the interface in both cases of continuous and dispersed interfaces. As a result, the bubbles broke up the thin PF5050 liquid film above them and rose up into the water layer. This bubble departure phenomenon, which does not occur in the ordinary pool boiling field on the solid heating wall, is very important to evaluate the heat transfer performance in the present direct-contact boiling system. For modeling this behavior, sizes of the bubbles were measured at the moment just after they were released into the water pool. Volumes of the bubbles were larger in the case of departing from the continuous liquid-liquid interface than from the droplets. This tendency could be explained by taking into account the buoyancy force acting on unit area of the thin PF5050 liquid film above the bubble before departure, which was one of the most important parameters for the liquid film breakdown. (author)

  3. 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.

  4. 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.

  5. 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.

  6. Liquid-liquid critical point in supercooled silicon

    NASA Astrophysics Data System (ADS)

    Vasisht, Vishwas V.; Saw, Shibu; Sastry, Srikanth

    2011-07-01

    A novel liquid-liquid phase transition has been investigated for a wide variety of pure substances, including water, silica and silicon. From computer simulations using the Stillinger-Weber (SW) classical empirical potential, Sastry and Angell demonstrated a first order liquid-liquid transition in supercooled silicon at zero pressure, supported by subsequent experimental and simulation studies. Whether the line of such first order transitions will terminate at a critical point, expected to lie at negative pressures, is presently a matter of debate. Here we report evidence for a liquid-liquid critical point at negative pressures, from computer simulations using the SW potential. We identify Tc~1,120+/-12K, Pc~-0.60+/-0.15GPa as the critical temperature and pressure. We construct the phase diagram of supercooled silicon, which reveals the interconnection between thermodynamic anomalies and the phase behaviour of the system as suggested in previous works. We also observe a strong relationship between local geometry (quantified by the coordination number) and diffusivity, both of which change dramatically with decreasing temperature and pressure.

  7. 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.

  8. Heat and mass transfer over slippery, superhydrophobic surfaces

    NASA Astrophysics Data System (ADS)

    Haase, A. Sander; Lammertink, Rob G. H.

    2016-04-01

    The classical Graetz-Nusselt problem is extended to describe heat and mass transfer over heterogeneously slippery, superhydrophobic surfaces. The cylindrical wall consists of segments with a constant temperature/concentration and areas that are insulating/impermeable. Only in the case of mass transport do the locations of hydrodynamic slip and mass exchange coincide. This makes advection near the mass exchanging wall segments larger than near the heat exchanging regions. Also the direction of radial fluid flow is reversed for heat and mass transport, which has an influence on the location where the concentration or temperature boundary layer is compressed or extended. As a result, mass transport is more efficient than heat transfer. Also the influence of axial diffusion on the Nusselt and Sherwood numbers is investigated for various Péclet numbers Pe. When Pe < 102, which is characteristic for heat transfer over superhydrophobic surfaces, axial conduction should be taken into account. For Pe ≥ 102, which are typical numbers for mass transport in microfluidic systems, axial diffusion can be neglected.

  9. 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.

  10. Mass transfer apparatus and method for separation of gases

    DOEpatents

    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.

  11. Heat and mass transfer considerations in advanced heat pump systems

    SciTech Connect

    Panchal, C.B.; Bell, K.J.

    1992-01-01

    Advanced heat-pump cycles are being investigated for various applications. However, the working media and associated thermal design aspects require new concepts for maintaining high thermal effectiveness and phase equilibrium for achieving maximum possible thermodynamic advantages. In the present study, the heat- and mass-transfer processes in two heat-pump systems -- those based on absorption processes, and those using refrigerant mixtures -- are analyzed. The major technical barriers for achieving the ideal performance predicted by thermodynamic analysis are identified. The analysis provides general guidelines for the development of heat- and mass-transfer equipment for advanced heat-pump systems.

  12. Heat and mass transfer considerations in advanced heat pump systems

    SciTech Connect

    Panchal, C.B.; Bell, K.J.

