WorldWideScience

Sample records for liquid sample introduction

  1. Flow system for liquid sample introduction in arc/spark excitation sources

    OpenAIRE

    Bellato, CR; Pasquini, C

    1996-01-01

    A flow system based on the monosegmented flow analysis (MSFA) approach is described for delivery of liquid samples to arc/spark excitation sources commonly used in spectrographs. A Carl Zeiss PGS-2 spectrograph, previously-automated in the laboratory by replacing its photographic plate detection system with a photodiode array, was employed, The sample is introduced via an injection port into the path to the excitation source, where the liquid sample plug (typically 50 mu l) is passed through ...

  2. Alternative sample-introduction technique to avoid breakthrough in gradient-elution liquid chromatography of polymers

    NARCIS (Netherlands)

    Reingruber, E.; Bedani, F.; Buchberger, W.; Schoenmakers, P.

    2010-01-01

    Gradient-elution liquid chromatography (GELC) is a powerful tool for the characterization of synthetic polymers. However, gradient-elution chromatograms often suffer from breakthrough phenomena. Breakthrough can be averted by using a sample solvent as weak as the mobile phase. However, this approach

  3. Short torch design for direct liquid sample introduction using conventional and micro-nebulizers for plasma spectrometry

    Science.gov (United States)

    Montaser, Akbar; Westphal, Craig S.; Kahen, Kaveh; Rutkowski, William F.

    2008-01-08

    An apparatus and method for providing direct liquid sample introduction using a nebulizer are provided. The apparatus and method include a short torch having an inner tube and an outer tube, and an elongated adapter having a cavity for receiving the nebulizer and positioning a nozzle tip of the nebulizer a predetermined distance from a tip of the outer tube of the short torch. The predetermined distance is preferably about 2-5 mm.

  4. Sample introduction systems for the analysis of liquid microsamples by ICP-AES and ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Todoli, Jose L. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Universidad de Alicante, 03080 Alicante (Spain)]. E-mail: jose.todoli@ua.es; Mermet, Jean M. [Spectroscopy Forever, 01390 Tramoyes (France)

    2006-03-15

    There are many fields in which the available sample volume is the limiting factor for an elemental analysis. Over the last ten years, sample introduction systems used in plasma spectrometry (i.e., Inductively Coupled Plasma Atomic Emission Spectrometry, ICP-AES, and Mass Spectrometry, ICP-MS) have evolved in order to expand the field of applicability of these techniques to the analysis of micro- and nanosamples. A full understanding of the basic processes occurring throughout the sample introduction system is absolutely necessary to improve analytical performance. The first part of the present review deals with fundamental studies concerning the different phenomena taking place from aerosol production to analyte excitation/ionization when the liquid consumption rate does not exceed 100 {mu}l/min. Existing sample introduction systems are currently far from the ideal and a significant effort has been made to develop new and efficient devices. Different approaches for continuously introducing small sample volumes (i.e., microsamples) have been reviewed and compared in the present work. Finally, applications as well as basic guidelines to select the best sample introduction system according to the sample particularities are given at the end of this review.

  5. Alternative sample-introduction technique to avoid breakthrough in gradient-elution liquid chromatography of polymers.

    Science.gov (United States)

    Reingruber, Eva; Bedani, Filippo; Buchberger, Wolfgang; Schoenmakers, Peter

    2010-10-15

    Gradient-elution liquid chromatography (GELC) is a powerful tool for the characterization of synthetic polymers. However, gradient-elution chromatograms often suffer from breakthrough phenomena. Breakthrough can be averted by using a sample solvent as weak as the mobile phase. However, this approach is only applicable to polymers for which a sufficiently strong solvent exists which is at the same time a weak eluent. Finding such a solvent for a given polymer can be laborious or may even be impossible. Besides, when working with comprehensive two-dimensional LC the effluent of the first dimension is the injection solvent of the second dimension. In this case, it is not possible to avoid breakthrough by adjusting the eluent strength of the second-dimension injection solvent. Therefore, another strategy to avert breakthrough has to be implemented. In this work, we successfully avoided breakthrough in GELC by mixing the mobile phase not before, but after the autosampler. This was demonstrated measuring a blend of poly(methyl methacrylate) standards with different molecular-weights as model mixture with comprehensive two-dimensional GELC×size-exclusion chromatography. The strategy is thought to be applicable to all substances with a sufficiently strong dependence of retention on mobile-phase composition. This typically applies to large molecules (synthetic and natural polymers) and allows efficient refocusing. Unretained and barely retained substances are not refocused and therefore suffer in the proposed setup from peak broadening. Copyright © 2010 Elsevier B.V. All rights reserved.

  6. Combination of dispersive liquid-liquid microextraction with flame atomic absorption spectrometry using microsample introduction for determination of lead in water samples

    Energy Technology Data Exchange (ETDEWEB)

    Naseri, Mohammad Taghi; Hemmatkhah, Payam; Hosseini, Mohammad Reza Milani [Department of Analytical Chemistry, Faculty of Chemistry, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Electroanalytical Chemistry Research Center, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Assadi, Yaghoub [Department of Analytical Chemistry, Faculty of Chemistry, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Electroanalytical Chemistry Research Center, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of)], E-mail: y_assadi@iust.ac.ir

    2008-03-03

    The dispersive liquid-liquid microextraction (DLLME) was combined with the flame atomic absorption spectrometry (FAAS) for determination of lead in the water samples. Diethyldithiophosphoric acid (DDTP), carbon tetrachloride and methanol were used as chelating agent, extraction solvent and disperser solvent, respectively. A new FAAS sample introduction system was employed for the microvolume nebulization of the non-flammable chlorinated organic extracts. Injection of 20 {mu}L volumes of the organic extract into an air-acetylene flame provided very sensitive spike-like and reproducible signals. Some effective parameters on the microextraction and the complex formation were selected and optimized. These parameters include extraction and disperser solvent type as well as their volume, extraction time, salt effect, pH and amount of the chelating agent. Under the optimized conditions, the enrichment factor of 450 was obtained from a sample volume of 25.0 mL. The enhancement factor, calculated as the ratio of the slopes of the calibration graphs with and without preconcentration, which was about 1000. The calibration graph was linear in the range of 1-70 {mu}g L{sup -1} with a detection limit of 0.5 {mu}g L{sup -1}. The relative standard deviation (R.S.D.) for seven replicate measurements of 5.0 and 50 {mu}g L{sup -1} of lead were 3.8 and 2.0%, respectively. The relative recoveries of lead in tap, well, river and seawater samples at the spiking level of 20 {mu}g L{sup -1} ranged from 93.8 to 106.2%. The characteristics of the proposed method were compared with those of the liquid-liquid extraction (LLE), cloud point extraction (CPE), on-line and off-line solid-phase extraction (SPE) as well as co-precipitation, based on bibliographic data. Operation simplicity, rapidity, low cost, high enrichment factor, good repeatability, and low consumption of the extraction solvent at a microliter level are the main advantages of the proposed method.

  7. Separation and determination of copper in bottled water samples by combination of dispersive liquid--liquid microextraction and microsample introduction flame atomic absorption spectrometry.

    Science.gov (United States)

    Citak, Demirhan; Tuzen, Mustafa

    2013-01-01

    A new and simple method for the determination of trace amounts of Cu(II) was developed by combination of dispersive liquid-liquid microextraction (DLLME) preconcentration and microsample introduction flame atomic absorption spectrometry. In this method, ethanol and chloroform were chosen as disperser and extraction solvents, respectively, and 1-nitroso-2-naphthol was used as the complexing agent. The factors affecting the extraction efficiency and determination of Cu(II), including extraction and disperser solvent nature and volume, concentration of the complexing agent, pH of the solution, extraction time, and matrix ions, were investigated. Under optimal conditions, the LOD for Cu(II) was 0.95 microg/L with a preconcentration factor of 70. The RSD was 1.9%. The accuracy of the developed DLLME method was verified by determination of Cu(II) in a certified reference material (NRCC-SLRS-4 river water). The relative error was -3.31%. The developed preconcentration procedure was successfully applied to the analysis of bottled drinking water samples.

  8. The impact of the introduction of liquid based cytology on the variation in the proportion of inadequate samples between GP practices

    Directory of Open Access Journals (Sweden)

    Jones Suzanne P

    2007-08-01

    Full Text Available Abstract Background Historically there has been a wide variation in the proportion of inadequate smears between general practices. Cervical screening in the UK is undergoing a fundamental change by moving from conventional to liquid based cytology (LBC. The main driver for this change has been a predicted reduction in the proportions of inadequate samples. This study investigates the effect of LBC on the variation in the proportion of inadequate samples between general practices using Shewhart's theory of variation and control charts. Methods Routinely collected cervical cytology data was obtained for all general practices in two localities in South Staffordshire for periods before and after the introduction of liquid based cytology. Control charts of the proportion of inadequate smears were plotted for the practices stratified by laboratory. A standardised measure of variation for all of the practices in each laboratory and each time period was also calculated. Results Following the introduction of liquid based cytology the overall proportion of inadequate samples in the two localities fell from 11.8 to 1.3% (p Conclusion A reduction in the proportion of inadequate samples has been realised in these localities. The reduction in the overall proportion of inadequate samples has also been accompanied by a reduction in variation between GP practices.

  9. Introduction to modern liquid chromatography

    National Research Council Canada - National Science Library

    Snyder, Lloyd R; Kirkland, J. J; Dolan, John W

    2010-01-01

    "High-performance liquid chromatography (HPLC) is today the leading technique for chemical analysis and related applications, with an ability to separate, analyze, and/or purify virtually any sample...

  10. Fully Automatic In-Syringe Magnetic Stirring-Assisted Dispersive Liquid-Liquid Microextraction Hyphenated to High-Temperature Torch Integrated Sample Introduction System-Inductively Coupled Plasma Spectrometer with Direct Injection of the Organic Phase.

    Science.gov (United States)

    Sánchez, Raquel; Horstkotte, Burkhard; Fikarová, Kateřina; Sklenářová, Hana; Maestre, Salvador; Miró, Manuel; Todolí, Jose-Luis

    2017-03-21

    A proof of concept study involving the online coupling of automatic dispersive liquid-liquid microextraction (DLLME) to inductively coupled plasma optical emission spectrometry (ICP OES) with direct introduction and analysis of the organic extract is herein reported for the first time. The flow-based analyzer features a lab-in-syringe (LIS) setup with an integrated stirring system, a Meinhard nebulizer in combination with a heated single-pass spray chamber, and a rotary injection valve, used as an online interface between the microextraction system and the detection instrument. Air-segmented flow was used for delivery of a fraction of the nonwater miscible extraction phase, 12 μL of xylene, to the nebulizer. All sample preparative steps including magnetic stirring assisted DLLME were carried out inside the syringe void volume as a size-adaptable yet sealed mixing and extraction chamber. Determination of trace level concentrations of cadmium, copper, lead, and silver as model analytes has been demonstrated by microextraction as diethyldithiophosphate (DDTP) complexes. The automatic LIS-DLLME method features quantitative metal extraction, even in troublesome sample matrixes, such as seawater, salt, and fruit juices, with relative recoveries within the range of 94-103%, 93-100%, and 92-99%, respectively. Furthermore, no statistically significant differences at the 0.05 significance level were found between concentration values experimentally obtained and the certified values of two serum standard reference materials.

  11. Introduction to liquid wall film atomization

    Directory of Open Access Journals (Sweden)

    Jícha Miroslav

    2012-04-01

    Full Text Available The objective of the article is an introduction to the theoretical study of atomization of droplets from the surface of a thin liquid film. The overview of basic principles of atomization prediction is complemented by the comparison of the calculations performed according to the selected approaches.

  12. Use of factorial design for evaluation of plasma conditions and comparison of two liquid sample introduction systems for an axially viewed inductively coupled plasma optical emission spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Trevizan, Lilian C. [Grupo de Analise Instrumental Aplicada, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, Sao Carlos, SP, 13650-970 (Brazil); Vieira, Edivan C. [Grupo de Analise Instrumental Aplicada, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, Sao Carlos, SP, 13650-970 (Brazil); Embrapa Pecuaria Sudeste, Sao Carlos, SP (Brazil); Nogueira, Ana Rita A. [Embrapa Pecuaria Sudeste, Sao Carlos, SP (Brazil); Nobrega, Joaquim A. [Grupo de Analise Instrumental Aplicada, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, Sao Carlos, SP, 13650-970 (Brazil)]. E-mail: djan@terra.com.br

    2005-06-30

    A factorial design was applied to evaluate plasma conditions employing the Mg II 280/Mg I 285 nm intensity ratio in an axially viewed inductively coupled plasma optical emission spectrometer using different sample introduction devices: a concentric or a V-groove nebulizer and a cyclonic or a Sturman-Masters spray chamber. Effects of nebulizer gas flow-rate on Mg II/Mg I ratio were different in each introduction system. Robust conditions were obtained at low nebulizer gas flow-rate when using concentric nebulizer with a cyclonic spray chamber or a concentric nebulizer and a Sturman-Masters spray chamber. However, when using a V-groove nebulizer with a Sturman-Masters spray chamber, Mg II/Mg I ratio increased at high nebulizer gas flow-rates. Recovery experiments for a milk standard reference material diluted in water-soluble tertiary amines in both robust and non-robust conditions indicated that the robust condition was reached at higher nebulizer gas flow-rates and led to better accuracy and precision when using a V-groove nebulizer.

  13. A microfluidic chip for ICPMS sample introduction.

    Science.gov (United States)

    Verboket, Pascal E; Borovinskaya, Olga; Meyer, Nicole; Günther, Detlef; Dittrich, Petra S

    2015-03-05

    This protocol discusses the fabrication and usage of a disposable low cost microfluidic chip as sample introduction system for inductively coupled plasma mass spectrometry (ICPMS). The chip produces monodisperse aqueous sample droplets in perfluorohexane (PFH). Size and frequency of the aqueous droplets can be varied in the range of 40 to 60 µm and from 90 to 7,000 Hz, respectively. The droplets are ejected from the chip with a second flow of PFH and remain intact during the ejection. A custom-built desolvation system removes the PFH and transports the droplets into the ICPMS. Here, very stable signals with a narrow intensity distribution can be measured, showing the monodispersity of the droplets. We show that the introduction system can be used to quantitatively determine iron in single bovine red blood cells. In the future, the capabilities of the introduction device can easily be extended by the integration of additional microfluidic modules.

  14. Estimating Aquatic Insect Populations. Introduction to Sampling.

    Science.gov (United States)

    Chihuahuan Desert Research Inst., Alpine, TX.

    This booklet introduces high school and junior high school students to the major groups of aquatic insects and to population sampling techniques. Chapter 1 consists of a short field guide which can be used to identify five separate orders of aquatic insects: odonata (dragonflies and damselflies); ephemeroptera (mayflies); diptera (true flies);…

  15. Theory of liquids and other disordered media a short introduction

    CERN Document Server

    Schirmacher, Walter

    2015-01-01

    This set of lectures provides an introduction to the structure, thermodynamics and dynamics of liquids, binary solutions and polymers at a level that will enable graduate students and non-specialist researchers to understand more specialized literature and to possibly start their own work in this field. Part I starts with the introduction of distribution functions, which describe the statistical arrangements of atoms or molecules in a simple liquid. The main concepts involve mean field theories like the Perkus-Yevick theory and the random phase approximation, which relate the forces to the distribution functions. In order to provide a concise, self-contained text, an understanding of the general statistical mechanics of an interacting many-body system is assumed. The fact that in a classic liquid the static and dynamic aspects of such a system can be discussed separately forms the basis of the two-fold structure of this approach. In order to allow polymer melts and solutions to be discussed, a short chapter a...

  16. A simple introduction to Markov Chain Monte-Carlo sampling

    NARCIS (Netherlands)

    van Ravenzwaaij, Don; Cassey, Pete; Brown, Scott D.

    2016-01-01

    Markov Chain Monte–Carlo (MCMC) is an increasingly popular method for obtaining information about distributions, especially for estimating posterior distributions in Bayesian inference. This article provides a very basic introduction to MCMC sampling. It describes what MCMC is, and what it can be us

  17. A simple introduction to Markov Chain Monte-Carlo sampling.

    Science.gov (United States)

    van Ravenzwaaij, Don; Cassey, Pete; Brown, Scott D

    2016-03-11

    Markov Chain Monte-Carlo (MCMC) is an increasingly popular method for obtaining information about distributions, especially for estimating posterior distributions in Bayesian inference. This article provides a very basic introduction to MCMC sampling. It describes what MCMC is, and what it can be used for, with simple illustrative examples. Highlighted are some of the benefits and limitations of MCMC sampling, as well as different approaches to circumventing the limitations most likely to trouble cognitive scientists.

  18. Spectroscopic analysis of bosentan in biological samples after a liquid-liquid microextraction

    Science.gov (United States)

    Sajedi-Amin, Sanaz; Assadpour-Zeynali, Karim; Panahi-Azar, Vahid; Kebriaeezadeh, Abbas; Khoubnasabjafari, Maryam; Ansarin, Khalil; Jouyban-Gharamaleki, Vahid; Jouyban, Abolghasem

    2015-01-01

    Introduction:Microextraction processes with UV-Vis measurement have been developed and validated for analysis of bosentan in biological samples. Methods:In this work, liquid–liquid microextraction procedures (DLLME & USAEME) were employed for cleanup, pre-concentration, and determination of bosentan in biological samples by UV-Vis spectroscopy at 270 nm. The method was validated and applied to the determination of bosentan in spiked serum, exhaled breath condensate and urine samples. Results:Various experimental factors including type of extraction and dispersive solvents and their volumes, pH, sonication time and centrifuging time were investigated. Under the optimum conditions, the method was linear in the range of 1.0–5.0 μg.mL-1, with coefficient of determination (R2) of > 0.998. The limit of detection (LOD) was 0.07 mg.L-1. Recovery of the target analyte in biological samples was 106.2%. The method could be easily applied for higher concentration of bosentan and needs more improvement for application in the pharmacokinetic investigations where more sensitive methods are required. Conclusion:A simple, low cost, precise and accurate spectrophotometric analysis of bosentan in biological samples after liquid-liquid microextraction were developed and validated for routine analyses. PMID:26929923

  19. Spectroscopic analysis of bosentan in biological samples after a liquid-liquid microextraction

    Directory of Open Access Journals (Sweden)

    Sanaz Sajedi-Amin

    2015-12-01

    Conclusion: A simple, low cost, precise and accurate spectrophotometric analysis of bosentan in biological samples after liquid-liquid microextraction were developed and validated for routine analyses.

  20. 40 CFR 761.269 - Sampling liquid PCB remediation waste.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Sampling liquid PCB remediation waste..., AND USE PROHIBITIONS Cleanup Site Characterization Sampling for PCB Remediation Waste in Accordance with § 761.61(a)(2) § 761.269 Sampling liquid PCB remediation waste. (a) If the liquid is single phase...

  1. A versatile and reproducible automatic injection system for liquid standard introduction: application to in-situ calibration

    Directory of Open Access Journals (Sweden)

    G. Isaacman

    2011-05-01

    Full Text Available The quantitation of trace organic compounds in ambient organic aerosol is difficult due to the chemical complexity of these mixtures, but is needed to provide insight into their sources and formation processes. Compound-level characterization of organic aerosols is typically performed through sample collection followed by gas or liquid chromatography. With these methods, introduction of liquid standards has long been used as an effective means of quantifying trace compounds, but automating this technique for use with in-situ instrumentation has not previously been achieved. Here we develop an automatic injection system (AutoInject for the introduction of liquids into a custom collection and analysis cell for improved quantitation in chromatographic measurements. The system consists of chilled reservoirs containing liquid standards from which a sample loop is loaded and then injected into the cell. The AutoInject is shown to have reproducibility over 106 injections with a relative standard deviation of 1.5 %, and have negligible injection-to-injection carryover. A 6-port selector allows injection of different liquid standards separately or simultaneously. Additionally, automatic injection of multiple sample loops is shown to generate a linear multi-point calibration curve. Tests conducted in this work focus on use with the Thermal desorption Aerosol Gas chromatograph (TAG, but the flexibility of the system allows it to be used for a variety of applications.

  2. Ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction for the separation and determination of estrogens in water samples by high-performance liquid chromatography with fluorescence detection.