    1992-08-01

    Advanced heat-pump cycles are being investigated for various applications. However, the working media and associated thermal design aspects require new concepts for maintaining high thermal effectiveness and phase equilibrium for achieving maximum possible thermodynamic advantages. In the present study, the heat- and mass-transfer processes in two heat-pump systems -- those based on absorption processes, and those using refrigerant mixtures -- are analyzed. The major technical barriers for achieving the ideal performance predicted by thermodynamic analysis are identified. The analysis provides general guidelines for the development of heat- and mass-transfer equipment for advanced heat-pump systems.

  13. 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.

  14. 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.

  15. 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

  16. FUNDAMENTAL MASS TRANSFER MODELS FOR INDOOR AIR POLLUTION SOURCES

    EPA Science Inventory

    The paper discusses a simple, fundamental mass transfer model, based on Fick's Law of Diffusion, for indoor air pollution wet sorbent-based sources. (Note: Models are needed to predict emissions from indoor sources. hile empirical approaches based on dynamic chamber data are usef...

  17. 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.

  18. 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.

  19. 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

  20. Analysis of Heat and Mass Transfer in a Desiccant Rotor

    NASA Astrophysics Data System (ADS)

    Hamamoto, Yoshinori; Murase, Sousuke; Akisawa, Atsushi; Kashiwagi, Takao; Okajima, Jirou; Matsuoka, Fumio

    The study aims at clarifying the local heat and mass transfer in the desiccant rotor, and at obtaining the design aspects of high efficient desiccant rotor and operation method. In the paper, theoretical analysis is performed for rotary dehumidifier. Both surface diffusion and mass transfer coefficient are considered in the model. It is examined that the results of calculation agree well with the experimental data. The local temperature, humidity and the amount of adsorbed water vapor are calculated. It is clarified that temperature and humidity of air in the rotor change clockwise between each inlet air condition on the psychrometric chart. The outlet temperature and humidity distribution of the rotor is clarified in the system showing the optimum rotor speed. Furthermore, it is clarified that local desorption rate is higher than adsorption rate. It is attributed to the increase of mass transfer coefficient and surface diffusivity of the rotor during desorption process. And, it is clarified that the influence of surface diffusion on amount of adsorbed water vapor is much larger than that of mass transfer coefficient.

  1. Dissociation and Mass Transfer Coefficients for Ammonia Volatilization Models

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  2. 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)

  3. Microfluidic droplet-based liquid-liquid extraction.

    PubMed

    Mary, Pascaline; Studer, Vincent; Tabeling, Patrick

    2008-04-15

    We study microfluidic systems in which mass exchanges take place between moving water droplets, formed on-chip, and an external phase (octanol). Here, no chemical reaction takes place, and the mass exchanges are driven by a contrast in chemical potential between the dispersed and continuous phases. We analyze the case where the microfluidic droplets, occupying the entire width of the channel, extract a solute-fluorescein-from the external phase (extraction) and the opposite case, where droplets reject a solute-rhodamine-into the external phase (purification). Four flow configurations are investigated, based on straight or zigzag microchannels. Additionally to the experimental work, we performed two-dimensional numerical simulations. In the experiments, we analyze the influence of different parameters on the process (channel dimensions, fluid viscosities, flow rates, drop size, droplet spacing, ...). Several regimes are singled out. In agreement with the mass transfer theory of Young et al. (Young, W.; Pumir, A.; Pomeau, Y. Phys. Fluids A 1989, 1, 462), we find that, after a short transient, the amount of matter transferred across the droplet interface grows as the square root of time and the time it takes for the transfer process to be completed decreases as Pe-2/3, where Pe is the Peclet number based on droplet velocity and radius. The numerical simulation is found in excellent consistency with the experiment. In practice, the transfer time ranges between a fraction and a few seconds, which is much faster than conventional systems. PMID:18351786

  4. Multidimensional mechanistic modeling of interfacial heat and mass transfer

    SciTech Connect

    Shaver, D. R.; Antal, S. P.; Podowski, M. Z.