    Science.gov (United States)

    Zhang, Rui; Wang, Chuanliu; Yue, Qiaohong; Zhou, Tiecheng; Li, Na; Zhang, Hanqi; Hao, Xiaoke

    2014-11-01

    An ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction method was proposed for the extraction and concentration of 17-α-estradiol, 17-β-estradiol-benzoate, and quinestrol in environmental water samples by high-performance liquid chromatography with fluorescence detection. 1-Hexyl-3-methylimidazolium tetrafluoroborate was applied as foaming agent in the foam flotation process and dispersive solvent in microextraction. The introduction of the ion-pairing and salting-out agent NH4 PF6 was beneficial to the improvement of recoveries for the hydrophobic ionic liquid phase and analytes. Parameters of the proposed method including concentration of 1-hexyl-3-methylimidazolium tetrafluoroborate, flow rate of carrier gas, floatation time, types and concentration of ionic liquids, salt concentration in samples, extraction time, and centrifugation time were evaluated. The recoveries were between 98 and 105% with relative standard deviations lower than 7% for lake water and well water samples. The isolation of the target compounds from the water was found to be efficient, and the enrichment factors ranged from 4445 to 4632. This developing method is free of volatile organic solvents compared with regular extraction. Based on the unique properties of ionic liquids, the application of foam floatation, and dispersive liquid-liquid microextraction was widened.

  3. Determination of four heterocyclic insecticides by ionic liquid dispersive liquid-liquid microextraction in water samples.

    Science.gov (United States)

    Liu, Yu; Zhao, Ercheng; Zhu, Wentao; Gao, Haixiang; Zhou, Zhiqiang

    2009-02-01

    A novel microextraction method termed ionic liquid dispersive liquid-liquid microextraction (IL-DLLME) combining high-performance liquid chromatography with diode array detection (HPLC-DAD) was developed for the determination of insecticides in water samples. Four heterocyclic insecticides (fipronil, chlorfenapyr, buprofezin, and hexythiazox) were selected as the model compounds for validating this new method. This technique combines extraction and concentration of the analytes into one step, and the ionic liquid was used instead of a volatile organic solvent as the extraction solvent. Several important parameters influencing the IL-DLLME extraction efficiency such as the volume of extraction solvent, the type and volume of disperser solvent, extraction time, centrifugation time, salt effect as well as acid addition were investigated. Under the optimized conditions, good enrichment factors (209-276) and accepted recoveries (79-110%) were obtained for the extraction of the target analytes in water samples. The calibration curves were linear with correlation coefficient ranged from 0.9947 to 0.9973 in the concentration level of 2-100 microg/L, and the relative standard deviations (RSDs, n=5) were 4.5-10.7%. The limits of detection for the four insecticides were 0.53-1.28 microg/L at a signal-to-noise ratio (S/N) of 3.

  4. Introduction

    DEFF Research Database (Denmark)

    Cromwell, Jennifer Adele; Choat, Malcolm

    2012-01-01

    Introduction to the section 'Thebes in Late Antiquity', which was organised by the authors (Choat and Cromwell)......Introduction to the section 'Thebes in Late Antiquity', which was organised by the authors (Choat and Cromwell)...

  5. Introduction

    DEFF Research Database (Denmark)

    Klitgård, Ebbe; Bayer, Gerd

    2011-01-01

    An introduction to "Narrative Developments from Chaucer to Defoe", including a review of recent research in the field.......An introduction to "Narrative Developments from Chaucer to Defoe", including a review of recent research in the field....

  6. Introduction

    DEFF Research Database (Denmark)

    2004-01-01

    The chapter gives an introduction to the book "Environmental planning and management : tools for a sustainable development".......The chapter gives an introduction to the book "Environmental planning and management : tools for a sustainable development"....

  7. Introduction

    DEFF Research Database (Denmark)

    Høgfeldt Hansen, Leif

    2016-01-01

    This introduction to South Korean architecture gives an overall view of the architecture done in the country in historic times as well as a general introduction to the culture of the country.......This introduction to South Korean architecture gives an overall view of the architecture done in the country in historic times as well as a general introduction to the culture of the country....

  8. Ionic liquid based dispersive liquid-liquid microextraction of aromatic amines in water samples

    Institute of Scientific and Technical Information of China (English)

    Yun Chang Fan; Zheng Liang Hu; Mei Lan Chen; Chao Shen Tu; Yan Zhu

    2008-01-01

    In this work, a new microextraction method termed ionic liquid based dispersive liquid-liquid microextraction (IL-DLLME) was demonstrated for the extraction of 2-methylaniline, 4-chloroaniline, 1-naphthylamine and 4-aminobiphenyl in aqueous matrices. After extraction the ionic liquid (IL) phase was injected directly into the high performance liquid chromatography (HPLC) system for determination. Some parameters that might affect the extraction efficiency were optimized. Under the optimum conditions, good linear relationship, sensitivity and reproducibility were obtained. The limits of detection (LOD, S/N = 3) for the four analytes were in the range of 0.45-2.6 μg L-1. The relative standard deviations (R.S.D., n = 6) were in the range of 6.2-9.8%. This method was applied for the analysis of the real water samples. The recoveries ranged from 93.4 to 106.4%. The main advantages of the method are high speed, high recovery, good repeatability and volatile organic solvent-free.

  9. Introduction to Sampling Theory via Low-Cost Transient Recorder.

    Science.gov (United States)

    Basano, L.; Ottonello, P.

    1981-01-01

    Describes an application of solid-state memories in a laboratory course, which enables students to build electronic devices. Also introduces the fundamentals of analog-to-digital conversion and sampling theory. (CS)

  10. Introduction

    DEFF Research Database (Denmark)

    Jensen, Rasmus Thybo; Moran, Dermot

    2012-01-01

    An introduction to a special issue of Phenomenology and the Cognitive Sciences dedicated to empathy and the direct perception approach to other minds......An introduction to a special issue of Phenomenology and the Cognitive Sciences dedicated to empathy and the direct perception approach to other minds...

  11. Introduction

    DEFF Research Database (Denmark)

    Søbjerg, Lene Mosegaard

    2016-01-01

    Introduction to anthology which provides the theoretical basis of an Erasmus+ project involving marginalised young people, practitioners, students and academics in co-creating a teaching module for the social professions.......Introduction to anthology which provides the theoretical basis of an Erasmus+ project involving marginalised young people, practitioners, students and academics in co-creating a teaching module for the social professions....

  12. On-line micro-volume introduction system developed for lower density than water extraction solvent and dispersive liquid-liquid microextraction coupled with flame atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Anthemidis, Aristidis N., E-mail: anthemid@chem.auth.gr [Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, Thessaloniki 54124 (Greece); Mitani, Constantina; Balkatzopoulou, Paschalia; Tzanavaras, Paraskevas D. [Laboratory of Analytical Chemistry, Department of Chemistry, Aristotle University, Thessaloniki 54124 (Greece)

    2012-07-06

    Highlights: Black-Right-Pointing-Pointer A dispersive liquid-liquid micro extraction method for lead and copper determination. Black-Right-Pointing-Pointer A micro-volume transportation system for extractant solvent lighter than water. Black-Right-Pointing-Pointer Analysis of natural water samples. - Abstract: A simple and fast preconcentration/separation dispersive liquid-liquid micro extraction (DLLME) method for metal determination based on the use of extraction solvent with lower density than water has been developed. For this purpose a novel micro-volume introduction system was developed enabling the on-line injection of the organic solvent into flame atomic absorption spectrometry (FAAS). The effectiveness and efficiency of the proposed system were demonstrated for lead and copper preconcentration in environmental water samples using di-isobutyl ketone (DBIK) as extraction solvent. Under the optimum conditions the enhancement factor for lead and copper was 187 and 310 respectively. For a sample volume of 10 mL, the detection limit (3 s) and the relative standard deviation were 1.2 {mu}g L{sup -1} and 3.3% for lead and 0.12 {mu}g L{sup -1} and 2.9% for copper respectively. The developed method was evaluated by analyzing certified reference material and it was applied successfully to the analysis of environmental water samples.

  13. Analysis of solids, liquids, and biological tissues using solids probe introduction at atmospheric pressure on commercial LC/MS instruments.

    Science.gov (United States)

    McEwen, Charles N; McKay, Richard G; Larsen, Barbara S

    2005-12-01

    Direct analysis of samples using atmospheric pressure ionization (API) provides a more rapid method for analysis of volatile and semivolatile compounds than vacuum solids probe methods and can be accomplished on commercial API mass spectrometers. With only a simple modification to either an electrospray (ESI) or atmospheric pressure chemical ionization (APCI) source, solid as well as liquid samples can be analyzed in seconds. The method acts as a fast solids/liquid probe introduction as well as an alternative to the new direct analysis in real time (DART) and desorption electrospray ionization (DESI) methods for many compound types. Vaporization of materials occurs in the hot nitrogen gas stream flowing from an ESI or APCI probe. Ionization of the thermally induced vapors occurs by corona discharge under standard APCI conditions. Accurate mass and mass-selected fragmentation are demonstrated as is the ability to obtain ions from biological tissue, currency, and other objects placed in the path of the hot nitrogen stream.

  14. The SAMPL2 blind prediction challenge: introduction and overview.

    Science.gov (United States)

    Geballe, Matthew T; Skillman, A Geoffrey; Nicholls, Anthony; Guthrie, J Peter; Taylor, Peter J

    2010-04-01

    The interactions between a molecule and the aqueous environment underpin any process that occurs in solution, from simple chemical reactions to protein-ligand binding to protein aggregation. Fundamental measures of the interaction between molecule and aqueous phase, such as the transfer energy between gas phase and water or the energetic difference between two tautomers of a molecule in solution, remain nontrivial to predict accurately using current computational methods. SAMPL2 represents the third annual blind prediction of transfer energies, and the first time tautomer ratios were included in the challenge. Over 60 sets of predictions were submitted, and each participant also attempted to estimate the error in their predictions, a task that proved difficult for most. The results of this blind assessment of the state of the field for transfer energy and tautomer ratio prediction both indicate where the field is performing well and point out flaws in current methods.

  15. Introduction

    DEFF Research Database (Denmark)

    Nielsen, Kirsten

    2009-01-01

    The introduction begins with a definition of normativity. Thereafter follows a presentation of the 10 articles of the book. These articles represent three areas: Reception and transformation of the Bible in literature, Reception and transformation of the Bible in philosophy, Reception and transfo......The introduction begins with a definition of normativity. Thereafter follows a presentation of the 10 articles of the book. These articles represent three areas: Reception and transformation of the Bible in literature, Reception and transformation of the Bible in philosophy, Reception...

  16. Introduction

    DEFF Research Database (Denmark)

    Petersen, Nils Holger; Sandbeck, Lars; Solten, Therese Bering

    2013-01-01

    Introduction to the Special Issue of Literature and Theology publishing articles based on selected papers from the international conference of the International Society for Religion, Literature and Culture (ISRLC) conference held at the Theological Faculty of the University of Copenhagen 19...

  17. Introduction

    DEFF Research Database (Denmark)

    Barwell, Richard; Clarkson, Philip; Halai, Anjum;

    2016-01-01

    This chapter provides the introduction to this ICMI Study 21 volume. It includes: a discussion of the place of this study and its topic within ICME; a discussion of what is meant by the study title; and a brief historical account of research on this topic in mathematics education. The chapter also...

  18. Introduction

    DEFF Research Database (Denmark)

    Ashbee, Edward; Dumbrell, John

    2017-01-01

    The introduction sets a framework for subsequent chapters by considering theories of change and the extent to which there was consequential change during the Obama years. It draws upon earlier scholarship to suggest that although there certainly was no “transformation” (when new interests secure ...

  19. Introduction

    DEFF Research Database (Denmark)

    Gjerdrum Pedersen, Esben Rahbek; Thusgaard Pedersen, Janni

    2013-01-01

    An introduction is presented in which the editors discuss various reports within the issue on topics including the shared value concept in the education and business, the role of corporate foundations in establishing cross-sector partnerships, and the mechanisms of governance in the cross-sector ...

  20. Introduction

    DEFF Research Database (Denmark)

    Høst, Jeppe Engset

    2015-01-01

    This chapter introduces the notion and theme of market-based fisheries management. The introduction of market mechanisms to distribute and manage fishing quota has internationally occurred since the 1980s but is increasingly on the political agenda. As privatization and transferability are promoted...... for efficiency and fleet adaptation, and on the other, quota markets are accused of causing concentration and disturbing social relations....

  1. Introduction

    DEFF Research Database (Denmark)

    Schmidt, Johannes Dragsbæk; Rasiah, Rajah

    2010-01-01

    This is a very interesting book. It is topical and is one of the few volumes that attempts to treat Southeast Asia as an integrated whole. The editors are methodologically ambitious, and they skillfully integrate a very large amount of diverse material in their introduction. I imagine that the book...

  2. Introduction

    NARCIS (Netherlands)

    Doreian, Patrick; Stokman, Frans N.

    2001-01-01

    Introduction to: The proceedings of a conference that was held on the analysis of repeated cross sections at the University of Nijmegen on June 15±16, 2000. This two-days meeting was attended by 75 participants from seven different countries (AUS, B, F, GER, NL, USA, UK) and from a wide array of aca

  3. Introduction

    DEFF Research Database (Denmark)

    Nielsen, Kirsten

    2009-01-01

    of the story about Esau and Jacob. The rest of the introduction presents the six (revised) papers from the conference that are published in this special issue. The authors of these papers are Marie Vejrup Nielsen, James H. Thrall, Alyda Faber, Hans Jørgen Frederiksen, Stefanie Knauss og Hugh S. Pyper ....

  4. Introduction

    DEFF Research Database (Denmark)

    Schmidt, Johannes Dragsbæk; Berg, Torsten Rødel

    2012-01-01

    The chapter includes a discussion about the play by Henrik Ibsen from 1879, A Doll's House, how it still proves to be relevant today to gender relations not only in Denmark but in Nepal as well. The introduction explains how Ibsen's play inspired two theater directors from Denmark and Nepal...

  5. Introduction

    DEFF Research Database (Denmark)

    Nielsen, Kirsten

    2009-01-01

    and Culture". In the introduction, I give my definitions of reception, transformation, transgression and norm. Taking Harold Bloom and Julia Kristeva as my point of departure, I give an example of reception and transformation in the Bible, showing how the Book of Job can be read as a tranformation...

  6. High-pressure liquid chromatography with direct injection of gas sample.

    Science.gov (United States)

    Astanin, Anton I; Baram, Grigory I

    2017-06-09

    The conventional method of using liquid chromatography to determine the composition of a gaseous mixture entails dissolving vapors in a suitable solvent, then obtaining a chromatograph of the resulting solution. We studied the direct introduction of a gaseous sample into a C18 reversed-phase column, followed by separation of the components by HPLC with UV detection. Since the chromatography was performed at high pressure, vapors readily dissolved in the eluent and the substances separated in the column as effectively as in liquid samples. Samples were injected into the column in two ways: a) through the valve without a flow stop; b) after stopping the flow and relieving all pressure. We showed that an injectable gas volume could reach 70% of column dead volume. When an injected gaseous sample volume was less than 10% of the column dead volume, the resulting peaks were symmetrical and the column efficiency was high. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Determination of sulfonamides in butter samples by ionic liquid magnetic bar liquid-phase microextraction high-performance liquid chromatography.

    Science.gov (United States)

    Wu, Lijie; Song, Ying; Hu, Mingzhu; Xu, Xu; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

    2015-01-01

    A novel, simple, and environmentally friendly pretreatment method, ionic liquid magnetic bar liquid-phase microextraction, was developed for the determination of sulfonamides in butter samples by high-performance liquid chromatography. The ionic liquid magnetic bar was prepared by inserting a stainless steel wire into the hollow of a hollow fiber and immobilizing ionic liquid in the micropores of the hollow fiber. In the extraction process, the ionic liquid magnetic bars were used to stir the mixture of sample and extraction solvent and enrich the sulfonamides in the mixture. After extraction, the analyte-adsorbed ionic liquid magnetic bars were readily isolated with a magnet from the extraction system. It is notable that the present method was environmentally friendly since water and only several microliters of ionic liquid were used in the whole extraction process. Several parameters affecting the extraction efficiency were investigated and optimized, including the type of ionic liquid, sample-to-extraction solvent ratio, the number of ionic liquid magnetic bars, extraction temperature, extraction time, salt concentration, stirring speed, pH of the extraction solvent, and desorption conditions. The recoveries were in the range of 73.25-103.85 % and the relative standard deviations were lower than 6.84 %. The experiment results indicated that the present method was effective for the extraction of sulfonamides in high-fat content samples.

  8. Cryogenic Liquid Sample Acquisition System for Remote Space Applications

    Science.gov (United States)

    Mahaffy, Paul; Trainer, Melissa; Wegel, Don; Hawk, Douglas; Melek, Tony; Johnson, Christopher; Amato, Michael; Galloway, John

    2013-01-01

    There is a need to acquire autonomously cryogenic hydrocarbon liquid sample from remote planetary locations such as the lakes of Titan for instruments such as mass spectrometers. There are several problems that had to be solved relative to collecting the right amount of cryogenic liquid sample into a warmer spacecraft, such as not allowing the sample to boil off or fractionate too early; controlling the intermediate and final pressures within carefully designed volumes; designing for various particulates and viscosities; designing to thermal, mass, and power-limited spacecraft interfaces; and reducing risk. Prior art inlets for similar instruments in spaceflight were designed primarily for atmospheric gas sampling and are not useful for this front-end application. These cryogenic liquid sample acquisition system designs for remote space applications allow for remote, autonomous, controlled sample collections of a range of challenging cryogenic sample types. The design can control the size of the sample, prevent fractionation, control pressures at various stages, and allow for various liquid sample levels. It is capable of collecting repeated samples autonomously in difficult lowtemperature conditions often found in planetary missions. It is capable of collecting samples for use by instruments from difficult sample types such as cryogenic hydrocarbon (methane, ethane, and propane) mixtures with solid particulates such as found on Titan. The design with a warm actuated valve is compatible with various spacecraft thermal and structural interfaces. The design uses controlled volumes, heaters, inlet and vent tubes, a cryogenic valve seat, inlet screens, temperature and cryogenic liquid sensors, seals, and vents to accomplish its task.

  9. Group extraction of organic compounds present in liquid samples

    Science.gov (United States)

    Jahnsen, Vilhelm J. (Inventor)

    1976-01-01

    An extraction device is disclosed comprising a tube containing a substantially inert, chemically non-reactive packing material with a large surface area to volume ratio. A sample which consists of organic compounds dissolved in a liquid, is introduced into the tube. As the sample passes through the packing material it spreads over the material's large surface area to form a thin liquid film which is held on the packing material in a stationary state. A particular group or family of compounds is extractable from the sample by passing a particular solvent system consisting of a solvent and selected reagents through the packing material. The reagents cause optimum conditions to exist for the compounds of the particular family to pass through the phase boundary between the sample liquid and the solvent of the solvent system. Thus, the compounds of the particular family are separated from the sample liquid and become dissolved in the solvent of the solvent system. The particular family of compounds dissolved in the solvent, representing an extract, exits the tube together with the solvent through the tube's nozzle, while the rest of the sample remains on the packing material in a stationary state. Subsequently, a different solvent system may be passed through the packing material to extract another family of compounds from the remaining sample on the packing material.

  10. ELISE NMR: Experimental liquid sealing of NMR samples

    Science.gov (United States)

    Wieruszeski, Jean-Michel; Landrieu, Isabelle; Hanoulle, Xavier; Lippens, Guy

    2006-08-01

    We present a simple, generally applicable approach to prevent sample evaporation when working at elevated temperatures in high resolution NMR. It consists of experimentally sealing the NMR sample by a second liquid (Experimental Liquid Sealing, ELISE). For aqueous samples, we identified the mineral oil commonly used in PCR application as the best candidate, because it contains only a very limited amount of water-soluble contaminants, is stable over time and heat resistant. The procedure does not interfere with shim settings, and is compatible with a wide variety of samples, including oligosaccharides and proteins. For chloroform samples, a simple drop of water allows to efficiently seal the sample, avoiding solvent evaporation even over lengthy time periods.

  11. Exclusive breastfeeding practices reported by mothers and the introduction of additional liquids

    Directory of Open Access Journals (Sweden)

    Alessandra Marcuz de Souza Campos

    2015-04-01

    Full Text Available Aim: To assess the concept of exclusive breastfeeding held by nursing women by comparing the period they consider that they perform it and the infants' age at the introduction of additional liquids. METHOD: Cross-sectional descriptive study conducted with 309 women who delivered babies at a university hospital in the interior of São Paulo, Brazil. The data were subjected to descriptive analysis; the variables of interest were crossed using the non-parametric Kruskal-Wallis test, the chi-square test and Fisher's exact test. RESULTS: Approximately 30% of the women reported having introduced additional liquids before the infants reached aged six months old, while asserting that they were performing exclusive breastfeeding. The following variables were associated with early introduction of liquids: lack of employment (p = 0.0386, younger maternal age (p = 0.0159 and first pregnancy (p = 0.003. CONCLUSION: The concept of exclusive breastfeeding might not be fully clear to women, as they seem to believe that it means not to feed the children other types of milk but that giving other liquids is allowed. These results show that promotion of breastfeeding should take beliefs and values into consideration to achieve effective dialogue and understanding with mothers.

  12. Introduction

    DEFF Research Database (Denmark)

    Petersen, Nils Holger; Sandbeck, Lars; Solten, Therese Bering

    2013-01-01

    Introduction to the Special Issue of Literature and Theology publishing articles based on selected papers from the international conference of the International Society for Religion, Literature and Culture (ISRLC) conference held at the Theological Faculty of the University of Copenhagen 19-21 Oc......-21 October 2012 with the theme: Cultures of Transition: Presence, Absence,Memory. The conference was organised by Nils Holger Petersen, Lars Sandbeck and Therese Bering Solten who were invited as guest editors for a volume of Literature and Theology based on the conference....

  13. Introduction

    DEFF Research Database (Denmark)

    Høst, Jeppe Engset

    2015-01-01

    This chapter introduces the notion and theme of market-based fisheries management. The introduction of market mechanisms to distribute and manage fishing quota has internationally occurred since the 1980s but is increasingly on the political agenda. As privatization and transferability are promoted...... internationally, and by big players, it becomes even more crucial to understand its social and environmental implications. This chapter looks at the broader lines in the fisheries research and discusses the diverging views on market-based fisheries management. On one side market mechanisms are promoted...... for efficiency and fleet adaptation, and on the other, quota markets are accused of causing concentration and disturbing social relations....

  14. Introduction

    DEFF Research Database (Denmark)

    2015-01-01

    This chapter presents an introduction to the microfluidics field and microfluidic biochips. We discuss the main fluid propulsion principles used by modern microfluidic platforms, with a focus on “digital” microfluidic biochips, which are the topic of this book. Digital microfluidic biochips...... manipulate the fluids as small “droplets” using electrokinetics, i.e., electrowetting-on-dielectric. Several application areas for biochips are discussed, and the motivation behind the work presented in this book is introduced. At the end of the chapter, we outline the structure of the book and an overview...

  15. Introduction

    DEFF Research Database (Denmark)

    Peder Pedersen, Claus; Dehs, Jørgen

    2013-01-01

    Introduction to When Architects and Designers Write / Draw / Build / ? This anthology highlights the potentials and challenges for research in architecture and design. The included essays are based on papers given at a symposium held at the Aarhus School of Architecture in 2011 and contain a number...... of topical positions ranging from the activist and academic to practice-based and artistically-based research by international and Danish researchers. The anthology is aimed at architects and designers, as well as others with an interest in the discussion of the concept of research in the fields...

  16. Introduction

    Directory of Open Access Journals (Sweden)

    Laurel Brake

    2013-04-01

    mso-fareast-language:JA;} When W. T. Stead died on the 'Titanic' he was the most famous Englishman on board. A mass of contradictions and a crucial figure in the history of the British press, Stead was a towering presence in the cultural life of late-Victorian and Edwardian society. In this introduction, we consider Stead as a ‘mass of contradictions’ and offer a few ways in which his prodigious output and activity might be understood.

  17. Applications of Liquid-Phase Microextraction in the Sample Preparation of Environmental Solid Samples

    Directory of Open Access Journals (Sweden)

    Helena Prosen

    2014-05-01

    Full Text Available Solvent extraction remains one of the fundamental sample preparation techniques in the analysis of environmental solid samples, but organic solvents are toxic and environmentally harmful, therefore one of the possible greening directions is its miniaturization. The present review covers the relevant research from the field of application of microextraction to the sample preparation of environmental solid samples (soil, sediments, sewage sludge, dust etc. published in the last decade. Several innovative liquid-phase microextraction (LPME techniques that have emerged recently have also been applied as an aid in sample preparation of these samples: single-drop microextraction (SDME, hollow fiber-liquid phase microextraction (HF-LPME, dispersive liquid-liquid microextraction (DLLME. Besides the common organic solvents, surfactants and ionic liquids are also used. However, these techniques have to be combined with another technique to release the analytes from the solid sample into an aqueous solution. In the present review, the published methods were categorized into three groups: LPME in combination with a conventional solvent extraction; LPME in combination with an environmentally friendly extraction; LPME without previous extraction. The applicability of these approaches to the sample preparation for the determination of pollutants in solid environmental samples is discussed, with emphasis on their strengths, weak points and environmental impact.

  18. Introduction

    Directory of Open Access Journals (Sweden)

    David Harris

    1990-11-01

    Full Text Available Since its foundation as an independent Institute within the University of London fifty-three years ago, the Institute of Archaeology has contributed to research in many aspects of the developing discipline in many different parts of the world. For the first thirty years of its existence it was exclusively a postgraduate research institution, and it has continued to give high priority to postgraduate studies since the introduction of undergraduate teaching in 1968. Today, one third of the 300 students enrolled at the Institute are postgraduates, over 50 of whom are research students registered for MPhil/PhD degrees. Most of the MA and MSc students also undertake their own research projects as part of the Master's degree. Institute postgraduates are thus involved in a multitude of diverse investigations, in Britain, continental Europe, Asia, Africa, Australasia and the Americas, and each year they make, collectively, a very substantial contribution to archaeological knowledge.

  19. Introduction

    DEFF Research Database (Denmark)

    Schmidt, Johannes Dragsbæk; Berg, Torsten Rødel

    2012-01-01

    The chapter includes a discussion about the play by Henrik Ibsen from 1879, A Doll's House, how it still proves to be relevant today to gender relations not only in Denmark but in Nepal as well. The introduction explains how Ibsen's play inspired two theater directors from Denmark and Nepal......, respectively to use it as point of departure for the creation of a trans-civilizational and intercultural dialogue. The intention of this chapter is to introduce the background of the collection of chapters, give broader perspectives about globalization and social change linked with debates about changing...... values and cultures in development and social policy and then enters the specific context and development trajectory in Nepal in recent years....

  20. Introduction

    OpenAIRE

    Ayeb, Habib

    2014-01-01

    En guise d’introduction, deux questions s’imposent : pourquoi un ouvrage sur les eaux du Jourdain ? Et pourquoi avoir adopté une formule qui privilégie essentiellement les données de base d’ordre quantitatives et chronologiques ? Disons d’entrée de jeu, pour répondre à la première interrogation, que malgré la médiatisation effrénée de la question de l’eau et des difficultés de partage des ressources hydrauliques dites internationales, aucun livre récent ne lui a été consacré en France. Le der...

  1. New high temperature plasmas and sample introduction systems for analytical atomic emission and mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Montaser, A.

    1992-01-01

    New high temperature plasmas and new sample introduction systems are explored for rapid elemental and isotopic analysis of gases, solutions, and solids using mass spectrometry and atomic emission spectrometry. Emphasis was placed on atmospheric pressure He inductively coupled plasmas (ICP) suitable for atomization, excitation, and ionization of elements; simulation and computer modeling of plasma sources with potential for use in spectrochemical analysis; spectroscopic imaging and diagnostic studies of high temperature plasmas, particularly He ICP discharges; and development of new, low-cost sample introduction systems, and examination of techniques for probing the aerosols over a wide range. Refs., 14 figs. (DLC)

  2. AFM fluid delivery/liquid extraction surface sampling/electrostatic spray cantilever probe

    Science.gov (United States)

    Van Berkel, Gary J.

    2015-06-23

    An electrospray system comprises a liquid extraction surface sampling probe. The probe comprises a probe body having a liquid inlet and a liquid outlet, and having a liquid extraction tip. A solvent delivery conduit is provided for receiving solvent liquid from the liquid inlet and delivering the solvent liquid to the liquid extraction tip. An open liquid extraction channel extends across an exterior surface of the probe body from the liquid extraction tip to the liquid outlet. An electrospray emitter tip is in liquid communication with the liquid outlet of the liquid extraction surface sampling probe. A system for analyzing samples, a liquid junction surface sampling system, and a method of analyzing samples are also disclosed.

  3. Introduction

    Science.gov (United States)

    Carotenuto, Luigi

    This chapter introduces the context, objectives and structure of the book. This book aims both to contribute to disseminate the knowledge about the scientific research conducted in space and to promote new exploitation of existing data in this field. While space experiments are characterised by a long time for preparation, high costs and few opportunities, significant scientific value is expected from the resulting data for almost scientific disciplines. In this context, ISS is a unique experimental environment for research. As part of its Seventh Framework Programme, the European Commission intends to support further exploitation and valorisation of space experimental data. This book was realised as part of the ULISSE project, co-funded by the European Union. The book intends to provide an introduction to space research with a focus on the experiments performed on the ISS and related disciplines. The book also intends to be a useful guide, not only for scientists but also for teachers, students and newcomers to space research activities.

  4. Removal of nitrogen compounds from Brazilian petroleum samples by oxidation followed by liquid-liquid extraction

    Energy Technology Data Exchange (ETDEWEB)

    Conceicao, L.; Pergher, S.B.C. [Universidade Regional Integrada do Alto Uruguai e das Misses (URI), Erechim, RS (Brazil). Dept. de Quimica], E-mail: pergher@uricer.edu.br; Oliveira, J.V. [Universidade Regional Integrada do Alto Uruguai e das Misses (URI), Erechim, RS (Brazil). Dept. de Engenharia dos Alimentos; Souza, W.F. [Petroleo Brasileiro S.A. (CENPES/PETROBRAS), Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

    2009-10-15

    This work reports liquid-liquid extraction of nitrogen compounds from oxidized and non-oxidized Brazilian petroleum samples. The experiments were accomplished in a laboratory-scale liquid-liquid apparatus in the temperature range of 303 K-323 K, using methanol, n-methyl-2-pyrrolidone (NMP) and N,Ndimethylformamide (DMF), and their mixtures as extraction solvents, employing solvent to sample volume ratios of 1:2, 1:1 and 2:1, exploring up to three separation stages. Results show that an increase in temperature, solvent to oil ratio, and number of equilibrium stages greatly improves the nitrogen removal from the oxidized sample (from 2600 to 200 ppm). The employed oxidation scheme is thus demonstrated to be an essential and efficient step of sample preparation for the selective liquid-liquid removal of nitrogen compounds. It is shown that the use of mixtures of DMF and NMP as well their use as co-solvents with methanol did not prove to be useful for selective nitrogen extraction since great oil losses were observed in the final process. (author)

  5. Thin liquid sample fabrication for neutron resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Noguere, G. [CEA Cadarache, F-13108 Saint Paul les Durance (France)], E-mail: gilles.noguere@cea.fr; Brusegan, A. [EC-JRC-IRMM, B-2440 Geel (Belgium); Lepretre, A. [CEA Saclay, F-91191 Gif sur Yvette (France); Lombard, T.; Lupo, J. [EC-JRC-IRMM, B-2440 Geel (Belgium)

    2008-03-11

    In neutron resonance spectroscopy, preparation of thin cylindrical samples of large diameter containing 10{sup -4}-10{sup -5} atoms per barn of raw materials in powder form make pressing a uniform thickness sample difficult. The use of liquid samples is a suitable alternative to overcome the technical limits inherent to the fabrication of pressed solid samples by compaction methods. This paper presents the fabrication of a 2 mm thick cylindrical sample, with a inner diameter of 65 mm, filled with an aqueous solution of lithium iodide. The sample was designed to measure the low neutron energy range of the {sup 127}I total cross-section by means of the neutron resonance transmission technique. The resonance shape analysis provided results consistent with those obtained by measuring a 17.5 mm thick lead iodine sample under the same experimental conditions as for LiI sample. Such liquid sample could be used to repeat similar measurements on a large variety of stable isotopes and low radioactive materials.

  6. Study of β-NMR for Liquid Biological Samples

    CERN Document Server

    Beattie, Caitlin

    2017-01-01

    β-NMR is an exotic form of NMR spectroscopy that allows for the characterization of matter based on the anisotropic β-decay of radioactive probe nuclei. This has been shown to be an effective spectroscopic technique for many different compounds, but its use for liquid biological samples is relatively unexplored. The work at the VITO line of ISOLDE seeks to employ this technique to study such samples. Currently, preparations are being made for an experiment to characterize DNA G-quadruplexes and their interactions with stabilizing cations. More specifically, the work in which I engaged as a summer student focused on the experiment’s liquid handling system and the stability of the relevant biological samples under vacuum.

  7. Pre-concentration of uranium from water samples by dispersive liquid-liquid micro-extraction

    Energy Technology Data Exchange (ETDEWEB)

    Khajeh, Mostafa; Nemch, Tabandeh Karimi [Zabol Univ. (Iran, Islamic Republic of). Dept. of Chemistry

    2014-07-01

    In this study, a simple and rapid dispersive liquid-liquid microextraction (DLLME) was developed for the determination of uranium in water samples prior to high performance liquid chromatography with diode array detection. 1-(2-pyridylazo)-2-naphthol (PAN) was used as complexing agent. The effect of various parameters on the extraction step including type and volume of extraction and dispersive solvents, pH of solution, concentration of PAN, extraction time, sample volume and ionic strength were studied and optimized. Under the optimum conditions, the limit of detection (LOD) and preconcentration factor were 0.3 μg L{sup -1} and 194, respectively. Furthermore, the relative standard deviation of the ten replicate was <2.6%. The developed procedure was then applied to the extraction and determination of uranium in the water samples.

  8. Laserspray ionization using an atmospheric solids analysis probe for sample introduction.

    Science.gov (United States)

    Zydel, Frank; Trimpin, Sarah; McEwen, Charles N

    2010-11-01

    A newly introduced high sensitivity laserspray (LSI) mass spectrometry (MS) method that uses laser ablation of a matrix/analyte mixture at atmospheric pressure (AP) to obtain multiply charged ions from nonvolatile as well as high-mass compounds is now implemented using a simple probe device. The probe used in the LSI approach was originally designed for sample introduction into an AP ionization source using the atmospheric solids analysis probe (ASAP) method. Multiply charged mass spectra of peptides and proteins in 2,5-dihydroxybenzoic acid matrix were readily obtained on two mass spectrometers from different manufacturers with sample introduction using melting point tubes. Here we demonstrate rapid analysis by placing four peptide and protein samples on a single melting point tube. Mass spectra were obtained at high-resolution and using ion mobility spectrometry/MS.

  9. Spectrophotometric determination of Sudan Blue II in environmental samples after dispersive liquid-liquid microextraction

    Directory of Open Access Journals (Sweden)

    Yunus Emre Unsal

    2014-01-01

    Full Text Available A dispersive liquid-liquid microextraction procedure coupled to spectrophotometry is described for the determination of the trace levels of Sudan Blue II. Analytical parameters, such as pH, volume of extraction solvent (carbon tetrachloride, volume of dispersant (ethanol, volume of sample, and extraction time, were optimized. Matrix effects were also investigated. Preconcentration factor was found to be 200. Detection limit and relative standard deviation (RSD were 0.55 µg L-1 and 3.9%, respectively. The procedure was successfully used for the determination of trace levels of Sudan Blue II in food, ink, antifreeze, and industrial waste-water samples.

  10. Micro-differential scanning calorimeter for liquid biological samples

    Science.gov (United States)

    Wang, Shuyu; Yu, Shifeng; Siedler, Michael S.; Ihnat, Peter M.; Filoti, Dana I.; Lu, Ming; Zuo, Lei

    2016-10-01

    We developed an ultrasensitive micro-DSC (differential scanning calorimeter) for liquid protein sample characterization. This design integrated vanadium oxide thermistors and flexible polymer substrates with microfluidics chambers to achieve a high sensitivity (6 V/W), low thermal conductivity (0.7 mW/K), high power resolutions (40 nW), and well-defined liquid volume (1 μl) calorimeter sensor in a compact and cost-effective way. We further demonstrated the performance of the sensor with lysozyme unfolding. The measured transition temperature and enthalpy change were in accordance with the previous literature data. This micro-DSC could potentially raise the prospect of high-throughput biochemical measurement by parallel operation with miniaturized sample consumption.

  11. Liquid sample delivery techniques for serial femtosecond crystallography.

    Science.gov (United States)

    Weierstall, Uwe

    2014-07-17

    X-ray free-electron lasers overcome the problem of radiation damage in protein crystallography and allow structure determination from micro- and nanocrystals at room temperature. To ensure that consecutive X-ray pulses do not probe previously exposed crystals, the sample needs to be replaced with the X-ray repetition rate, which ranges from 120 Hz at warm linac-based free-electron lasers to 1 MHz at superconducting linacs. Liquid injectors are therefore an essential part of a serial femtosecond crystallography experiment at an X-ray free-electron laser. Here, we compare different techniques of injecting microcrystals in solution into the pulsed X-ray beam in vacuum. Sample waste due to mismatch of the liquid flow rate to the X-ray repetition rate can be addressed through various techniques.

  12. Analysis of Currently Available Analgesic Tablets by Modern Liquid Chromatography: An Undergraduate Laboratory Introduction to HPLC.

    Science.gov (United States)

    Kagel, R. A.; Farwell, S. O.

    1983-01-01

    Background information, procedures, and results, are provided for an undergraduate experiment in which analgesic tablets are analyzed using liquid chromatography. The experiment, an improved, modified version of the Waters Associates Inc. experiment, is simple to prepare, requiring little glassware and minimal sample manipulation by students. (JN)

  13. Analysis of Currently Available Analgesic Tablets by Modern Liquid Chromatography: An Undergraduate Laboratory Introduction to HPLC.

    Science.gov (United States)

    Kagel, R. A.; Farwell, S. O.

    1983-01-01

    Background information, procedures, and results, are provided for an undergraduate experiment in which analgesic tablets are analyzed using liquid chromatography. The experiment, an improved, modified version of the Waters Associates Inc. experiment, is simple to prepare, requiring little glassware and minimal sample manipulation by students. (JN)

  14. Introduction

    Science.gov (United States)

    Cohen, E. G. D.

    deduced for irreversible processes (C. Jarzynski). The survey of non-equilibrium steady states in statistical mechanics of classical and quantum systems employs heat bath models and the random matrix theory input. The quantum heat bath analysis and derivation of fluctuation-dissipation theorems is performed by means of the influence functional technique adopted to solve quantum master equations (D. Kusnezov). Chapter II deals with an issue of relaxation and its dynamical theory in both classical and quantum contexts. Pollicott-Ruelle resonance background for the exponential decay scenario is discussed for irreversible processes of diffusion in the Lorentz gas and multibaker models (P. Gaspard). The Pollicott-Ruelle theory reappears as a major inspiration in the survey of the behaviour of ensembles of chaotic systems, with a focus on model systems for which no rigorous results concerning the exponential decay of correlations in time is available (S. Fishman). The observation, that non-equilibrium transport processes in simple classical chaotic systems can be described in terms of fractal structures developing in the system phase space, links their formation and properties with the entropy production in the course of diffusion processes displaying a low dimensional deterministic (chaotic) origin (J. R. Dorfman). Chapter III offers an introduction to the theory of dynamical semigroups. Asymptotic properties of Markov operators and Markov semigroups acting in the set of probability densities (statistical ensemble notion is implicit) are analyzed. Ergodicity, mixing, strong (complete) mixing and sweeping are discussed in the familiar setting of "noise, chaos and fractals" (R. Rudnicki). The next step comprises a passage to quantum dynamical semigroups and completely positive dynamical maps, with an ultimate goal to introduce a consistent framework for the analysis of irreversible phenomena in open quantum systems, where dissipation and decoherence are crucial concepts (R

  15. Determination of Organic Pollutants in Small Samples of Groundwaters by Liquid-Liquid Extraction and Capillary Gas Chromatography

    DEFF Research Database (Denmark)

    Harrison, I.; Leader, R.U.; Higgo, J.J.W.

    1994-01-01

    A method is presented for the determination of 22 organic compounds in polluted groundwaters. The method includes liquid-liquid extraction of the base/neutral organics from small, alkaline groundwater samples, followed by derivatisation and liquid-liquid extraction of phenolic compounds after...

  16. Biological Fingerprinting of Herbal Samples by Means of Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    Łukasz Cieśla

    2012-01-01

    Full Text Available Biological chromatographic fingerprinting is a relatively new concept in the quality control of herbal samples. Originally it has been developed with the application of HPLC, and recently herbal samples' biological profiles have been obtained by means of thin-layer chromatography (TLC. This paper summarizes the application of liquid chromatographic techniques for the purpose of biological fingerprint analysis (BFA of complex herbal samples. In case of biological TLC fingerprint, which is a relatively novel solution, perspectives of its further development are outlined in more detail. Apart from already published data, some novel results are also shown and briefly discussed. The paper aims at drawing scientists' attention to the unique solutions offered by biological fingerprint construction.