    2012-07-01

    A combined theoretical and computational study in modeling multidimensional, diabatic vapor/liquid flows is presented. Models have been developed governing kinematic aspects of multiphase flow as well as interfacial mass and heat transfer for flows of condensable gas (vapor) and liquids. The modeling formulation is based on the Reynolds averaged Navier-Stokes (RANS) type multi-field approach which utilizes a complete set of conservation equations for each fluid component 1. The modeled interfacial interactions include energy, mass, and momentum transfer. Emphasis in the model development work has been placed on the mechanisms governing coupled interfacial heat and mass transfer between the liquid and vapor fields (condensation and/or boiling). A method for tracking changes in bubble size is presented and tested. Locally based models of multidimensional effects have been analyzed, including distributions of fluid temperatures and volume fractions. The overall model accounts for both kinematic and thermodynamic nonequilibrium between the component fluids including superheated vapor. The model has been implemented in the NPHASE-CMFD computer code. Results from the kinematic model are compared to experimental data and good agreement is demonstrated. The heat and mass transfer model is parametrically tested to show the multidimensional effects on the rate of heat and mass transfer. These effects are explained in terms of local characteristics of the two-phase flow. The model is applied to a scenario of saturated vapor injected into a subcooled flow through a heated, porous wall. This provides a reasonable approximation to subcooled boiling. The results are found to be dependent on the partitioning of the wall heat flux between direct liquid heating and vapor generation. However, the observed dependencies are explained and the modeling is considered consistent. (authors)

  5. Mass transfer experiments on single irregular-shaped particles

    SciTech Connect

    Ramezan, M. ); Kale, S.R. ); Anderson, R.J. )

    1991-01-01

    Mass transfer from irregular-shaped naphthalene particles (100-200 {mu}m in size) was studied in an electrodynamic balance. Charged particles were suspended in an electrostatic field directly in line with a calibrated air jet. Mass and size change histories were obtained under ambient conditions, and under steady- and pulsed-flow conditions. For natural convection, the time-averaged Sherwood number was similar to that for spheres. Forced-convection Sherwood number under steady-flow conditions was strongly dependent on particle shape and particle Reynolds number, and was consistently higher than values predicted for spheres at comparable Reynolds numbers. This paper validates the technique and indicates the shape effect on mass transfer from single particles.

  6. 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)

  7. 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.

  8. 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)

  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. PMID:27320727

  10. 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

  11. Simplified Simulation of Mass Transfer in Double White Dwarf Systems

    NASA Astrophysics Data System (ADS)

    Vannah, Sara; Frank, Juhan

    2016-01-01

    The behavior both stable and unstable mass transfer in semi-detached double white dwarfs triggers a cornucopia of astrophysical phenomena including Type Ia supernovae and AM CVn stars. Current 3D hydrodynamic simulations of the evolution these systems following the mass transfer, binary orbital parameters, and the self-consistent gravitational field over several tens of orbital periods have produced a wealth of data. However, these simulations can take weeks to months in high-performance computing platforms to execute. To help with the interpretation of results of such large scale simulations, and to enable a quick exploration of binary parameter space, we have developed a Mathematica code that integrates forward in time a system of 5 ODEs describing the orbit-averaged evolution of the binary separation as well as the radius, mass, and spin angular momentum of both components of the binary. By adjusting a few parameters describing the mass transfer as a function of the Roche-lobe overflow and the strength of the tidal coupling between the orbit and component spins we are able to obtain approximate fits to previously run hydrodynamic simulations. This simplified simulation is able to run simulations similar to the hydrodynamic versions in a matter of seconds on a dual-core PC or Mac computer.

  12. Mixing and mass transfer considerations in highly viscous fermentations

    SciTech Connect

    Applegate, M.A.; Flatt, J.H.

    1995-12-01

    Highly viscous microbial fermentations pose difficult scale-up challenges for the industrial biochemical engineer. Incomplete bulk mixing and poor oxygen mass transfer often limit fermentor titers and productivities. Lower heat transfer coefficients coupled with higher rates of heat generation through viscous dissipation further confound operational difficulties. Practical approaches to alleviating these factors will be discussed using examples from viscoelastic gellan, welan, and xanthan gum fermentations. In addition, a summary of the effects of power input, aeration, media manipulation, and genetic modifications will be discussed.