  17. Fast differential scanning calorimetry of liquid samples with chips

    DEFF Research Database (Denmark)

    Splinter, R.; van Herwaarden, A. W.; van Wetten, I. A.

    2015-01-01

    Based on a modified version of standard chips for fast differential scanning calorimetry, DSC of liquid samples has been performed at temperature scan rates of up to 1000 °C/s. This paper describes experimental results with the protein lysozyme, bovine serum, and olive oil. The heating and cooling....... The bovine serum measurements show two main peaks, in good agreement with standard DSC measurements. Olive oil has been measured, with good agreement for the cooling curve and qualitative agreement for the heater curve, compared to DSC measurements....

  18. Analysis of liquid samples using dried-droplet laser ablation inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Do, Trong-Mui; Hsieh, Hui-Fang; Chang, Wei-Ciang [Department of Biomedical Engineering and Environmental Sciences, National Tsing Hua University, Hsinchu, 30013 Taiwan (China); Chang, E.-E. [Department of Biochemistry, Taipei Medical University, Taipei City, 11031 Taiwan (China); Wang, Chu-Fang, E-mail: cfwang@mx.nthu.edu.tw [Department of Biomedical Engineering and Environmental Sciences, National Tsing Hua University, Hsinchu, 30013 Taiwan (China); Institute of Nuclear Engineering and Science, National Tsing Hua University, Hsinchu 30013, Taiwan (China)

    2011-08-15

    In this study we developed a dried-droplet method for laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method provides accurate and precise results when building calibration curves and determining elements of interest in real liquid samples. After placing just 1 {mu}L of a liquid standard solution or a real sample onto the filter surface and then converting the solution into a very small, thin dry spot, the sample could be applied as an analytical subject for LA. To demonstrate the feasibility of this proposed method, we used LA-ICP-MS and conventional ICP-MS to determine the levels of 13 elements (Li, V, Mn, Co, Ni, Cu, Zn, As, Mo, Cd, Sb, Tl, and Pb) in five water samples. The correlation coefficients obtained from the various calibration curves ranged from 0.9920 ({sup 205}Tl) to 0.9998 ({sup 51}V), sufficient to allow the determination of a wide range of elements in the samples. We also investigated the effects of Methylene Blue (MB) and the NaCl concentration on the elemental analyses. MB could be used as an indicator during the ablation process; its presence in the samples only negligibly influenced the intensities of the signals of most of the tested elements. Notably, high NaCl contents led to signal suppression for some of the elements. In comparison with the established sample introduction by nebulization, our developed technique abrogates the need for time-consuming sample preparation and reduces the possibility of sample contamination.

  19. Determination of trace lead in biological and water samples with dispersive liquid-liquid microextraction preconcentration.

    Science.gov (United States)

    Liang, Pei; Sang, Hongbo

    2008-09-01

    A new method for the determination of trace lead was developed by dispersive liquid-liquid microextraction preconcentration and graphite furnace atomic absorption spectrometry. In the proposed approach, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) was used as a chelating agent, and carbon tetrachloride and ethanol were selected as extraction and dispersive solvents. Some factors influencing the extraction efficiency of lead and its subsequent determination, including extraction and dispersive solvent type and volume, pH of sample solution, concentration of the chelating agent, and extraction time, were studied and optimized. Under the optimum conditions, the enrichment factor of this method for lead was reached at 78. The detection limit for lead was 39 ng L(-1) (3 sigma), and the relative standard deviation (RSD) was 3.2% (n=7, c=10 ng mL(-1)). The method was successfully applied to the determination of trace amounts of lead in human urine and water samples.

  20. Methods of liquid phase microextraction for the determination of cadmium in environmental samples.

    Science.gov (United States)

    Pires Santos, Analú; das Graças Andrade Korn, Maria; Azevedo Lemos, Valfredo

    2017-08-09

    Liquid phase microextraction (LPME) has been widely used in extraction and preconcentration systems as an excellent alternative to conventional liquid phase extraction. In this work, a critical review is presented on liquid phase microextraction techniques used in the determination of cadmium in environmental samples. LPME techniques are classified into three main groups: single-drop liquid phase microextraction (SDME), hollow fiber liquid phase microextraction (HF-LPME), and dispersive liquid-liquid microextraction (DLLME). Methods involving these liquid phase microextraction techniques are described, addressing advantages and disadvantages, samples, figures of merit, and trends.

  1. Nanoliter viscometer for analyzing blood plasma and other liquid samples.

    Science.gov (United States)

    Srivastava, Nimisha; Davenport, Robertson D; Burns, Mark A

    2005-01-15

    We have developed a microfabricated nanoliter capillary viscometer that quickly, easily, and inexpensively measures the viscosity of liquids. The measurement of viscosity is based on capillary pressure-driven flow inside microfluidic channels (depth approximately 30 microm and width approximately 300 microm). Accurate and precise viscosity measurements can be made in less than 100 s while using only 600 nL of liquid sample. The silicon-glass hybrid device (18 mm by 15 mm) contains on-chip components that measure the driving capillary pressure difference and the relevant geometrical parameters; these components make the nanoliter viscometer completely self-calibrating, robust, and easy to use. Several different microfabricated viscometers were tested using solutions with viscosities ranging from 1 to 5 cP, a range relevant to biological fluids (urine, blood, blood plasma, etc.). Blood plasma samples collected from patients with the symptoms of hyperviscosity syndrome were tested on the nanoliter capillary viscometer to an accuracy of 3%. Such self-calibrating nanoliter viscometers may have widespread applications in chemical, biological, and medical laboratories as well as in personal health care.

  2. Analysis of chlorpheniramine in human urine samples using dispersive liquid-liquid microextraction combined with high-performance liquid chromatography

    Directory of Open Access Journals (Sweden)

    Mehdi Maham

    2014-09-01

    Full Text Available A simple and environmentally friendly microextraction technique was used for determination of chlorpheniramine (CPM, an antihistamine drug, in human urine samples using dispersive liquid-liquid microextraction (DLLME followed by high performance liquid chromatography with diode array detection (HPLC-DAD. In this extraction technique, an appropriate mixture of acetonitrile (disperser solvent and carbon tetrachloride (extraction solvent was rapidly injected into the urine sample containing the target analyte. Tiny droplets of extractant were formed and dispersed into the sample solution and then sedimented at the bottom of the conical test tube by centrifugation. Under optimal conditions, the calibration curve was linear in the range of 0.055-5.5 µg mL-1, with a detection limit of 16.5 ng mL-1. This proposed method was successfully applied to the analysis of real urine samples. Low consumption of toxic organic solvents, simplicity of operation, low cost and acceptable figures of merit are the main advantages of the proposed technique.

  3. Determination of Organic Pollutants in Small Samples of Groundwaters by Liquid-Liquid Extraction and Capillary Gas Chromatography

    DEFF Research Database (Denmark)

    Harrison, I.; Leader, R.U.; Higgo, J.J.W.;

    1994-01-01

    A method is presented for the determination of 22 organic compounds in polluted groundwaters. The method includes liquid-liquid extraction of the base/neutral organics from small, alkaline groundwater samples, followed by derivatisation and liquid-liquid extraction of phenolic compounds after...... neutralisation. The extracts were analysed by capillary gas chromatography. Dual detection by flame Ionisation and electron capture was used to reduce analysis time....

  4. Development of a robust ionic liquid-based dispersive liquid-liquid microextraction against high concentration of salt for preconcentration of trace metals in saline aqueous samples: Application to the determination of Pb and Cd

    Energy Technology Data Exchange (ETDEWEB)

    Yousefi, Seyed Reza [School of Chemistry, University College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Shemirani, Farzaneh, E-mail: shemiran@khayam.ut.ac.ir [School of Chemistry, University College of Science, University of Tehran, Tehran (Iran, Islamic Republic of)

    2010-06-11

    A new ionic liquid-based dispersive liquid-liquid microextraction method was developed for preconcentration and determination of compounds in aqueous samples containing very high salt concentrations. This method can solve the problems associated with the limited application of the conventional IL-based DLLME in these samples. This is believed to arise from dissolving of the ionic liquids in aqueous samples with high salt content. In this method, the robustness of microextraction system against high salt concentration (up to 40%, w/v) is increased by introducing a common ion of the ionic liquid into the sample solution. The proposed method was applied satisfactorily to the preconcentration of lead and cadmium in saline samples. After preconcentration, the settled IL-phase was dissolved in 100 {mu}L ethanol and aspirated into the flame atomic absorption spectrometer (FAAS) using a home-made microsample introduction system. Several variables affecting the microextraction efficiency were investigated and optimized. Under the optimized conditions and preconcentration of only 10 mL of sample, the enhancement factors of 273 and 311 and the detection limits of 0.6 {mu}g L{sup -1} and 0.03 {mu}g L{sup -1} were obtained for lead and cadmium, respectively. Validation of the method was performed by both an analysis of a certified reference material (CRM) and comparison of results with those obtained by ISO standard method.

  5. Scanning calorimeter for nanoliter-scale liquid samples

    Science.gov (United States)

    Olson, E. A.; Efremov, M. Yu.; Kwan, A. T.; Lai, S.; Petrova, V.; Schiettekatte, F.; Warren, J. T.; Zhang, M.; Allen, L. H.

    2000-10-01

    We introduce a scanning calorimeter for use with a single solid or liquid sample with a volume down to a few nanoliters. Its use is demonstrated with the melting of 52 nL of indium, using heating rates from 100 to 1000 K/s. The heat of fusion was measured to within 5% of the bulk value, and the sensitivity of the measurement was ±7 μW. The heat of vaporization of water was measured in the scanning mode to be within ±23% of the bulk value by actively vaporizing water droplets from 2 to 100 nL in volume. Results within 25% were obtained for the heat of vaporization by using the calorimeter in a heat-conductive mode and measuring the passive evaporation of water. Temperature measurements over a period of 10 h had a standard deviation of 3 mK.

  6. Extraction of pesticides in water samples using vortex-assisted liquid-liquid microextraction.

    Science.gov (United States)

    Jia, Chunhong; Zhu, Xiaodan; Wang, Jihua; Zhao, Ercheng; He, Min; Chen, Li; Yu, Pingzhong

    2010-09-10

    A simple solvent microextraction method termed vortex-assisted liquid-liquid microextraction (VALLME) coupled with gas chromatography micro electron-capture detector (GC-microECD) has been developed and used for the pesticide residue analysis in water samples. In the VALLME method, aliquots of 30 microL toluene used as extraction solvent were directly injected into a 25 mL volumetric flask containing the water sample. The extraction solvent was dispersed into the water phase under vigorously shaking with the vortex. The parameters affecting the extraction efficiency of the proposed VALLME such as extraction solvent, vortex time, volumes of extraction solvent and salt addition were investigated. Under the optimum condition, enrichment factors (EFs) in a range of 835-1115 and limits of detection below 0.010 microg L(-1) were obtained for the determination of target pesticides in water. The calculated calibration curves provide high levels of linearity yielding correlation coefficients (r(2)) greater than 0.9958 with the concentration level ranged from 0.05 to 2.5 microg L(-1). Finally, the proposed method has been successfully applied to the determination of pesticides from real water samples and acceptable recoveries over the range of 72-106.3% were obtained.

  7. New high temperature plasmas and sample introduction systems for analytical atomic emission and mass spectrometry

    Science.gov (United States)

    Montaser, A.

    This research follows a multifaceted approach, from theory to practice, to the investigation and development of novel helium plasmas, sample introduction systems, and diagnostic techniques for atomic and mass spectrometries. During the period January 1994 - December 1994, four major sets of challenging research programs were addressed that each included a number of discrete but complementary projects: (1) The first program is concerned with fundamental and analytical investigations of novel atmospheric-pressure helium inductively coupled plasmas (He ICPS) that are suitable for the atomization-excitation-ionization of elements, especially those possessing high excitation and ionization energies, for the purpose of enhancing sensitivity and selectivity of analytical measurements. (2) The second program includes simulation and computer modeling of He ICPS. The aim is to ease the hunt for new helium plasmas by predicting their structure and fundamental and analytical properties, without incurring the enormous cost for extensive experimental studies. (3) The third program involves spectroscopic imaging and diagnostic studies of plasma discharges to instantly visualize their prevailing structures, to quantify key fundamental properties, and to verify predictions by mathematical models. (4) The fourth program entails investigation of new, low-cost sample introduction systems that consume micro- to nanoliter quantity of sample solution in plasma spectrometries. A portion of this research involves development and applications of novel diagnostic techniques suitable for probing key fundamental properties of aerosol prior to and after injection into high-temperature plasmas. These efforts, still in progress, collectively offer promise of solving singularly difficult analytical problems that either exist now or are likely to arise in the future in the various fields of energy generation, environmental pollution, material science, biomedicine and nutrition.

  8. Quantitative on-line concentration for capillary electrophoresis with inkjet sample introduction technique.

    Science.gov (United States)

    Rang, Ying; Zeng, Hulie; Nakajima, Hizuru; Kato, Shungo; Uchiyama, Katsumi

    2015-08-01

    A quantitative sample introduction method based upon inkjet injection was applied to capillary electrophoresis coupled with stacking and sweeping on-line concentration techniques. Methylxanthines were used as model compounds for the proof-of-concept of the method. The volume of injected sample could be easily manipulated by controlling the number of ejected droplets in the injection procedure. Under optimized conditions, a linear relationship between the ejected droplet number and peak area was obtained when the droplet number introduced into the capillary was less than 100. Under optimized quantitative on-line concentration conditions, the limits of detection for theobromine, caffeine, and theophylline were 1.0, 2.0, and 1.0 μM, respectively. The inkjet injection system was evaluated by comparing it with conventional injection methods. The electropherogram of the inkjet injection mode was the same as that for hydrodynamic injection mode, and no sample discrimination was observed compared with the electrokinetic injection mode. The established method was applied to the determination of methylxanthines in bottled green tea. The recoveries of theobromine, caffeine, and theophylline were 94.1, 110.6, and 86.8%, respectively. We conclude that proposed method can be used for quantitative concentration for capillary electrophoresis, thus resulting in an improved accuracy.

  9. Radial line-scans as representative sampling strategy in dried-droplet laser ablation of liquid samples deposited on pre-cut filter paper disks

    Energy Technology Data Exchange (ETDEWEB)

    Nischkauer, Winfried [Institute of Chemical Technologies and Analytics, Vienna University of Technology, Vienna (Austria); Department of Analytical Chemistry, Ghent University, Ghent (Belgium); Vanhaecke, Frank [Department of Analytical Chemistry, Ghent University, Ghent (Belgium); Bernacchi, Sébastien; Herwig, Christoph [Institute of Chemical Engineering, Vienna University of Technology, Vienna (Austria); Limbeck, Andreas, E-mail: Andreas.Limbeck@tuwien.ac.at [Institute of Chemical Technologies and Analytics, Vienna University of Technology, Vienna (Austria)

    2014-11-01

    Nebulising liquid samples and using the aerosol thus obtained for further analysis is the standard method in many current analytical techniques, also with inductively coupled plasma (ICP)-based devices. With such a set-up, quantification via external calibration is usually straightforward for samples with aqueous or close-to-aqueous matrix composition. However, there is a variety of more complex samples. Such samples can be found in medical, biological, technological and industrial contexts and can range from body fluids, like blood or urine, to fuel additives or fermentation broths. Specialized nebulizer systems or careful digestion and dilution are required to tackle such demanding sample matrices. One alternative approach is to convert the liquid into a dried solid and to use laser ablation for sample introduction. Up to now, this approach required the application of internal standards or matrix-adjusted calibration due to matrix effects. In this contribution, we show a way to circumvent these matrix effects while using simple external calibration for quantification. The principle of representative sampling that we propose uses radial line-scans across the dried residue. This compensates for centro-symmetric inhomogeneities typically observed in dried spots. The effectiveness of the proposed sampling strategy is exemplified via the determination of phosphorus in biochemical fermentation media. However, the universal viability of the presented measurement protocol is postulated. Detection limits using laser ablation-ICP-optical emission spectrometry were in the order of 40 μg mL{sup −1} with a reproducibility of 10 % relative standard deviation (n = 4, concentration = 10 times the quantification limit). The reported sensitivity is fit-for-purpose in the biochemical context described here, but could be improved using ICP-mass spectrometry, if future analytical tasks would require it. Trueness of the proposed method was investigated by cross-validation with

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

    Science.gov (United States)

    Farajzadeh, Mir Ali; Abbaspour, Maryam

    2017-11-01

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

  11. Introduction of liquid-based cytology and human papillomavirus testing in cervical cancer screening in Luxembourg.

    Science.gov (United States)

    Latsuzbaia, Ardashel; Hebette, Gaëtan; Fischer, Marc; Arbyn, Marc; Weyers, Steven; Vielh, Philippe; Schmitt, Fernando; Mossong, Joël

    2017-05-01

    In 2014, liquid-based cytology with HPV triage replaced conventional cytology. The aim of our study was to compare conventional and liquid-based cytology (LBC), estimate the prevalence of abnormal cervical cytology and high risk HPV (hrHPV) infection and their correlation, among screened women in Luxembourg. Between the first January 2013 and 31st December 2015, 315,868 cervical samples from 150,815 women (mean age 42.2 years) were investigated by the national cytology laboratory. Slides were prepared and screened according to European Guidelines. All cytological results were classified according to the Bethesda 2001 system terminology. The prevalence of abnormal cervical lesions was as follows: atypical squamous cells of undetermined significance (ASC-US), 1.3%; low-grade squamous intraepithelial lesion (LSIL), 1.9%; high-grade squamous intraepithelial lesion (HSIL), 0.4%. The detection rate of cytological lesions was significantly higher with LBC than with conventional cytology. Based on 11,838 samples with concomitant cytology and HPV testing, hrHPV was detected in 9.5, 45.3, 70.0, and 92.6% of women with negative cytology, ASC-US, LSIL, and HSIL, respectively. More cervical lesions were identified using LBC compared to conventional cytology. HrHPV infection was correlated with the severity of intraepithelial lesions. The current findings provide important information to evaluate the prevention of cervical cancer in Luxembourg and for monitoring the future impact of HPV vaccination. Diagn. Cytopathol. 2017;45:384-390. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  12. Liquid Water from First Principles: Validation of Different Sampling Approaches

    Energy Technology Data Exchange (ETDEWEB)

    Mundy, C J; Kuo, W; Siepmann, J; McGrath, M J; Vondevondele, J; Sprik, M; Hutter, J; Parrinello, M; Mohamed, F; Krack, M; Chen, B; Klein, M

    2004-05-20

    A series of first principles molecular dynamics and Monte Carlo simulations were carried out for liquid water to assess the validity and reproducibility of different sampling approaches. These simulations include Car-Parrinello molecular dynamics simulations using the program CPMD with different values of the fictitious electron mass in the microcanonical and canonical ensembles, Born-Oppenheimer molecular dynamics using the programs CPMD and CP2K in the microcanonical ensemble, and Metropolis Monte Carlo using CP2K in the canonical ensemble. With the exception of one simulation for 128 water molecules, all other simulations were carried out for systems consisting of 64 molecules. It is found that the structural and thermodynamic properties of these simulations are in excellent agreement with each other as long as adiabatic sampling is maintained in the Car-Parrinello molecular dynamics simulations either by choosing a sufficiently small fictitious mass in the microcanonical ensemble or by Nos{acute e}-Hoover thermostats in the canonical ensemble. Using the Becke-Lee-Yang-Parr exchange and correlation energy functionals and norm-conserving Troullier-Martins or Goedecker-Teter-Hutter pseudopotentials, simulations at a fixed density of 1.0 g/cm{sup 3} and a temperature close to 315 K yield a height of the first peak in the oxygen-oxygen radial distribution function of about 3.0, a classical constant-volume heat capacity of about 70 J K{sup -1} mol{sup -1}, and a self-diffusion constant of about 0.1 Angstroms{sup 2}/ps.

  13. Selective extraction of emerging contaminants from water samples by dispersive liquid-liquid microextraction using functionalized ionic liquids.

    Science.gov (United States)

    Yao, Cong; Li, Tianhao; Twu, Pamela; Pitner, William R; Anderson, Jared L

    2011-03-25

    Functionalized ionic liquids containing the tris(pentafluoroethyl)trifluorophosphate (FAP) anion were used as extraction solvents in dispersive liquid-liquid microextraction (DLLME) for the extraction of 14 emerging contaminants from water samples. The extraction efficiencies and selectivities were compared to those of an in situ IL DLLME method which uses an in situ metathesis reaction to exchange 1-butyl-3-methylimidazolium chloride (BMIM-Cl) to 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMIM-NTf(2)). Compounds containing tertiary amine functionality were extracted with high selectivity and sensitivity by the 1-(6-amino-hexyl)-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (HNH(2)MPL-FAP) IL compared to other FAP-based ILs and the BMIM-NTf(2) IL. On the other hand, polar or acidic compounds without amine groups exhibited higher enrichment factors using the BMIM-NTf(2) IL. The detection limits for the studied analytes varied from 0.1 to 55.1 μg/L using the traditional IL DLLME method with the HNH(2)MPL-FAP IL as extraction solvent, and from 0.1 to 55.8 μg/L using in situ IL DLLME method with BMIM-Cl+LiNTf(2) as extraction solvent. A 93-fold decrease in the detection limit of caffeine was observed when using the HNH(2)MPL-FAP IL compared to that obtained using in situ IL DLLME method. Real water samples including tap water and creek water were analyzed with both IL DLLME methods and yielded recoveries ranging from 91% to 110%.

  14. Quantitation of antioxidants in water samples using ionic liquid dispersive liquid-liquid microextraction followed by high-performance liquid chromatography-ultraviolet detection.

    Science.gov (United States)

    Sobhi, Hamid Reza; Kashtiaray, Amir; Farahani, Hadi; Farahani, Mohammad Reza

    2011-01-01

    A simple and efficient method, ionic liquid-based dispersive liquid-liquid microextraction combined with high-performance liquid chromatography-ultraviolet detection (HPLC-UV), has been applied for the extraction and determination of some antioxidants (Irganox 1010, Irganox 1076 and Irgafos 168) in water samples. The microextraction efficiency factors were investigated and optimized: 1-hexyl-3-methylimidazolium hexafluorophosphate [C(6)MIM][PF(6)] (0.06 g) as extracting solvent, methanol (0.5 mL) as disperser solvent without salt addition. Under the selected conditions, enrichment factors up to 48-fold, limits of detection (LODs) of 5.0-10.0 ng/mL and dynamic linear ranges of 25-1500 ng/mL were obtained. A reasonable repeatability (RSD≤11.8%, n=5) with satisfactory linearity (r(2)≥0.9954) of the results illustrated a good performance of the presented method. The accuracy of the method was tested by the relative recovery experiments on spiked samples, with results ranging from 85 to 118%. Finally, the method was successfully applied for determination of the analytes in several real water samples. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Radial line-scans as representative sampling strategy in dried-droplet laser ablation of liquid samples deposited on pre-cut filter paper disks

    Science.gov (United States)

    Nischkauer, Winfried; Vanhaecke, Frank; Bernacchi, Sébastien; Herwig, Christoph; Limbeck, Andreas

    2014-11-01

    Nebulising liquid samples and using the aerosol thus obtained for further analysis is the standard method in many current analytical techniques, also with inductively coupled plasma (ICP)-based devices. With such a set-up, quantification via external calibration is usually straightforward for samples with aqueous or close-to-aqueous matrix composition. However, there is a variety of more complex samples. Such samples can be found in medical, biological, technological and industrial contexts and can range from body fluids, like blood or urine, to fuel additives or fermentation broths. Specialized nebulizer systems or careful digestion and dilution are required to tackle such demanding sample matrices. One alternative approach is to convert the liquid into a dried solid and to use laser ablation for sample introduction. Up to now, this approach required the application of internal standards or matrix-adjusted calibration due to matrix effects. In this contribution, we show a way to circumvent these matrix effects while using simple external calibration for quantification. The principle of representative sampling that we propose uses radial line-scans across the dried residue. This compensates for centro-symmetric inhomogeneities typically observed in dried spots. The effectiveness of the proposed sampling strategy is exemplified via the determination of phosphorus in biochemical fermentation media. However, the universal viability of the presented measurement protocol is postulated. Detection limits using laser ablation-ICP-optical emission spectrometry were in the order of 40 μg mL- 1 with a reproducibility of 10 % relative standard deviation (n = 4, concentration = 10 times the quantification limit). The reported sensitivity is fit-for-purpose in the biochemical context described here, but could be improved using ICP-mass spectrometry, if future analytical tasks would require it. Trueness of the proposed method was investigated by cross-validation with

  16. Ionic liquids for improving the extraction of NSAIDs in water samples using dispersive liquid-liquid microextraction by high performance liquid chromatography-diode array-fluorescence detection.

    Science.gov (United States)

    Toledo-Neira, Carla; Álvarez-Lueje, Alejandro

    2015-03-01

    A rapid, sensitive and efficient analytical method based on the use of ionic liquids for determination of non-steroidal anti-inflammatory drugs (NSAIDs) in water samples was developed. High-performance liquid chromatography equipped with a diode array and fluorescence detector was used for quantification of ketoprofen, ibuprofen and diclofenac in tap and river water samples. This new method relies on the use of two ionic liquids with multiple functionalities: one functions as an extraction solvent (1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), and the other changes the polarity in the aqueous medium (1-butyl-3-methylimidazolium tetrafluoroborate, ([BMIM][BF4]). Factors such as the type and volume of the ILs and dispersive solvent, sample volume, and centrifugation time were investigated and optimized. The optimized method exhibited good precision, with relative standard deviation values between 2% and 3%, for the three NSAIDs. Limits of detection achieved for all of the analytes were between 17 and 95 ng mL(-1), and the recoveries ranged from 89% to 103%. Furthermore, the enrichment factors ranged from 49 to 57. The proposed method was successfully applied to the analysis of NSAIDs in tap and river water samples.

  17. Combination of counter current salting-out homogenous liquid-liquid extraction and dispersive liquid-liquid microextraction as a novel microextraction of drugs in urine samples.

    Science.gov (United States)

    Akramipour, Reza; Fattahi, Nazir; Pirsaheb, Meghdad; Gheini, Simin

    2016-02-15

    The counter current salting-out homogenous liquid-liquid extraction (CCSHLLE) joined with the dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) has been developed as a high preconcentration technique for the determination of different drugs in urine samples. Amphetamines were employed as model compounds to assess the extraction procedure and were determined by high performance liquid chromatography-ultraviolet detection (HPLC-UV). In this method, initially, NaCl as a separation reagent is filled into a small column and a mixture of urine and acetonitrile is passed through the column. By passing the mixture, NaCl is dissolved and the fine droplets of acetonitrile are formed due to salting-out effect. The produced droplets go up through the remained mixture and collect as a separated layer. Then, the collected acetonitrile is removed with a syringe and mixed with 30.0μL 1-undecanol (extraction solvent). In the second step, the 5.00mLK2CO3 solution (2% w/v) is rapidly injected into the above mixture placed in a test tube for further DLLME-SFO. Under the optimum conditions, calibration curves are linear in the range of 1-3000μgL(-1) and limit of detections (LODs) are in the range of 0.5-2μgL(-1). The extraction recoveries and enrichment factors ranged from 78 to 84% and 157 to 168, respectively. Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 100μgL(-1) of amphetamines were in the range of 3.5-4.5% and 4-5%, respectively. The method was successfully applied for the determination of amphetamines in the actual urine samples. The relative recoveries of urine samples spiked with amphetamine and methamphetamine are 90-108%.

  18. Liquid-liquid extraction assisted by a carbon nanoparticles interface. Electrophoretic determination of atrazine in environmental samples.

    Science.gov (United States)

    Caballero-Díaz, Encarnación; Simonet, Bartolomé; Valcárcel, Miguel

    2013-10-21

    A novel method for the determination of atrazine, using liquid-liquid extraction assisted by a nanoparticles film formed in situ and composed of organic solvent stabilized-carbon nanoparticles, is described. The presence of nanoparticles located at the liquid-liquid interface reinforced the extraction of analyte from matrix prior to capillary electrophoresis (CE) analysis. Some influential experimental variables were optimized in order to enhance the extraction efficiency. The developed procedure confirmed that carbon nanoparticles, especially multi-walled carbon nanotubes, are suitable to be used in sample treatment processes introducing new mechanisms of interaction with the analyte. The application of the proposed preconcentration method followed by CE detection enabled the determination of atrazine in spiked river water providing acceptable RSD values (11.6%) and good recoveries (about 87.0-92.0%). Additionally, a similar extraction scheme was tested in soil matrices with a view to further applications in real soil samples.

  19. An electrodeless system for measurement of liquid sample dielectric properties in radio frequency band.

    Science.gov (United States)

    Hartwig, V; Giovannetti, G; Vanello, N; Costantino, M; Landini, L; Benassi, A

    2006-01-01

    An electrodeless measurement system based on a resonant circuit is proposed for the measurement of dielectric properties of liquid samples at RF (radio frequency). Generally, properties as dielectric constant, loss factor and conductivity are measured by parallel plate capacitor cells: this method has several limitations in the case of particular liquid samples and in the range of radiofrequencies. Our method is based on the measurements of resonance frequency and quality factor of a LC resonant circuit in different measuring conditions, without and with the liquid sample placed inside a test tube around which the home made coil is wrapped. The measurement is performed using a network analyzer and a dual loop probe, inductively coupled with the resonant circuit. One of the advantages of this method is the contactless between the liquid sample and the measurement electrodes. In this paper the measurement system is described and test measurements of conventional liquids dielectric properties are reported.

  20. Interface for the rapid analysis of liquid samples by accelerator mass spectrometry

    Science.gov (United States)

    Turteltaub, Kenneth; Ognibene, Ted; Thomas, Avi; Daley, Paul F; Salazar Quintero, Gary A; Bench, Graham

    2014-02-04

    An interface for the analysis of liquid sample having carbon content by an accelerator mass spectrometer including a wire, defects on the wire, a system for moving the wire, a droplet maker for producing droplets of the liquid sample and placing the droplets of the liquid sample on the wire in the defects, a system that converts the carbon content of the droplets of the liquid sample to carbon dioxide gas in a helium stream, and a gas-accepting ion source connected to the accelerator mass spectrometer that receives the carbon dioxide gas of the sample in a helium stream and introduces the carbon dioxide gas of the sample into the accelerator mass spectrometer.

  1. Combining Laser Ablation/Liquid Phase Collection Surface Sampling and High-Performance Liquid Chromatography Electrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ovchinnikova, Olga S [ORNL; Kertesz, Vilmos [ORNL; Van Berkel, Gary J [ORNL

    2011-01-01

    This paper describes the coupling of ambient pressure transmission geometry laser ablation with a liquid phase sample collection method for surface sampling and ionization with subsequent mass spectral analysis. A commercially available autosampler was adapted to produce a liquid droplet at the end of the syringe injection needle while in close proximity to the surface to collect the sample plume produced by laser ablation. The sample collection was followed by either flow injection or a high performance liquid chromatography (HPLC) separation of the extracted components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the analytical utility of this coupling, thin films of a commercial ink sample containing rhodamine 6G and of mixed isobaric rhodamine B and 6G dyes on glass microscope slides were analyzed. The flow injection and HPLC/ESI-MS analysis revealed successful laser ablation, capture and, with HPLC, the separation of the two compounds. The ablated circular area was about 70 m in diameter for these experiments. The spatial sampling resolution afforded by the laser ablation, as well as the ability to use sample processing methods like HPLC between the sample collection and ionization steps, makes this combined surface sampling/ionization technique a highly versatile analytical tool.

  2. Is liquid heparin comparable to dry balanced heparin for blood gas sampling in intensive care unit?

    Directory of Open Access Journals (Sweden)

    Viswas Chhapola

    2014-01-01

    Full Text Available Introduction: Blood gas (BG analysis is required for management of critically ill patients in emergency and intensive care units. BG parameters can be affected by the type of heparin formulations used-liquid heparin (LH or dry balanced heparin (DBH. This study was conducted to determine whether blood gas, electrolyte, and metabolite estimations performed by using DBH and LH are comparable. Materials and Methods: A prospective study was conducted at pediatric intensive care unit (PICU of a tertiary care hospital. Paired venous samples were collected from 35 consecutive children in commercially prepared DBH syringes and custom-prepared LH syringes. Samples were immediately analyzed by blood gas analyzer and compared for pH, pCO 2 , pO 2 , HCO 3 - , Na + , K + , Cl - , and lactate. Paired comparisons were done and agreement was assessed by Bland-Altman difference plots. The 95% limits of absolute agreement (LOA were compared with the specifications for total allowable error (TEa. Results: The P values were significant for all measured parameters, with the exception of pCO 2 and K +. Bland-Altman difference plots showed wide LOA for pCO 2 , pO 2 , HCO3 - , Na + , K + , and Cl - when compared against TEa. For pCO 2 , HCO3 - , Na + , K + , and Cl - , 40%, 23%, 77%, 34%, and 54% of samples were outside the TEa limits, respectively, with LH. Conclusion: Our study showed that there is poor agreement between LH and DBH for the BG parameters pCO2, pO2, HCO3 - , K + , Na + , and Cl - and, thus, are not comparable. But for pH and lactate, LH and DBH can be used interchangeably.

  3. Determination of eight fluoroquinolones in groundwater samples with ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction prior to high-performance liquid chromatography and fluorescence detection.

    Science.gov (United States)

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

    2012-10-20

    An ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of eight fluoroquinolones (marbofloxacin, norfloxacin, ciprofloxacin, lomefloxacin, danofloxacin, enrofloxacin, oxolinic acid and nalidixic acid) in groundwater, using high-performance liquid chromatography with fluorescence detection (HPLC-FD). The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.4 mL of methanol), which increased the extraction efficiency and reduced the equilibrium time. For the DLLME procedure, the IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)MIM] [PF(6)]) and methanol (MeOH) were used as extraction and disperser solvent, respectively. By comparing [C(8)MIM] [PF(6)] with 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM] [PF(6)]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)MIM] [PF(6)]) as extraction solvents, it was observed that when using [C(8)MIM] [PF(6)] the cloudy solution was formed more readily than when using [C(6)MIM] [PF(6)] or [C(4)MIM] [PF(6)]. 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 optimised. A slight increase in the recoveries of fluoroquinolones was observed when an ice-water bath extraction step was included in the analytical procedure (85-107%) compared to those obtained without this step (83-96%). Under the optimum conditions, linearity of the method was observed over the range 10-300 ng L(-1) with correlation coefficient >0.9981. The proposed method has been found to have excellent sensitivity with limit of detection between 0.8 and 13 ng L(-1) and precision with relative standard deviation values between 4.8 and 9.4% (RSD, n=5). Good enrichment factors (122-205) and recoveries (85

  4. Improved methods for measuring thermal parameters of liquid samples using photothermal infrared radiometry

    Science.gov (United States)

    Kuriakose, Maju; Depriester, Michael; Dadarlat, Dorin; Sahraoui, Abdelhak Hadj

    2013-02-01

    High accuracy, non-contact measuring methods for finding thermal properties of liquid samples using photothermal infrared radiometry (PTR) are presented. The use of transparent windows to confine micro volume liquid samples and the implementation of front and/or back signal detection procedures helped the successful implementation of the PTR technique for measuring liquids with high proficiency. We present two configurations, the so-called back-front photothermal infrared radiometry and back photothermal infrared radiometry to find thermal diffusivity and thermal effusivity of liquid samples. Sensitivity studies and error analyses included prove the robustness of each method. As an illustration of the temperature and electric field varying studies, we have included the experimental results on a 5CB (4-cyano-4‧-pentylbiphenyl) liquid crystal.

  5. Unsatisfactory rate in liquid-based cervical samples as compared to conventional smears: A study from tertiary care hospital

    Directory of Open Access Journals (Sweden)

    Nalini Gupta

    2016-01-01

    Full Text Available Background: Developed countries adopted liquid-based cytology (LBC cervical cytology, partly because of its lower proportions of unsatisfactory (U/S/inadequate samples. This study was carried out to evaluate effect on the rate of U/S samples after introduction of LBC in our laboratory. Materials and Methods: An audit of U/S cervical samples was performed, which included split samples (n = 1000, only conventional Pap smear (CPS smears (n = 1000, and only LBC samples (n = 1000. The smears were reviewed by two observers independently, and adequacy for the samples was assessed as per The Bethesda System 2001. The reasons for U/S rate in split samples were categorized into various cytologic and/or technical reasons. Results: U/S rate was far less in only LBC samples (1.2% as compared to only CPS (10.5% cases. Cases in the satisfactory but limited category were also less in only LBC (0.4% as compared to only CPS (3.2% samples. The main reasons for U/S smears in split samples were low cell count (37.2% in CPS; 58.8% in LBC. The second main reason was low cellularity with excess blood and only excess blood in CPS samples. Conclusion: There was a significant reduction of U/S rate in LBC samples as compared to CPS samples, and the difference was statistically significant. The main cause of U/S samples in LBC was low cellularity indicating a technical fault in sample collection. The main cause of U/S rate in CPS was low cellularity followed by low cellularity with excess blood. Adequate training of sample takers and cytologists for the precise cell count to determine adequacy in smears can be of great help in reducing U/S rate.

  6. Unsatisfactory rate in liquid-based cervical samples as compared to conventional smears: A study from tertiary care hospital

    Science.gov (United States)

    Gupta, Nalini; Bhar, Vikrant S.; Rajwanshi, Arvind; Suri, Vanita

    2016-01-01

    Background: Developed countries adopted liquid-based cytology (LBC) cervical cytology, partly because of its lower proportions of unsatisfactory (U/S)/inadequate samples. This study was carried out to evaluate effect on the rate of U/S samples after introduction of LBC in our laboratory. Materials and Methods: An audit of U/S cervical samples was performed, which included split samples (n = 1000), only conventional Pap smear (CPS) smears (n = 1000), and only LBC samples (n = 1000). The smears were reviewed by two observers independently, and adequacy for the samples was assessed as per The Bethesda System 2001. The reasons for U/S rate in split samples were categorized into various cytologic and/or technical reasons. Results: U/S rate was far less in only LBC samples (1.2%) as compared to only CPS (10.5%) cases. Cases in the satisfactory but limited category were also less in only LBC (0.4%) as compared to only CPS (3.2%) samples. The main reasons for U/S smears in split samples were low cell count (37.2% in CPS; 58.8% in LBC). The second main reason was low cellularity with excess blood and only excess blood in CPS samples. Conclusion: There was a significant reduction of U/S rate in LBC samples as compared to CPS samples, and the difference was statistically significant. The main cause of U/S samples in LBC was low cellularity indicating a technical fault in sample collection. The main cause of U/S rate in CPS was low cellularity followed by low cellularity with excess blood. Adequate training of sample takers and cytologists for the precise cell count to determine adequacy in smears can be of great help in reducing U/S rate. PMID:27382408

  7. Going Beyond, Going Further: An Inexpensive Experiment for the Introduction of High Performance Liquid Chromatography.

    Science.gov (United States)

    Bidlingmeyer, Brian A.; Warren, F. Vincent, Jr.

    1984-01-01

    Background information, materials needed, laboratory procedures, and typical results are provided for five high performance liquid chromatography experiments (three isocratic and two step gradient separations). Suggestions for further experimentation are also provided, including quantitative determinations and separation of charged solutes. (JN)

  8. Imaging soft samples in liquid with tuning fork based shear force microscopy

    NARCIS (Netherlands)

    Rensen, W.H.J.; van Hulst, N.F.; Kammer, S.B.

    2000-01-01

    We present a study of the dynamic behavior of tuning forks and the application of tuning fork based shear force microscopy o­n soft samples in liquid. A shift in resonance frequency and a recovery of the tip vibration amplitude have been observed upon immersion into liquid. Conservation of the

  9. An Interface for the Direct Coupling of Small Liquid Samples to AMS.

    Science.gov (United States)

    Ognibene, T J; Thomas, A T; Daley, P F; Bench, G; Turteltaub, K W

    2015-10-15

    We describe the moving wire interface attached to the 1-MV AMS system at LLNL's Center for Accelerator Mass Spectrometry for the analysis of nonvolatile liquid samples as either discrete drops or from the direct output of biochemical separatory instrumentation, such as high-performance liquid chromatography. Discrete samples containing at least a few 10s of nanograms of carbon and as little as 50 zmol (14)C can be measured with a 3-5% precision in a few minutes. The dynamic range of our system spans approximately 3 orders in magnitude. Sample to sample memory is minimized by the use of fresh targets for each discrete sample or by minimizing the amount of carbon present in a peak generated by an HPLC containing a significant amount of (14)C. Liquid Sample AMS provides a new technology to expand our biomedical AMS program by enabling the capability to measure low-level biochemicals in extremely small samples that would otherwise be inaccessible.