  13. Mass transfer at gas-evolving surfaces in electrolysis

    SciTech Connect

    Dees, D.W.; Tobias, C.W.

    1983-09-01

    A novel micro-mosaic electrode was developed to resolve time-dependent, mass-transfer distribution in the close vicinity of bubble phenomena. The electrode, prepared on a silicon wafer using integrated circuit manufacturing technology, consists of a 10 by 10 matrix of coplanar, electrically isolated, square platinum segments on 100 micron centers, surrounded by a relatively large buffer segment. A computer-actuated data acquisition and control system was assembled and the software developed to monitor the current to each of the segments and control the potential of selected segments. The utility of the electrode to examine interfacial mass transport phenomena which have characteristic lengths as small as 100 microns has been clearly demonstrated. The effect of a single hydrogen bubble disengagement and of the coalescence of two bubbles, on the limiting current of the reduction of ferric to ferrous ion was measured using the micro-mosaic electrode in a horizontal: facing-up orientation. In the absence of gas evolution, large regular fluctuations in the limiting current to the segments with a period of 29 sec were observed. This periodic behavior is attributed to free convection: a cellular fluid motion moving across the electrode with a velocity of 40 microns/second. It was found that the mass-transfer enhancement due to bubble disengagement is small when compared to that due to coalescence. Increases in the mass-transfer rate of more than an order of magnitude over the free convection limiting current were observed for the coalescence phenomena. Two theoretical models were developed to account for the observed effect of a bubble disengagement on the mass transfer-rate to the surface.

  14. 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.

  15. 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. PMID:24287814

  16. Mass transfer and magnetic braking in Sco X-1

    NASA Astrophysics Data System (ADS)

    Pavlovskii, K.; Ivanova, N.

    2016-02-01

    Sco X-1 is a low-mass X-ray binary (LMXB) that has one of the most precisely determined set of binary parameters such as the mass accretion rate, companions mass ratio and the orbital period. For this system, as well as for a large fraction of other well-studied LMXBs, the observationally-inferred mass accretion rate is known to strongly exceed the theoretically expected mass transfer (MT) rate. We suggest that this discrepancy can be solved by applying a modified magnetic braking prescription, which accounts for increased wind mass-loss in evolved stars compared to main sequence stars. Using our MT framework based on MESA, we explore a large range of binaries at the onset of the MT. We identify the subset of binaries for which the MT tracks cross the Sco X-1 values for the mass ratio and the orbital period. We confirm that no solution can be found for which the standard magnetic braking can provide the observed accretion rates, while wind-boosted magnetic braking can provide the observed accretion rates for many progenitor binaries that evolve to the observed orbital period and mass ratio.

  17. Heat and Mass Transfer in a Freezing Unsaturated Porous Medium

    NASA Astrophysics Data System (ADS)

    Jame, Yih-Wu; Norum, Donald I.

    1980-08-01

    A numerical simulation of a laboratory experiment involving coupled heat and mass transfer in a horizontal porous medium column with one end subjected to a temperature below 0°C has been carried out. The model is essentially that of Harlan (1973) and is solved numerically by the finite difference method using the Crank-Nicholson scheme. The solution yields temperature, liquid water content, and ice content profiles along the column as a function of time. Comparison of the experimental results and the simulation analysis results shows that Harlan's model, with some modification in the hydraulic conductivity of the frozen medium, can be used successfully to simulate numerically the coupled heat and mass transfer processes when ice lensing does not occur.

  18. Nonlinear analysis of capillary instability with heat and mass transfer

    NASA Astrophysics Data System (ADS)

    Awasthi, Mukesh Kumar; Agrawal, G. S.

    2012-06-01

    The nonlinear capillary instability of the cylindrical interface between the vapor and liquid phases of a fluid is studied when there is heat and mass transfer across the interface, using viscous potential flow theory. The fluids are considered to be viscous and incompressible with different kinematic viscosities. Both asymmetric and axisymmetric disturbances are considered. The analysis is based on the method of multiple scale perturbation and the nonlinear stability is governed by first-order nonlinear partial differential equation. The stability conditions are obtained and discussed theoretically as well as numerically. Regions of stability and instability have been shown graphically indicating the effect of various parameters. It has been observed that the heat and mass transfer has stabilizing effect on the stability of the system in the nonlinear analysis for both axisymmetric as well as asymmetric disturbances.