  10. Transmission electron microscope cells for use with liquid samples

    Energy Technology Data Exchange (ETDEWEB)

    Khalid, Waqas; Alivisatos, Paul A.; Zettl, Alexander K.

    2016-08-09

    This disclosure provides systems, methods, and devices related to transmission electron microscopy cells for use with liquids. In one aspect a device includes a substrate, a first graphene layer, and a second graphene layer. The substrate has a first surface and a second surface. The first surface defines a first channel, a second channel, and an outlet channel. The first channel and the second channel are joined to the outlet channel. The outlet channel defines a viewport region forming a though hole in the substrate. The first graphene layer overlays the first surface of the substrate, including an interior area of the first channel, the second channel, and the outlet channel. The second graphene layer overlays the first surface of the substrate, including open regions defined by the first channel, the second channel, and the outlet channel.

  11. Comparison of a high temperature torch integrated sample introduction system with a desolvation system for the analysis of microsamples through inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Sánchez, Raquel; Cañabate, Águeda; Bresson, Carole; Chartier, Frédéric; Isnard, Hélène; Maestre, Salvador; Nonell, Anthony; Todolí, José-Luis

    2017-03-01

    This work describes for the first time the comparison of the analytical performances obtained with a high temperature torch integrated sample introduction system (hTISIS) against those found with a commercially available desolvation system (APEX) associated with inductively coupled plasma mass spectrometry (ICP-MS). A double pass spray chamber was taken as the reference system. Similar detection limits and sensitivities were obtained in continuous injection mode at low liquid flow rates for the APEX and hTISIS operating at high temperatures. In contrast, in the air-segmented injection mode, the detection limits obtained with hTISIS at high temperatures were up to 12 times lower than those found for the APEX. Regarding memory effects, wash out times were shorter in continuous mode and peaks were narrower in air segmented mode for the hTISIS as compared to the APEX. Non spectral interferences (matrix effects) were studied with 10% nitric acid, 2% methanol, for an ICP multielemental solution and a hydro-organic matrix containing 70% (v/v) acetonitrile in water, 15 mmol L- 1 ammonium acetate and 0.5% formic acid containing lanthanide complexes. In all the cases, matrix effects were less severe for the hTISIS operating at 200 °C and the APEX than for the double pass spray chamber. Finally, two spiked reference materials (sea water and Antartic krill) were analyzed. The hTISIS operating at 200 °C gave the best results compared to those obtained with the APEX and the double pass spray chamber. In conclusion, despite the simplicity of the hTISIS, it provided, at low liquid flow rates, results similar to or better than those obtained with the by other sample introduction systems.

  12. Optical properties of planar nematic liquid crystals samples which are parallel oriented by nanofibers

    Science.gov (United States)

    Yusuf, Yusril; Kusumasari, Ervanggis Minggar; Ula, Nur Mufidatul; Jahidah, Khannah; Triyana, Kuwat; Sosiati, Harini; Harsojo

    2016-04-01

    Optical properties of two nematic liquid crystals, i.e., 4-methoxybenzylidene-4-butylaniline (MBBA) and 4-cyano-4'-pentylbiphenyl (5 CB) which are parallel oriented by nanofibers has been successfully performed. Planar samples of liquid crystals were made using polyvinyl alcohol (PVA) nanofiber from electrospinning process. Electrospinning method was modified using copper (Cu) as gap collector. These planar samples area are 15 mm x 25 mm. Optical characteristic of these samples were studied by using optical polarizing microscope. The optical intensity changes by a rotationof crossed polarizers is observed. The sinusoidal intensity change was observedin these samples as such as in the planar sample prepared by the rubbing method.

  13. Fully Automated Laser Ablation Liquid Capture Sample Analysis using NanoElectrospray Ionization Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lorenz, Matthias [ORNL; Ovchinnikova, Olga S [ORNL; Van Berkel, Gary J [ORNL

    2014-01-01

    RATIONALE: Laser ablation provides for the possibility of sampling a large variety of surfaces with high spatial resolution. This type of sampling when employed in conjunction with liquid capture followed by nanoelectrospray ionization provides the opportunity for sensitive and prolonged interrogation of samples by mass spectrometry as well as the ability to analyze surfaces not amenable to direct liquid extraction. METHODS: A fully automated, reflection geometry, laser ablation liquid capture spot sampling system was achieved by incorporating appropriate laser fiber optics and a focusing lens into a commercially available, liquid extraction surface analysis (LESA ) ready Advion TriVersa NanoMate system. RESULTS: Under optimized conditions about 10% of laser ablated material could be captured in a droplet positioned vertically over the ablation region using the NanoMate robot controlled pipette. The sampling spot size area with this laser ablation liquid capture surface analysis (LA/LCSA) mode of operation (typically about 120 m x 160 m) was approximately 50 times smaller than that achievable by direct liquid extraction using LESA (ca. 1 mm diameter liquid extraction spot). The set-up was successfully applied for the analysis of ink on glass and paper as well as the endogenous components in Alstroemeria Yellow King flower petals. In a second mode of operation with a comparable sampling spot size, termed laser ablation/LESA , the laser system was used to drill through, penetrate, or otherwise expose material beneath a solvent resistant surface. Once drilled, LESA was effective in sampling soluble material exposed at that location on the surface. CONCLUSIONS: Incorporating the capability for different laser ablation liquid capture spot sampling modes of operation into a LESA ready Advion TriVersa NanoMate enhanced the spot sampling spatial resolution of this device and broadened the surface types amenable to analysis to include absorbent and solvent resistant

  14. Use of Dispersive Liquid-Liquid Microextraction and UV-Vis Spectrophotometry for the Determination of Cadmium in Water Samples

    Directory of Open Access Journals (Sweden)

    J. Pérez-Outeiral

    2014-01-01

    Full Text Available A simple and inexpensive method for cadmium determination in water using dispersive liquid-liquid microextraction and ultraviolet-visible spectrophotometry was developed. In order to obtain the best experimental conditions, experimental design was applied. Calibration was made in the range of 10–100 μg/L, obtaining good linearity (R2 = 0.9947. The obtained limit of detection based on calibration curve was 8.5 μg/L. Intra- and interday repeatability were checked at two levels, obtaining relative standard deviation values from 9.0 to 13.3%. The enrichment factor had a value of 73. Metal interferences were also checked and tolerable limits were evaluated. Finally, the method was applied to cadmium determination in real spiked water samples. Therefore, the method showed potential applicability for cadmium determination in highly contaminated liquid samples.

  15. Determination of trace amount of lead in industrial and municipal effluent water samples based on dispersive liquid-liquid extraction

    Energy Technology Data Exchange (ETDEWEB)

    Shirkhanloo, H. [Iranian Petroleum Industry Health Research Institute, Occupational and Environmental Health Research Center, Tehran (Iran, Islamic Republic of); Sedighi, K.; Mousavi, H. Z., E-mail: hzmousavi@semnan.ac.ir [Semnan University, College of Science, Department of Chemistry, Semnan (Iran, Islamic Republic of)

    2014-10-01

    In this study, a simple, sensitive and accurate method was developed for the determination of lead ion by combining ionic liquid dispersive liquid-liquid extraction (Il-DLL E) with flame atomic absorption spectrometry. Tetraethyl thiuram disulfide (Tetd), acetone and 1-octyl-3m ethylimidazolium hexafluorophosphate [(C{sub 8}MIM) (PF{sub 6})] were used as the chelating agent, dispersive and extraction solvent, respectively. Under the optimal conditions, the calibration graph was linear in the range of 5-190 μg L{sup -1} of lead and the detection limit was 0.8 μg L{sup -1} with a sample volume of 200 ml. The proposed method was validated by the analysis of one certified reference material and applied successfully to the determination of lead in real water samples. (Author)

  16. A miniature condensed-phase membrane introduction mass spectrometry (CP-MIMS) probe for direct and on-line measurements of pharmaceuticals and contaminants in small, complex samples.

    Science.gov (United States)

    Duncan, Kyle D; Willis, Megan D; Krogh, Erik T; Gill, Christopher G

    2013-06-15

    High-throughput, automated analytical measurements are desirable in many analytical scenarios, as are rapid sample pre-screening techniques to identify 'positive' samples for subsequent measurements using more time-consuming conventional methodologies (e.g., liquid chromatography/mass spectrometry (LC/MS)). A miniature condensed-phase membrane introduction mass spectrometry (CP-MIMS) probe for the direct and continuous, on-line measurement of pharmaceuticals and environmental contaminants in small, complex samples is presented. A miniature polydimethylsiloxane hollow fibre membrane (PDMS-HFM) probe is coupled with an electrospray ionization (ESI) triple quadrupole mass spectrometer. Analytes are transported from the probe to the ESI source by a methanol acceptor phase. The probe can be autosampler mounted and directly inserted in small samples (≥400 μL) allowing continuous and simultaneous pptr-ppb level detection of target analytes (chlorophenols, triclosan, gemfibrozil, nonylphenol) in complex samples (artificial urine, beer, natural water, waste water, plant tissue). The probe has been characterized and optimized for acceptor phase flow rate, sample mixing and probe washing. Signal response times, detection limits and calibration data are given for selected ion monitoring (SIM) and tandem mass spectrometry (MS/MS) measurements of target analytes at trace levels. Comparisons with flow cell type CP-MIMS systems are given. Analyte depletion effects are evaluated for small samples (≥400 μL). On-line measurements in small volumes of complex samples, temporally resolved reaction monitoring and in situ/in vivo demonstrations are presented. The miniature CP-MIMS probe developed was successfully used for the direct, on-line detection of target analytes in small volumes (40 mL to 400 μL) of complex samples at pptr to low ppb levels. The probe can be readily automated as well as deployed for in situ/in vivo monitoring, including reaction monitoring, small sample

  17. Data compliation report: K West Basin fuel storage canister liquid samples

    Energy Technology Data Exchange (ETDEWEB)

    Trimble, D.J.

    1995-12-21

    Sample analysis data from the 222-S Laboratory are reported. The data are for liquid samples taken from spent fuel storage canisters in the 105 K West Basin during March 1995. An analysis and data report from the Special Analytical Studies group of Westinghouse Hanford Company regarding these samples is also included. Data analysis is not included herein.

  18. Hexagonal sampling in the infrared domain: an introduction to array set addressing

    Science.gov (United States)

    Rummelt, Nicholas I.; Barrows, Geoffrey L.; Massie, Mark A.

    2011-06-01

    It has been known since the early 1960s that hexagonal sampling is the optimal sampling approach for isotropically band-limited images, providing a 13.4% improvement in sampling efficiency over rectangular sampling. Despite this fact and other significant advantages of hexagonal sampling, rectangular sampling is still used for virtually all modern digital image processing systems. This is arguably due to the lack of an efficient addressing system for hexagonal grids. Array set addressing (ASA) is a recent advance in addressing hexagonal grids that allows image processing techniques to be performed efficiently on hexagonally sampled images. This paper will describe ASA and discuss its advantages. With ASA, a renewed interest in sensors that sample hexagonally is occurring. We will describe a new visible imager that simultaneously samples both hexagonally and rectangularly. This novel research tool has the ability to provide real imagery that can be used to quantitatively compare the performance of an image processing operation on both hexagonally sampled and rectangularly sampled images. We will also describe current efforts and plans for future visible sensors that sample hexagonally. The advantages of hexagonal sampling are not limited to the visible domain and should be equally realizable in the infrared domain. This paper will discuss considerations for developing infrared sensors that sample hexagonally. On-focal plane array (FPA) processing, readout architectures, detector materials, and bump-bonding are among the topics to be discussed.

  19. Double-salting out assisted liquid-liquid extraction (SALLE) HPLC method for estimation of temozolomide from biological samples.

    Science.gov (United States)

    Jain, Darshana; Athawale, Rajani; Bajaj, Amrita; Shrikhande, Shruti

    2014-11-01

    The role of temozolomide (TMZ) in treatment of high grade gliomas, melanomas and other malignancies is being defined by the current clinical developmental trials. Temozolomide belongs to the group of alkylating agents and is prescribed to patients suffering from most aggressive forms of brain tumors. The estimation techniques for temozolomide from the extracted plasma or biological samples includes high-performance liquid chromatography with UV detection (HPLC-UV), micellar electrokinetic capillary chromatography (MKEC) and liquid chromatography coupled to mass spectroscopy (LC-MS). These methods suffer from disadvantages like low resolution, low sensitivity, low recovery or cost involvement. An analytical method possessing capacity to estimate low quantities of TMZ in plasma samples with high extraction efficiency (%) and high resolution with cost effectiveness needs to be developed. Cost effective, robust and low plasma component interfering HPLC method using salting out liquid-liquid extraction (SALLE) technique was developed and validated for estimation of drug from plasma samples. The extraction efficiency (%) with conventional LLE technique with methanol, ethyl acetate, dichloromethane and acetonitrile was found to be 5.99±2.45, 45.39±4.56, 46.04±1.14 and 46.23±3.67 respectively. Extraction efficiency (%) improved with SALLE where sodium chloride was used as an electrolyte and was found to be 6.80±5.56, 52.01±3.13, 62.69±2.11 and 69.20±1.18 with methanol, ethyl acetate, dichloromethane and acetonitrile as organic solvent. Upon utilization of two salts for extraction (double salting liquid-liquid extraction) the extraction efficiency (%) was further improved and was twice of LLE. It was found that double salting liquid-liquid extraction technique yielded extraction efficiency (%) of 11.71±5.66, 55.62±3.44, 77.28±2.89 and 87.75±0.89. Hence a method based on double SALLE was developed for quantification of TMZ demonstrating linearity in the range of

  20. An environmentally friendly method for the determination of triazine herbicides in estuarine seawater samples by dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Rodríguez-González, N; Beceiro-González, E; González-Castro, M J; Muniategui-Lorenzo, S

    2015-01-01

    A fast, simple, sensitive and green chemistry method using dispersive liquid-liquid microextraction (DLLME) for the simultaneous determination of seven triazine herbicides (ametryn, atrazine, cyanazine, propazine, simazine, simetryn and terbuthylazine) in estuarine seawater samples has been developed. DLLME was carried out using a small volume of seawater (25 mL) and 300 μL of 1-octanol. Herbicide concentrations were determined by liquid chromatography-diode array detection, and results were confirmed by liquid chromatography-electrospray ionisation tandem spectrometry analysis. The analytical features of the proposed method were satisfactory with repeatability 0.999 for all the analytes except for simazine (0.9975). Limits of quantification ranged between 0.19 and 1.12 μg L(-1). The method was applied to the analysis of seawater samples from ten points susceptible to contamination by triazines from estuary of A Coruña (Galicia, NW of Spain). The levels of the seven triazines were below the LODs in the analysed samples. Use of proposed method will allow for monitoring of triazines at levels below the regulatory limits set by the European Directive 2008/105/EC of 2 and 4 μg L(-1) for atrazine and simazine, respectively.

  1. [Diagnosis of amniotic fluid embolism with blood samples by liquid-based cytology technique].

    Science.gov (United States)

    Liu, Bao-qin; Deng, Jian-qiang; Hou, An-chao; Cai, Ji-feng

    2014-12-01

    To establish the diagnosis of amniotic fluid embolism with blood samples by liquid-based cytology technique and to study the validity of method. The blood samples were collected from patients who suffered from amniotic fluid embolism. The components of amniotic fluid in blood samples were examined with blood smear by two direct smear methods (supernatant smear, sediment smear) and two liquid-based cytology methods (automatic smear, manual smear). The positive detection rate of each method was calculated. The positive detection rates of two liquid-based cytology methods (84.6% and 92.3%, respectively) were much higher than those of two direct methods (53.8% and 61.5%, respectively). The liquid-based cytology technique could improve the positive detection rate of amniotic fluid embolism.

  2. Low cost methodology for estrogens monitoring in water samples using dispersive liquid-liquid microextraction and HPLC with fluorescence detection.

    Science.gov (United States)

    Lima, Diana L D; Silva, Carla Patrícia; Otero, Marta; Esteves, Valdemar I

    2013-10-15

    A new low cost methodology for estrogens' analysis in water samples was developed in this work. Based on dispersive liquid-liquid microextraction followed by high-performance liquid chromatography with fluorescence detection, the developed method is fast, cheap, easy-to-use, uses low volumes of organic solvents and has the possibility of a large number of samples to be extracted in parallel. Under optimum conditions (sample volume: 8 mL; extraction solvent: 200 μL of chlorobenzene; dispersive solvent: 2000 μL of acetone), the enrichment factor and extraction recoveries were 145 and 72% for 17β-estradiol (E2) and 178 and 89% for 17α-ethinylestradiol (EE2), respectively. Limits of detection of 2.0 ng L(-1) for E2 and 6.5 ng L(-1) for EE2 were achieved, allowing the detection and quantification of these compounds in surface and waste water samples with concentrations from 12 to 32 ng L(-1) for E2 and from 11 to 18 ng L(-1) for EE2. Also, recovery tests were performed to evaluate possible matrix effects. Recoveries between 98% and 106% were obtained using humic acids (HA) to simulate the effect of organic matter, and between 86% and 120% in real water samples.

  3. Rapid determination of lead and cadmium in sewage sludge samples using electrothermal atomic absorption spectrometry with slurry sample introduction

    Energy Technology Data Exchange (ETDEWEB)

    Lopez-Garcia, I.; Vinas, P.; Arroyo-Cortez, J.; Hernandez-Cordoba, M. [Dept. of Analytical Chem., Univ. of Murcia (Spain)

    2000-08-01

    Lead and cadmium concentrations in sewage sludge samples are determined by suspending the ground samples in a solution containing 10% (v/v) concentrated hydrofluoric acid, 1% (v/v) concentrated nitric acid, 0.5% (m/v) dihydrogen ammonium phosphate and 0.1% (m/v) sodium hexametaphosphate. Aliquots of 20 {mu}L of these suspensions (4 mg/mL) are diluted to 1000 {mu}L with the same solution and then injected into the electrothermal atomizer. The drying stage is performed by programming a 400 C temperature, a ramp time of 20 s and a hold time of 15 s on the power supply of the atomizer. No ashing step is used. Platform atomization is carried out at 1600 and 1800 C for Pb and Cd, respectively. Calibration is performed using aqueous standards in the 5-75 and 0.2- 5 {mu}g/L Pb and Cd ranges, respectively. Results obtained for three certified reference materials and four samples demonstrate the reliability of the procedures described. (orig.)

  4. Reversed-phase vortex-assisted liquid-liquid microextraction: a new sample preparation method for the determination of amygdalin in oil and kernel samples.

    Science.gov (United States)

    Hosseini, Mohammad; Heydari, Rouhollah; Alimoradi, Mohammad

    2015-02-01

    A novel, simple, and rapid reversed-phase vortex-assisted liquid-liquid microextraction coupled with high-performance liquid chromatography has been introduced for the extraction, clean-up, and preconcentration of amygdalin in oil and kernel samples. In this technique, deionized water was used as the extracting solvent. Unlike the reversed-phase dispersive liquid-liquid microextraction, dispersive solvent was eliminated in the proposed method. Various parameters that affected the extraction efficiency, such as extracting solvent volume and its pH, vortex, and centrifuging times were evaluated and optimized. The calibration curve shows good linearity (r(2) = 0.9955) and precision (RSD < 5.2%) in the range of 0.07-20 μg/mL. The limit of detection and limit of quantitation were 0.02 and 0.07 μg/mL, respectively. The recoveries were in the range of 96.0-102.0% with relative standard deviation values ranging from 4.0 to 5.1%. Unlike the conventional extraction methods for plant extracts, no evaporative and re-solubilizing operations were needed in the proposed technique. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Introduction to Mars Sampling Handling Workshop Series. Workshop on Life Detection: Issues and Topics

    Science.gov (United States)

    Rummel, John D.

    2001-01-01

    Before martian soil and rock samples can be distributed to the research community, the returned materials will initially be quarantined and examined in a proposed BSL-4 containment facility to assure that no putative martian microorganisms or attendant potential biohazards exist. During the initial quarantine, state-of-the-art life detection and biohazard testing of the returned martian samples will be conducted. Life detection, as defined here in regard to Mars sample return missions, is the detection of living organisms and/or materials that have been derived from living organisms that may be present in the sample.

  6. Ultrasound-assisted dispersive liquid-liquid microextraction combined with high-performance liquid chromatography-fluorescence detection for sensitive determination of biogenic amines in rice wine samples.

    Science.gov (United States)

    Huang, Ke-Jing; Wei, Cai-Yun; Liu, Wei-Li; Xie, Wan-Zhen; Zhang, Jun-Feng; Wang, Wei

    2009-09-18

    Ultrasound-assisted dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography-fluorescence detection was used for the extraction and determination of three biogenic amines including octopamine, tyramine and phenethylamine in rice wine samples. Fluorescence probe 2,6-dimethyl-4-quinolinecarboxylic acid N-hydroxysuccinimide ester was applied for derivatization of biogenic amines. Acetonitrile and 1-octanol were used as disperser solvent and extraction solvent, respectively. Extraction conditions including the type of extraction solvent, the volume of extraction solvent, ultrasonication time and centrifuging time were optimized. After extraction and centrifuging, analyte was injected rapidly into high-performance liquid chromatography and then detected with fluorescence. The calibration graph of the proposed method was linear in the range of 5-500 microg mL(-1) (octopamine and tyramine) and 0.025-2.5 microg mL(-1) (phenethylamine). The relative standard deviations were 2.4-3.2% (n=6) and the limits of detection were in the range of 0.02-5 ng mL(-1). The method was applied to analyze the rice wine samples and spiked recoveries in the range of 95.42-104.56% were obtained. The results showed that ultrasound-assisted dispersive liquid-liquid microextraction was a very simple, rapid, sensitive and efficient analytical method for the determination of trace amount of biogenic amines.

  7. Direct sampling of metastatic ovarian carcinoma masquerading as endocervical adenocarcinoma in liquid-based cytology cervical sample

    Science.gov (United States)

    Gupta, Nalini; Bhar, Vikrant; Dey, Pranab; Rajwanshi, Arvind; Suri, Vanita

    2014-01-01

    Cervical sample is routinely taken to identify squamous dysplastic lesions of the cervix. Glandular lesions are far less commonly reported on cervical samples. The most common glandular lesion reported on cervical smear is endocervical adenocarcinoma, followed by endometrial adenocarcinoma. Direct sampling by Cervex brush is possible even in endometrial adenocarcinoma, if the tumor directly involves lower uterine segment/endocervical canal. Metastases to cervix are rare but have occasionally been reported in previous reports. We wish to highlight in this case, metastatic ovarian carcinoma directly sampled in cervical liquid-based cytology (LBC) sample, which mimicked cytomorphologically a well-differentiated endocervical adenocarcinoma. To the best of our knowledge, a similar case has not been previously published in SurePath LBC sample. PMID:25538388

  8. Aluminium sensitized spectrofluorimetric determination of fluoroquinolones in milk samples coupled with salting-out assisted liquid-liquid ultrasonic extraction

    Science.gov (United States)

    Xia, Qinghai; Yang, Yaling; Liu, Mousheng

    2012-10-01

    An aluminium sensitized spectrofluorimetric method coupled with salting-out assisted liquid-liquid ultrasonic extraction for the determination of four widely used fluoroquinolones (FQs) namely norfloxacin (NOR), ofloxacin (OFL), ciprofloxacin (CIP) and gatifloxacin (GAT) in bovine raw milk was described. The analytical procedure involves the fluorescence sensitization of aluminium (Al3+) by complexation with FQs, salting-out assisted liquid-liquid ultrasonic extraction (SALLUE), followed by spectrofluorometry. The influence of several parameters on the extraction (the salt species, the amount of salt, pH, temperature and phase volume ratio) was investigated. Under optimized experimental conditions, the detection limits of the method in milk varied from 0.009 μg/mL for NOR to 0.016 μg/mL for GAT (signal-to-noise ratio (S/N) = 3). The relative standard deviations (RSD) values were found to be relatively low (0.54-2.48% for four compounds). The calibration graph was linear from 0.015 to 2.25 μg/mL with coefficient of determinations not less than 0.9974. The methodology developed was applied to the determination of FQs in bovine raw milk samples. The main advantage of this method is simple, accurate and green. The method showed promising applications for analyzing polar analytes especially polar drugs in various sample matrices.

  9. Sensitive spectrophotometric determination of Co(II) using dispersive liquid-liquid micro-extraction method in soil samples.

    Science.gov (United States)

    Hasanpour, Foroozan; Hadadzadeh, Hassan; Taei, Masoumeh; Nekouei, Mohsen; Mozafari, Elmira

    2016-05-01

    Analytical performance of conventional spectrophotometer was developed by coupling of effective dispersive liquid-liquid micro-extraction method with spectrophotometric determination for ultra-trace determination of cobalt. The method was based on the formation of Co(II)-alpha-benzoin oxime complex and its extraction using a dispersive liquid-liquid micro-extraction technique. During the present work, several important variables such as pH, ligand concentration, amount and type of dispersive, and extracting solvent were optimized. It was found that the crucial factor for the Co(II)-alpha benzoin oxime complex formation is the pH of the alkaline alcoholic medium. Under the optimized condition, the calibration graph was linear in the ranges of 1.0-110 μg L(-1) with the detection limit (S/N = 3) of 0.5 μg L(-1). The preconcentration operation of 25 mL of sample gave enhancement factor of 75. The proposed method was applied for determination of Co(II) in soil samples.

  10. Introduction to the theory of soft matter from ideal gases to liquid crystals

    CERN Document Server

    Selinger, Jonathan V

    2016-01-01

    This book presents the theory of soft matter to students at the advanced undergraduate or beginning graduate level. It provides a basic introduction to theoretical physics as applied to soft matter, explaining the concepts of symmetry, broken symmetry, and order parameters; phases and phase transitions; mean-field theory; and the mathematics of variational calculus and tensors. It is written in an informal, conversational style, which is accessible to students from a diverse range of backgrounds. The book begins with a simple “toy model” to demonstrate the physical significance of free energy. It then introduces two standard theories of phase transitions—the Ising model for ferromagnetism and van der Waals theory of gases and liquids—and uses them to illustrate principles of statistical mechanics. From those examples, it moves on to discuss order, disorder, and broken symmetry in many states of matter, and to explain the theoretical methods that are used to model the phenomena. It concludes with a cha...

  11. A hydrophobic ionic liquid compartmentalized sampling/labeling and its separation techniques in polydimethylsiloxane microchip capillary electrophoresis.

    Science.gov (United States)

    Quan, Hong Hua; Li, Ming; Huang, Yan; Hahn, Jong Hoon

    2017-01-01

    This paper demonstrates a novel compartmentalized sampling/labeling method and its separation techniques using a hydrophobic ionic liquid (IL)-1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imidate (BmimNTf2 )-as the immiscible phase, which is capable of minimizing signal losses during microchip capillary electrophoresis (MCE). The MCE device consists of a silica tube connected to a straight polydimethylsiloxane (PDMS) separation channel. Poly(diallyldimethylammonium chloride) (PDDAC) was coated on the inner surface of channel to ease the introduction of IL plugs and enhance the IL wetting on the PDMS surface for sample releasing. Electroosmotic flow (EOF)-based sample compartmentalization was carried out through a sequenced injection into sampling tubes with the following order: leading IL plug/sample segment/terminal IL plug. The movement of the sample segment was easily controlled by applying an electrical voltage across both ends of the chip without a sample volume change. This approach effectively prevented analyte diffusion before injection into MCE channels. When the sample segment was manipulated to the PDDAC-modified PDMS channel, the sample plug then was released from isolation under EOF while IL plugs adsorbed onto channel surfaces owing to strong adhesion. A mixture of flavin adenine nucleotides (FAD) and flavin mononucleotides (FMN) was successfully separated on a 2.5 cm long separation channel, for which the theoretical numbers of plates were 15 000 and 17 000, respectively. The obtained peak intensity was increased 6.3-fold over the corresponding value from conventional electrokinetic injection with the same sampling time. Furthermore, based on the compartmented sample segment serving as an interim reactor, an on-chip fluorescence labeling is demonstrated. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Development of a portable mass spectrometer characterized by discontinuous sample gas introduction, a low-pressure dielectric barrier discharge ionization source, and a vacuumed headspace technique.

    Science.gov (United States)

    Kumano, Shun; Sugiyama, Masuyuki; Yamada, Masuyoshi; Nishimura, Kazushige; Hasegawa, Hideki; Morokuma, Hidetoshi; Inoue, Hiroyuki; Hashimoto, Yuichiro

    2013-05-21

    The present study has attempted to downscale a mass spectrometer in order to make it portable and enable onsite analysis with it. The development of a small mass spectrometer required the use of a compact pump whose displacement was small, decreasing the sensitivity of that spectrometer. To get high sensitivity with a small mass spectrometer, we have integrated novel techniques: a highly sensitive ionization source and efficient extraction of sample vapor. The low-pressure dielectric barrier discharge ionization (LP-DBDI) source made it possible to increase the conductance between the source and the mass analyzer, compared with ambient ionization sources, enhancing the efficiency of the ion transfer from the ionization source to the mass analyzer. We have also developed a vacuumed headspace method efficiently transporting the sample vapor to the ionization source. The sensitivity was further enhanced by also using a discontinuous sample gas introduction technique. A prototype portable mass spectrometer using those novel techniques was found to be sensitive enough to detect 0.1 ppm methamphetamine, 1 ppm amphetamine, 1 ppm 3,4-methylenedioxymethamphetamine, and 10 ppm cocaine in liquid.

  13. The lead-liquid argon sampling calorimeter of the SLD detector

    Energy Technology Data Exchange (ETDEWEB)

    Axen, D.; Bougerolle, S.; Sobie, R. (Univ. British Columbia, Vancouver, BC (Canada)); Eigen, G.; De Jongh, F.; Hitlin, D.; Kelsey, M.; Klein, M.; Mincer, A.; Wisniewski, W.; Wolf, R. (California Inst. of Technology, Pasadena, CA (United States)); Arroyo, C.; Au, Y.; Baltay, C.; Bolton, T.; Bazarko, A.; Camilleri, L.; Hyatt, E.; Manly, S.; Rabinowitz, S.; Rowson, P.C.; Seligman, S.; Shaevitz, M.H.; Smith, S.; Steiner, R.V. (Columbia Univ., Nevis Lab., Irvington, NY (United States)); Abt, I.; Alzofon, D.; Arnett, D.; Barrera, F.; Bell, R.; Bes, S.C.; Bogart, J.; Breidenbach, M.; Candia, A.; Claus, R.; Cutler, H.; Davis, R.; Dubois, R.; Foss, M.; Fox, J.; Fox, M.; Gioumousis, A.; Grebenyuk, A.; Haller, G.; Hamilton, V.; Hodgson, J.; Huffer, M.; Junk, T.; Kim, P.; Labs, J.; Neal, H.; Nelson, D.; Nordby, M.; Paffrath, L.; Putallaz, G.; Rogers, H.; Russell, J.J.; Saez, P.; Seward, P.; Sherden, D.; Skarpaas, K.; Schindler, R.H.; Waite, A.P.; Watt, R. (Stanford Linear Accelerator Center, CA

    1993-05-01

    The lead-liquid argon sampling calorimeter of the SLD detector is one of the largest detectors employing cryogenic liquids now in operation. This paper details the design and performance considerations, the mechanical and cryogenic systems, the absorber design and tower segmentation, the data acquisition electronics, and the control systems of the detector. The initial operational performance of the device is discussed. Detailed resolution studies will be presented in a later paper. (orig.).

  14. Study on Introduction of CO2 Free Energy to Japan with Liquid Hydrogen

    Science.gov (United States)

    Kamiya, Shoji; Nishimura, Motohiko; Harada, Eichi

    In Japan, both CO2(Carbon dioxide) emission reduction and energy security are the very important social issues after Fukushima Daiichi accident. On the other hand, FCV (Fuel Cell Vehicle)using hydrogen will be on the market in 2015. Introducing large mass hydrogen energy is being expected as expanding hydrogen applications, or solution to energy issues of Japan.And then,the Japanese government announced the road map for introducing hydrogen energy supply chain in this June,2014. Under these circumstances, imported CO2 free hydrogen will be one of the solutions for energy security and CO2 reduction, if the hydrogen price is affordable. To achieve this, Kawasaki Heavy Industries, Ltd. (KHI) performed a feasibility studyon CO2-free hydrogen energy supply chainfrom Australian brown coal linked with CCS (Carbon dioxide Capture and Storage) to Japan. In the study, hydrogen production systems utilizing brown coal gasificationandLH2 (liquid hydrogen)systems as storing and transporting hydrogen are examined.This paper shows the possibilityof realizingthe CO2 free hydrogen supply chain, the cost breakdown of imported hydrogen cost, its cost competitiveness with conventionalfossil, andLH2systems as key technologies of the hydrogen energy chain.

  15. Introduction to grayscale calibration and related aspects of medical imaging grade liquid crystal displays.

    Science.gov (United States)

    Fetterly, Kenneth A; Blume, Hartwig R; Flynn, Michael J; Samei, Ehsan

    2008-06-01

    Consistent presentation of digital radiographic images at all locations within a medical center can help ensure a high level of patient care. Currently, liquid crystal displays (LCDs) are the electronic display technology of choice for viewing medical images. As the inherent luminance (and thereby perceived contrast) properties of different LCDs can vary substantially, calibration of the luminance response of these displays is required to ensure that observer perception of an image is consistent on all displays. The digital imaging and communication in medicine (DICOM) grayscale standard display function (GSDF) defines the luminance response of a display such that an observer's perception of image contrast is consistent throughout the pixel value range of a displayed image. The main purpose of this work is to review the theoretical and practical aspects of calibration of LCDs to the GSDF. Included herein is a review of LCD technology, principles of calibration, and other practical aspects related to calibration and observer perception of images presented on LCDs. Both grayscale and color displays are considered, and the influence of ambient light on calibration and perception is discussed.

  16. Calibration of a liquid scintillation counter to assess tritium levels in various samples

    CERN Document Server

    Al-Haddad, M N; Abu-Jarad, F A

    1999-01-01

    An LKB-Wallac 1217 Liquid Scintillation Counter (LSC) was calibrated with a newly adopted cocktail. The LSC was then used to measure tritium levels in various samples to assess the compliance of tritium levels with the recommended international levels. The counter was calibrated to measure both biological and operational samples for personnel and for an accelerator facility at KFUPM. The biological samples include the bioassay (urine), saliva, and nasal tests. The operational samples of the light ion linear accelerator include target cooling water, organic oil, fomblin oil, and smear samples. Sets of standards, which simulate various samples, were fabricated using traceable certified tritium standards. The efficiency of the counter was obtained for each sample. The typical range of the efficiencies varied from 33% for smear samples down to 1.5% for organic oil samples. A quenching curve for each sample is presented. The minimum detectable activity for each sample was established. Typical tritium levels in bio...

  17. Measurement of actinides in environmental samples by Photo-Electron Rejecting Alpha Liquid Scintillation

    Energy Technology Data Exchange (ETDEWEB)

    Cadieux, J.R. [Westinghouse Savannah River Co., Aiken, SC (United States); Clark, S. [Savannah River Ecology Lab., Univ. of Georgia (United States); Fjeld, R.A.; Reboul, S.; Sowder, A. [Clemson Univ., SC (United States). Dept. of Environmental Systems Engineering

    1994-05-01

    This work describes the adaptation of extractive scintillation with a Photo-Electron Rejecting Alpha Liquid Scintillation (PERALS) (ORDELA, Inc.) spectrometer to the analysis of actinides in environmental samples from the Savannah River Site (SRS). Environmental quality assurance standards and actual water samples were treated by one of two methods; either a two step direct extraction, or for more complex samples, pretreatment by an extraction chromatographic separation prior to measurement of the alpha activity by PERALS.

  18. Feasibility of corona discharge ion mobility spectrometry for direct analysis of samples extracted by dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Jafari, Mohammad T; Riahi, Farhad

    2014-05-23

    The capability of corona discharge ionization ion mobility spectrometry (CD-IMS) for direct analysis of the samples extracted by dispersive liquid-liquid microextraction (DLLME) was investigated and evaluated, for the first time. To that end, an appropriate new injection port was designed and constructed, resulting in possibility of direct injection of the known sample volume, without tedious sample preparation steps (e.g. derivatization, solvent evaporation, and re-solving in another solvent…). Malathion as a test compound was extracted from different matrices by a rapid and convenient DLLME method. The positive ion mobility spectra of the extracted malathion were obtained after direct injection of carbon tetrachloride or methanol solutions. The analyte responses were compared and the statistical results revealed the feasibility of direct analysis of the extracted samples in carbon tetrachloride, resulting in a convenient methodology. The coupled method of DLLME-CD-IMS was exhaustively validated in terms of sensitivity, dynamic range, recovery, and enrichment factor. Finally, various real samples of apple, river and underground water were analyzed, all verifying the feasibility and success of the proposed method for the easy extraction of the analyte using DLLME separation before the direct analysis by CD-IMS.

  19. A new treatment by dispersive liquid-liquid microextraction for the determination of parabens in human serum samples.

    Science.gov (United States)

    Vela-Soria, F; Ballesteros, O; Rodríguez, I; Zafra-Gómez, A; Ballesteros, L; Cela, R; Navalón, A

    2013-09-01

    Alkyl esters of p-hydroxybenzoic acid (parabens) are a family of compounds that have been in use since the 1920s as preservatives in cosmetic formulations, with one of the lowest rates of skin problems reported in dermatological patients. However, in the last few years, many scientific publications have demonstrated that parabens are weak endocrine disruptors, meaning that they can interfere with the function of endogenous hormones, increasing the risk of breast cancer. In the present work, a new sample treatment method is introduced based on dispersive liquid-liquid microextraction for the extraction of the most commonly used parabens (methyl-, ethyl-, propyl-, and butylparaben) from human serum samples followed by separation and quantification using ultrahigh performance liquid chromatography-tandem mass spectrometry. The method involves an enzymatic treatment to quantify the total content of parabens. The extraction parameters (solvent and disperser solvent, extractant and dispersant volume, pH of the sample, salt addition, and extraction time) were accurately optimized using multivariate optimization strategies. Ethylparaben ring (13)C6-labeled was used as surrogate. Limits of quantification ranging from 0.2 to 0.7 ng mL(-1) and an interday variability (evaluated as relative standard deviations) from 3.8 to 11.9 % were obtained. The method was validated using matrix-matched calibration standard and a spike recovery assay. Recovery rates for spiked samples ranged from 96 to 106 %, and a good linearity up to concentrations of 100 ng mL(-1) was obtained. The method was satisfactorily applied for the determination of target compounds in human serum samples.

  20. Liquid Phase Micro-Extraction of Linear Alkylbenzene Sulfonate Anionic Surfactants in Aqueous Samples

    OpenAIRE

    2011-01-01

    Hollow fiber liquid phase micro-extraction (LPME) of linear alkylbenzene sulfonates (LAS) from aqueous samples was studied. Ion pair extraction of C10, C11, C12 and C13 homologues was facilitated with trihexylamine as ion-pairing agent, using di-n-hexylether as solvent for the supported liquid membrane (SLM). Effects of extraction time, acceptor buffer concentration, stirring speed, sample volume, NaCl and humic acids were studied. At 10–50 μg L−1 linear R2-coefficients were 0.99 for C10 and ...

  1. Determination of chlorophenols in honey samples using in-situ ionic liquid-dispersive liquid-liquid microextraction as a pretreatment method followed by high-performance liquid chromatography.

    Science.gov (United States)

    Fan, Chen; Li, Nai; Cao, Xueli

    2015-05-01

    In-situ ionic liquid-dispersive liquid-liquid microextraction (IL-DLLME) method was developed as a pretreatment method for the detection of six chlorophenols (CPs) in honey samples. The hydrophobic ionic liquid [C4MIM][NTf2], formed in-situ by the hydrophilic ionic liquid [C4MIM][BF4] and the ion exchange reagent LiNTf2 was used as the microextractant solvent of CPs from honey sample. Then the enriched analytes were back-extracted into 40 μL of 0.14 M NaOH solution and finally subjected to analysis by high-performance liquid chromatography. The method showed low limit of detection of CPs, 0.8-3.2 μg/L and high enrichment factor, 34-65 with the recoveries range from 91.60% to 114.33%. The method is simple, rapid, environmentally friendly and with high extraction efficiency.

  2. Multiple functional ionic liquids based dispersive liquid-liquid microextraction combined with high performance chromatography for the determination of phenolic compounds in water samples.