  19. 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. PMID:18321130

  20. 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.

  1. Conjugate mixed convection heat and mass transfer in brick drying

    NASA Astrophysics Data System (ADS)

    Suresh, H. N.; Aswatha Narayana, P. A.; Seetharamu, K. N.

    In this study, a numerical methodology for the solution of conjugate heat and mass transfer problem is presented. Fluid flow, heat and mass transfer over a rectangular brick due to transient laminar mixed convection has been numerically simulated. The coupled non-linear partial differential equations, for both gas phase and solid are solved using finite element procedure. Flow is assumed to be incompressible, two-dimensional, laminar. Analysis has been carried out at a Reynolds number of 200 with Pr=0.71. The effect of buoyancy on the brick drying has been investigated. Velocity vectors, streamlines in the flow field and temperature and moisture contours and temperature distribution along the solid surface are presented. It is observed that there is considerable effect of buoyancy during drying. The results indicate a non-uniform drying of the brick with the leading edge drying faster than the rest of the brick.

  2. 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.

  3. The impact of separated flow on heat and mass transfer

    SciTech Connect

    Goldstein, R.J.; Jabbari, M.Y.

    1990-01-01

    An investigation of the effect of flow separation on heat (or mass) transfer is underway. This research, sponsored by the Department of Energy (Contract No. FG02-87ER13800), is planned to enhance our understanding of the fundamental mechanisms governing the process. This report summarizes previous accomplishments and briefly describes works done during period May 1, 1989 through April 30, 1990. Future plans and studies under preparation are also mentioned. 8 refs., 7 figs.

  4. 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. PMID:20432097

  5. [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. PMID:16250442

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Modelling mass transfer and agitator performance in multiturbine fermentors.

    PubMed

    Bader, F G

    1987-07-01

    A methodology for mathematically analyzing agitator performance and mass transfer in large multiturbine production fermentors is presented. The application of this approach provides a method for determining axial dissolved oxygen profiles under conditions of known mass transfer rates as a function of agitation-aeration characteristics. A stagewise approach is used which divides the fermentor into a series of mixing cells. This allows for each turbine and mixing cell to be individually optimized. The model also permits the determination of the mass transfer coefficient for each turbine based upon limited dissolved oxygen data. The primary limitation of this approach rests in the limited data and correlations available for multiturbine systems. The structure of the modelling approach can serve as a basis for testing single turbine correlations and adapting them to multiturbine systems. The step-by-step details of the mathematical analysis are presented and interpreted. A series of computer simulations demonstrate the effect of typical fermentor operating variables on the axial dissolved oxygen profile. Further simulations demonstrate the effect of modifying agitator blade numbers on the dissolved oxygen profile and agitator power requirement. PMID:18576581

  11. 2D and 3D Mass Transfer Simulations in β Lyrae System

    NASA Astrophysics Data System (ADS)

    Nazarenko, V. V.; Glazunova, L. V.; Karetnikov, V. G.

    2001-12-01

    2D and 3D mass transfer simulations of the mass transfer in β Lyrae binary system. We have received that from a point L3 40 per cent of mass transfer from L1-point is lost.The structure of a gas envelope, around system is calculated.3-D mass transfer simulations has shown presence the spiral shock in the disk around primary star's and a jet-like structures (a mass flow in vertical direction) over a stream.

  12. A Comparison of Stellar Mass-Transfer & Merger Simulations

    NASA Astrophysics Data System (ADS)

    Tohline, Joel E.; Motl, P.; Diehl, S.; Even, W.; Clayton, G.; Fryer, C.

    2011-01-01

    We present detailed comparisons of 3D stellar mass-transfer and merger simulations that have been carried out using two very different numerical hydrodynamic algorithms -- a finite-volume "grid" code (typically using 4M cylindrical grid cells) and a smoothed-particle hydrodynamics (SPH) code (typically using 1M particles). In all cases the initial binary models contain synchronously rotating, n = 3/2 polytropic stars of a specified mass ratio (q = Mdonor/Maccretor) that are in circular orbit with one star (the donor) marginally filling its Roche lobe. In our "base" set of 8 comparison simulations, we have followed the evolution of binaries having four different initial mass ratios (q0 = 1.3, 0.7, 0.5, 0.4) and each is evolved using two different equations of state: polytropic (P) and ideal-gas (I). In addition, some evolutions are repeated using a different numerical resolution and/or a different initial episode of "driving" to initiate mass-transfer. In the case of the binary systems with q0 = 1.3 and q0 = 0.7, the codes show a remarkable level of quantitative agreement; in the former case, the two stars merge and, in the latter case, the donor gets tidally disrupted. Binary systems with q0 = 0.5 or 0.4 enter a long phase (> 10-20 orbits) of stable mass-transfer during which the binary separation steadily increases; tidal disruption of the donor may ultimately occur if sufficiently deep contact is made between the Roche lobe and the donor during an initial episode of "driving." This work has been supported by grants AST-0708551 and DGE-0504507 from the U.S. National Science Foundation; by grants NNX07AG84G and NNX10AC72G from NASA's ATP program; and by grants of high-performance computing time on the TeraGrid, at LSU and across LONI (Louisiana Optical Network Initiative).

  13. 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

  14. Plasmonic ruler at the liquid-liquid interface.

    PubMed

    Turek, Vladimir A; Cecchini, Michael P; Paget, Jack; Kucernak, Anthony R; Kornyshev, Alexei A; Edel, Joshua B

    2012-09-25

    We report on a simple, fast, and inexpensive method to study adsorption and desorption of metallic nanoparticles at a liquid/liquid interface. These interfaces provide an ideal platform for the formation of two-dimensional monolayers of nanoparticles, as they form spontaneously and are defect-correcting, acting as 2D "nanoparticle traps". Such two-dimensional, self-assembled nanoparticle arrays have a vast range of potential applications in displays, catalysis, plasmonic rulers, optoelectronics, sensors, and detectors. Here, we show that 16 nm diameter gold nanoparticles can be controllably adsorbed to a water/1,2-dichloroethane interface, and that we can control the average interparticle spacing at the interface over the range 6-35 nm. The particle density and average interparticle spacing are experimentally assessed by measuring the optical plasmonic response of the nanoparticles in the bulk and at the interface and by comparing the experimental data with existing theoretical results. PMID:22900717

  15. Liquid-Liquid Phase Transition in Nanoconfined Silicon Carbide.

    PubMed

    Wu, Weikang; Zhang, Leining; Liu, Sida; Ren, Hongru; Zhou, Xuyan; Li, Hui

    2016-03-01

    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. PMID:26859609

  16. 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.

  17. 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

  18. Mathematical modeling heat and mass transfer processes in porous media

    NASA Astrophysics Data System (ADS)

    Akhmed-Zaki, Darkhan

    2013-11-01

    On late development stages of oil-fields appears a complex problem of oil-recovery reduction. One of solution approaches is injecting of surfactant together with water in the form of active impurities into the productive layer - for decreasing oil viscosity and capillary forces between ``oil-water'' phases system. In fluids flow the surfactant can be in three states: dissolved in water, dissolved in oil and adsorbed on pore channels' walls. The surfactant's invasion into the reservoir is tracked by its diffusion with reservoir liquid and mass-exchange with two phase (liquid and solid) components of porous structure. Additionally, in this case heat exchange between fluids (injected, residual) and framework of porous medium has practical importance for evaluating of temperature influences on enhancing oil recovery. Now, the problem of designing an adequate mathematical model for describing a simultaneous flowing heat and mass transfer processes in anisotropic heterogeneous porous medium -surfactant injection during at various temperature regimes has not been fully researched. In this work is presents a 2D mathematical model of surfactant injections into the oil reservoir. Description of heat- and mass transfer processes in a porous media is done through differential and kinetic equations. For designing a computational algorithm is used modify version of IMPES method. The sequential and parallel computational algorithms are developed using an adaptive curvilinear meshes which into account heterogeneous porous structures. In this case we can evaluate the boundaries of our process flows - fronts (``invasion'', ``heat'' and ``mass'' transfers), according to the pressure, temperature, and concentration gradient changes.

  19. 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

  20. 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.

  1. 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. PMID:26840001

  2. 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

  3. 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

  4. Coarsening of sand ripples in mass transfer models.

    PubMed

    Hellén, E K O; Krug, J

    2002-07-01

    Coarsening of sand ripples is studied in a one-dimensional stochastic model, where neighboring ripples exchange mass with algebraic rates, Gamma(m) approximately m(gamma), and ripples of zero mass are removed from the system. For gamma<0, ripples vanish through rare fluctuations and the average ripple mass grows as (t) approximately -gamma(-1)ln(t). Temporal correlations decay as t(-1/2) or t(-2/3) depending on the symmetry of the mass transfer, and asymptotically the system is characterized by a product measure. The stationary ripple mass distribution is obtained exactly. For gamma>0, ripple evolution is linearly unstable, and the noise in the dynamics is irrelevant. For gamma=1, the problem is solved on the mean-field level, but the mean-field theory does not adequately describe the full behavior of the coarsening. In particular, it fails to account for the numerically observed universality with respect to the initial ripple size distribution. The results are not restricted to sand ripple evolution since the model can be mapped to zero range processes, urn models, exclusion processes, and cluster-cluster aggregation. PMID:12241351

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. Heat and mass transfer intensification in coaxial reactor

    NASA Astrophysics Data System (ADS)

    Ananyev, D. V.; Halitova, G. R.

    2014-04-01

    The work considers heat and mass transfer in the homophasic polymerization reactor. The reactor is a coaxial channel with internal tube in the form of a channel of confusor-diffuser type. The authors compared the degree of polymer transformation in the intensified coaxial reactor with internal tube of confusor-diffuser type and the reactor with constant rectilinear longitudinal section. It was found that in coaxial channels with internal tube of confusor-diffuser type, it is possible to reach high values of the transformation degree and to improve the quality of the obtained polymer.

  10. Increasing peritoneal contact area during dialysis improves mass transfer.

    PubMed

    Flessner, M F; Lofthouse, J; Williams, A

    2001-10-01

    Previous studies in mice demonstrated that relatively large volumes in the peritoneal cavity made contact with only 40% of the anatomic peritoneum and that this contact area (A(contact)) could be increased with use of a surfactant, dioctyl sodium sulfosuccinate (DSS). To investigate the hypothesis that mass transfer rates during peritoneal dialysis are dependent on the area of peritoneum in contact with the dialysis solution, rats were dialyzed for 2 h with a solution that contained (14)C-mannitol, with or without 0.02% DSS. The mass transfer-area coefficients (MTAC) were determined to be (mean +/- SEM, ml/min): no DSS, 0.163 +/- 0.008; with DSS, 0.247 +/- 0.006 (P < 0.002). DSS also caused an increase in total protein loss over 2 h (mean +/- SEM, mg): no DSS, 83.8 +/- 15.8; DSS, 159.5 +/- 6.3 (P < 0.001). In a separate set of animals, the ratio (R) of A(contact) to anatomic area in each plane was measured as in the previous study R(mean) (mean +/- SEM) and equaled 0.466 +/- 0.075, no DSS; 0.837 +/- 0.074, with DSS. The ratio of MTAC (1.52) and protein loss (1.90) approximate the ratio of R(mean(S)) (1.78). Because MTAC = mass transfer coefficient (MTC) x A(contact), small peritoneal transport chambers were used to determine MTC for (14)C-mannitol and fluorescein isothiocyanate-albumin. MTC(mannitol) did not change significantly with the addition of DSS. MTC(albumin) (cm/min x 10(4), mean +/- SEM) equaled 1.47 +/- 0.45 without DSS and 1.78 +/- 0.52 with DSS (P < 0.04). It was concluded that DSS increases the mass transfer rates of mannitol and protein by increasing A(contact), whereas protein transport is further augmented by an apparent increase in the barrier permeability to protein. PMID:11562413