    Science.gov (United States)

    Sun, Jian-Nan; Chen, Juan; Shi, Yan-Ping

    2014-07-01

    A new mode of ionic liquid based dispersive liquid-liquid microextraction (IL-DLLME) is developed. In this work, [C6MIm][PF6] was chosen as the extraction solvent, and two kinds of hydrophilic ionic liquids, [EMIm][BF4] and [BSO3HMIm][OTf], functioned as the dispersive solvent. So in the whole extraction procedure, no organic solvent was used. With the aid of SO3H group, the acidic compound was extracted from the sample solution without pH adjustment. Two phenolic compounds, namely, 2-naphthol and 4-nitrophenol were chosen as the target analytes. Important parameters affecting the extraction efficiency, such as the type of hydrophilic ionic liquids, the volume ratio of [EMIm][BF4] to [BSO3HMIm][OTf], type and volume of extraction solvent, pH value of sample solution, sonication time, extraction time and centrifugation time were investigated and optimized. Under the optimized extraction conditions, the method exhibited good sensitivity with the limits of detection (LODs) at 5.5 μg L(-1)and 10.0 μg L(-1) for 4-nitrophenol and 2-naphthol, respectively. Good linearity over the concentration ranges of 24-384 μg L(-1) for 4-nitrophenol and 28-336 μg L(-1) for 2-naphthol was obtained with correlation coefficients of 0.9998 and 0.9961, respectively. The proposed method can directly extract acidic compound from environmental sample or even more complex sample matrix without any pH adjustment procedure.

  3. Ionic liquid-based dispersive liquid-liquid microextraction and enhanced spectrophotometric determination of molybdenum (VI) in water and plant leaves samples by FO-LADS.

    Science.gov (United States)

    Gharehbaghi, Maysam; Shemirani, Farzaneh

    2011-02-01

    A new simple and rapid ionic liquid-based dispersive liquid-liquid microextraction (IL-DLLME) has been applied to preconcentrate trace levels of molybdenum (VI) as a prior step to its enhanced determination by fiber optic-linear array detection spectrophotometry (FO-LADS). In this method, a small amount of [Hmim][Tf(2)N] (1-hexyl-3-methylimmidazolium bis (trifluormethylsulfonyl) imid) as an extraction solvent was applied to extract molybdenum - pyrogallol red complex, which was formed in an aqueous solution in the presence of N-cetyl-N-N-N-trimethyl ammonium chloride as a sensitizing agent. Under optimum conditions, enhancement factor, detection limit and relative standard deviation (n=5, for 30 μg L(-1) of molybdenum (VI)) in 10 mL water sample were 72.6, 1.43 μg L(-1) and 2.8%, respectively.

  4. Determination of Zinc Ions in Environmental Samples by Dispersive Liquid- Liquid Micro Extraction and Atomic Absorption Spectroscopy

    Directory of Open Access Journals (Sweden)

    F. Arabi

    2012-11-01

    Full Text Available In this work preconcentration of the Zn ions was investigated in water sample by Dispersive liquid- liquid micro extraction (DLLME using chloroform as an extraction solvent, methanol as a disperser solvent and 8-Hydroxyquinoline as a chelating agent. The determination of extracted ions was done by graphite furnace atomic absorption spectrometry. The influence of various analytical parameters including pH, extraction and disperser solvent type and volume and concentration of the chelating agent on the extraction efficiency of analyses was investigated. After extraction, the enrichment factor was 26 and the detection limit of the method was 0.0033 µg l-1 and the relative standard deviations (R.S.D for five determinations of 1 ng/ml Zn were 7.41%. 

  5. A new device for magnetic stirring-assisted dispersive liquid-liquid microextraction of UV filters in environmental water samples.

    Science.gov (United States)

    Zhang, Ping-Ping; Shi, Zhi-Guo; Yu, Qiong-Wei; Feng, Yu-Qi

    2011-02-15

    A new method based on dispersive liquid-liquid microextraction (DLLME) in combination with high-performance liquid chromatography (HPLC) has been developed for the analysis of UV filters. A specially designed flask, which has two narrow open necks with one of them having a capillary tip, was employed to facilitate the DLLME process. By adopting such a device, the extraction and subsequent phase separation were conveniently achieved. A binary solvent system of water sample and low-density extraction solvent (1-octanol) was used for the DLLME and no disperser solvent was involved. The extraction was accelerated by magnetic agitation of the two phases. After extraction, phase separation of the extraction solvent from the aqueous sample was easily achieved by leaving the extraction system statically for a while. No centrifugation step involving in classical DLLME was necessary. The analyte-enriched phase, floating above the sample solution, was elevated and concentrated into the narrow open tip of the flask by adding pure water into it via the other port, which was withdrawn with a microsyringe for the subsequent HPLC analysis. Under the optimized conditions, the limits of detection for the analytes were in range of 0.2-0.8ngmL(-1) .The linearity ranges were 8-20,000 ng mL(-1) for HB, 7-20,000 ng mL(-1) for DB, 8-10,000 ng mL(-1) for BP and 5-20,000 ng mL(-1) for HMB, respectively. Enrichment factors ranging from 59 to 107 folders were obtained for the analytes. The relative standard deviations (n=3) at a spiked level of 80 ng mL(-1) were between 1.4 and 4.8%. The proposed magnetic stirring-assisted DLLME method was successfully applied to the analysis of lake water samples.

  6. Determination of estrogenic mycotoxins in environmental water samples by low-toxicity dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Emídio, Elissandro Soares; da Silva, Claudia Pereira; de Marchi, Mary Rosa Rodrigues

    2015-04-24

    A novel, simple, rapid and eco-friendly method based on dispersive liquid-liquid microextraction using a bromosolvent was developed to determine six estrogenic mycotoxins (zearalenone, zearalanone, α-zearalanol, β-zearalanol, α-zearalenol and β-zearalenol) in water samples by liquid chromatography-electrospray ionization tandem mass spectrometry in the negative mode (LC-ESI-MS/MS). The optimal conditions for this method include the use of 100 μL bromocyclohexane as an extraction solvent (using a non-dispersion solvent), 10 mL of aqueous sample (adjusted to pH 4), a vortex extraction time of 2 min, centrifugation for 10 min at 3500 rpm and no ionic strength adjustment. The calibration function was linear and was verified by applying the Mandel fitting test with a 95% confidence level. No matrix effect was observed. According to the relative standard deviations (RSDs), the precision was better than 13% for the repeatability and intermediate precision. The average recoveries of the spiked compounds ranged from 81 to 118%. The method limits of detection (LOD) and quantification (LOQ) considering a 125-fold pre-concentration step were 4-20 and 8-40 ng L(-1), respectively. Next, the method was applied to the analysis of the environmental aqueous samples, demonstrating the presence of β-zearalanol and zearalanone in the river water samples.

  7. Fast, simple and efficient salting-out assisted liquid-liquid extraction of naringenin from fruit juice samples prior to their enantioselective determination by liquid chromatography.

    Science.gov (United States)

    Magiera, Sylwia; Kwietniowska, Ewelina

    2016-11-15

    In this study, an easy, simple and efficient method for the determination of naringenin enantiomers in fruit juices after salting-out-assisted liquid-liquid extraction (SALLE) and high-performance liquid chromatography (HPLC) with diode-array detection (DAD) was developed. The sample treatment is based on the use of water-miscible acetonitrile as the extractant and acetonitrile phase separation under high-salt conditions. After extraction, juice samples were incubated with hydrochloric acid in order to achieve hydrolysis of naringin to naringenin. The hydrolysis parameters were optimized by using a half-fraction factorial central composite design (CCD). After sample preparation, chromatographic separation was obtained on a Chiralcel® OJ-RH column using the mobile phase consisting of 10mM aqueous ammonium acetate:methanol:acetonitrile (50:30:20; v/v/v) with detection at 288nm. The average recovery of the analyzed compounds ranged from 85.6 to 97.1%. The proposed method was satisfactorily used for the determination of naringenin enantiomers in various fruit juices samples.

  8. Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Fernández, Elena; Vidal, Lorena; Costa-García, Agustín; Canals, Antonio

    2016-04-07

    A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid-liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L(-1) of mercury. Standard addition calibration curves using standards between 0 and 20 μg L(-1) gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L(-1), and from 1.1 to 1.3 μg L(-1), respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10-20 μg L(-1)). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L(-1) as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).

  9. Ionic liquid based dispersive liquid-liquid microextraction coupled with micro-solid phase extraction of antidepressant drugs from environmental water samples.

    Science.gov (United States)

    Ge, Dandan; Lee, Hian Kee

    2013-11-22

    Ionic liquid-dispersive liquid-liquid microextraction combined with micro-solid phase extraction (IL-DLLME-μ-SPE), and high-performance liquid chromatography (HPLC) was developed for the determination of tricyclic antidepressants (TCAs) in water samples. Two hundred microliters of an organic solvent (as disperser solvent) and 20 μl of 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate were injected into a 5.0 ml sample for sonication-assisted DLLME. After this, a μ-SPE device, containing a novel material zeolite imidazolate framework 4 (ZIF-4), was added into the sample solution and 1 min of vortex-assisted extraction was performed. After 5 min of sonication-assisted desorption, 10 μl of desorption solvent was injected into a HPLC system for analysis. A characteristic property of DLLME-VA-μ-SPE is that any organic solvent and solid sorbent immiscible with water can be used. Special apparatus, or conical-bottom test tubes, and tedious procedures conventionally associated with DLLME such as centrifugation, or refrigeration of solvent are not necessary in the present approach. A novel material, ZIF-4 was employed as μ-SPE sorbent. Under the optimized conditions, the calibration curves were linear in the range of 1-1000 μg/L. The relative standard deviations and the limits of detection were in the range of 1.5% and 7.8% and 0.3 and 1 μg/L, respectively. The relative recoveries of canal water samples, spiked with drugs, were in the range of 94.3% and 114.7%. The results showed that IL-DLLME-μ-SPE was suitable for the determination of TCAs in water samples.

  10. Introduction to project MIDTAL: its methods and samples from Arcachon Bay, France.

    Science.gov (United States)

    Kegel, Jessica U; Del Amo, Yolanda; Medlin, Linda K

    2013-10-01

    Microalgae worldwide regularly cause harmful effects, considered from the human perspective, in that they cause health problems and economic damage to fisheries and tourism. Cyanobacteria cause similar problems in freshwaters. These episodes encompass a broad range of phenomena collectively referred to as "harmful algal blooms" (HABs). For adequate management of these phenomena, monitoring of microalgae is required. However, effective monitoring is time-consuming because cell morphology as determined by light microscopy may be insufficient to give definitive species and toxin attribution. In the European Union FP7 project MIDTAL (Microarrays for the Detection of Toxic Algae), we achieved rapid species identification using rRNA genes as the target. These regions can be targeted for probe design to recognise species or even strains. We also included antibody reactions to specific toxins produced by these microalgae because, even when cell numbers are low, toxins can be present and can accumulate in the shellfish. Microarrays are the state-of-the-art technology in molecular biology for the processing of bulk samples for detection of target RNA/DNA sequences. After 36 months, we have completed RNA-cell number-signal intensity calibration curves for 18 HAB species and the analysis of monthly field samples from five locations from year 1. Results from one location, Arcachon Bay (France), are reported here and compared favourably with cell counts in most cases. In general, the microarray was more sensitive than the cell counts, and this is likely a reflection in the difference in water volume analysed with the volume filtered for the microarray an order of magnitude greater.

  11. An interface for the direct coupling of small liquid samples to AMS

    Energy Technology Data Exchange (ETDEWEB)

    Ognibene, T.J., E-mail: ognibene1@llnl.gov [Center for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, 7000 East Ave, Livermore, CA 94551 (United States); Thomas, A.T.; Daley, P.F.; Bench, G. [Center for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, 7000 East Ave, Livermore, CA 94551 (United States); Turteltaub, K.W. [Biology and Biotechnology Division, Lawrence Livermore National Laboratory, 7000 East Ave, Livermore, CA 94551 (United States)

    2015-10-15

    We describe the moving wire interface attached to the 1-MV AMS system at LLNL’s Center for Accelerator Mass Spectrometry for the analysis of nonvolatile liquid samples as either discrete drops or from the direct output of biochemical separatory instrumentation, such as high-performance liquid chromatography (HPLC). Discrete samples containing at least a few 10 s of nanograms of carbon and as little as 50 zmol {sup 14}C can be measured with a 3–5% precision in a few minutes. The dynamic range of our system spans approximately 3 orders in magnitude. Sample to sample memory is minimized by the use of fresh targets for each discrete sample or by minimizing the amount of carbon present in a peak generated by an HPLC containing a significant amount of {sup 14}C. Liquid sample AMS provides a new technology to expand our biomedical AMS program by enabling the capability to measure low-level biochemicals in extremely small samples that would otherwise be inaccessible.

  12. An interface for the direct coupling of small liquid samples to AMS

    Science.gov (United States)

    Ognibene, T. J.; Thomas, A. T.; Daley, P. F.; Bench, G.; Turteltaub, K. W.

    2015-10-01

    We describe the moving wire interface attached to the 1-MV AMS system at LLNL's Center for Accelerator Mass Spectrometry for the analysis of nonvolatile liquid samples as either discrete drops or from the direct output of biochemical separatory instrumentation, such as high-performance liquid chromatography (HPLC). Discrete samples containing at least a few 10 s of nanograms of carbon and as little as 50 zmol 14C can be measured with a 3-5% precision in a few minutes. The dynamic range of our system spans approximately 3 orders in magnitude. Sample to sample memory is minimized by the use of fresh targets for each discrete sample or by minimizing the amount of carbon present in a peak generated by an HPLC containing a significant amount of 14C. Liquid sample AMS provides a new technology to expand our biomedical AMS program by enabling the capability to measure low-level biochemicals in extremely small samples that would otherwise be inaccessible.

  13. In-situ metathesis reaction combined with ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction method for the determination of phenylurea pesticides in water samples.

    Science.gov (United States)

    Zhang, Jiaheng; Liang, Zhe; Li, Songqing; Li, Yubo; Peng, Bing; Zhou, Wenfeng; Gao, Haixiang

    2012-08-30

    A novel microextraction technique, named in-situ metathesis reaction, combined with ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction was developed for the determination of five phenylurea pesticides (i.e., diuron, diflubenzuron, teflubenzuron, flufenoxuron, and chlorfluazuron) in environmental water samples. In the developed method, 360 μL LiNTf(2) aqueous solution (0.162 g/mL) was added to the sample solution containing a small amount of [C(6)MIM]Cl (0.034 g) to form a water-immiscible ionic liquid, [C(6)MIM]NTf(2), as extraction solution. The mixed solutions were placed in an ultrasonic water bath at 150 W for 4min and centrifuged at 3500 rpm for 10 min to achieve phase separation. After centrifugation, fine droplets of the extractant phase settled to the bottom of the centrifuge tube and were directly injected into the high-performance liquid chromatography system for analysis. The quantity of [C(6)MIM]Cl, the molar ratio of [C(6)MIM]Cl and LiNTf(2), ionic strength, ultrasound time, and centrifugation time, were optimized using a Plackett-Burman design. Significant factors obtained were optimized by employing a central composite design. The optimized technique provides good repeatability (RSD 2.4 to 3.5%), linearity (0.5 μg/L to 500 μg/L), low LODs (0.06 μg/L to 0.08 μg/L) and great enrichment factor (244 to 268). The developed method can be applied in routine analysis for the determining of phenylurea pesticides in environmental samples.

  14. A new dispersive liquid-liquid microextraction using ionic liquid based microemulsion coupled with cloud point extraction for determination of copper in serum and water samples.

    Science.gov (United States)

    Arain, Salma Aslam; Kazi, Tasneem Gul; Afridi, Hassan Imran; Arain, Mariam Shahzadi; Panhwar, Abdul Haleem; Khan, Naeemullah; Baig, Jameel Ahmed; Shah, Faheem

    2016-04-01

    A simple and rapid dispersive liquid-liquid microextraction procedure based on ionic liquid assisted microemulsion (IL-µE-DLLME) combined with cloud point extraction has been developed for preconcentration copper (Cu(2+)) in drinking water and serum samples of adolescent female hepatitits C (HCV) patients. In this method a ternary system was developed to form microemulsion (µE) by phase inversion method (PIM), using ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and nonionic surfactant, TX-100 (as a stabilizer in aqueous media). The Ionic liquid microemulsion (IL-µE) was evaluated through visual assessment, optical light microscope and spectrophotometrically. The Cu(2+) in real water and aqueous acid digested serum samples were complexed with 8-hydroxyquinoline (oxine) and extracted into IL-µE medium. The phase separation of stable IL-µE was carried out by the micellar cloud point extraction approach. The influence of of different parameters such as pH, oxine concentration, centrifugation time and rate were investigated. At optimized experimental conditions, the limit of detection and enhancement factor were found to be 0.132 µg/L and 70 respectively, with relative standard deviation <5%. In order to validate the developed method, certified reference materials (SLRS-4 Riverine water) and human serum (Sero-M10181) were analyzed. The resulting data indicated a non-significant difference in obtained and certified values of Cu(2+). The developed procedure was successfully applied for the preconcentration and determination of trace levels of Cu(2+) in environmental and biological samples.

  15. Sensitive determination of sertraline by capillary electrophoresis with dispersive liquid-liquid microextraction and field-amplified sample stacking.

    Science.gov (United States)

    Huang, Shiou-Wen; Hsieh, Ming-Mu; Chang, Sarah Y

    2012-11-15

    A novel method for the determination of sertraline using dispersive liquid-liquid microextraction (DLLME) coupled with capillary electrophoresis (CE) was developed. Acetone and dichloromethane were used as the disperser solvent and extraction solvent, respectively. A mixture of the extraction and disperser solvents was rapidly injected into a 1.0 mL aqueous sample to form a cloudy solution. After the extraction, sertraline was analyzed using CE that was equipped with UV detection. A 74-fold improvement in the sensitivity was observed when DLLME was used to extract sertraline. Since the DLLME extract residue was redissolved with 5 μL of water that contained 20% methanol, the detection sensitivity was further enhanced through the use of field-amplified sample stacking (FASS). A 11-fold improvement in the sensitivity was obtained when FASS was used to on-line concentrate sertraline. Under optimal extraction and stacking conditions, the calibration curve, which ranged from 0.01 to 1 μM was observed to be linear. The limit of detection (LOD) at a signal-to-noise ratio of 3 was 2.5 nM for sertraline. An approximately 814-fold improvement in the sensitivity was observed for sertraline compare with injection of standard solution without the DLLME and FASS procedures. This developed method was successfully applied to the determination of sertraline in human urine samples.

  16. Determination of parabens in beverage samples by dispersive liquid-liquid microextraction based on solidification of floating organic droplet.

    Science.gov (United States)

    Hou, Fang; Deng, Xiaoying; Jiang, Xinyu; Yu, Jingang

    2014-01-01

    A simple and efficient method for dispersive liquid-liquid microextraction of methylparaben, ethylparaben, propylparaben and butylparaben in real beverage samples was developed. It is making use of solidified floating organic droplets of 1-dodecanol which has low density and a proper melting point. Parameters influencing the extraction efficiency, such as the type of extraction and dispersive solvent, the volume of extraction and dispersive solvent, salt effect, pH, extraction time, were optimized and resulted in enrichment factors (EFs) of 84 for methylparaben, 103 for ethylparaben, 115 for propylparaben and 126 for butylparaben. The limits of detection for parabens were 1.52, 1.06, 0.32 and 0.17 ng/mL, respectively. Excellent linearity with coefficients of correlation from 0.9970 to 0.9997 was observed in the concentration range of 5-1,000 ng/mL. The repeatability of the proposed method expressed as relative standard deviations (RSDs) ranged from 2.54 to 3.89% (n = 5). The relative recoveries for parabens in beverage samples were good and in the ranges of 89.8-109.9, 90.2-107.3, 90.9-101.7 and 92.3-118.1%, respectively. Thus, the proposed method has excellent potential for the determination of parabens in beverage samples. © The Author [2013]. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  17. Dispersive Liquid-Liquid Microextraction of Bismuth in Various Samples and Determination by Flame Atomic Absorption Spectrometry

    Directory of Open Access Journals (Sweden)

    Teslima Daşbaşı

    2016-01-01

    Full Text Available A dispersive liquid-liquid microextraction method for the determination of bismuth in various samples by flame atomic absorption spectrometry is described. In this method, crystal violet was used as counter positive ion for BiCl4- complex ion, chloroform as extraction solvent, and ethanol as disperser solvent. The analytical parameters that may affect the extraction efficiency like acidity of sample, type and amount of extraction and disperser solvents, amount of ligand, and extraction time were studied in detail. The effect of interfering ions on the analyte recovery was also investigated. The calibration graph was linear in the range of 0.040–1.00 mg L−1 with detection limit of 4.0 μg L−1 (n=13. The precision as relative standard deviation was 3% (n=11, 0.20 mg L−1 and the enrichment factor was 74. The developed method was applied successfully for the determination of bismuth in various water, pharmaceutical, and cosmetic samples and the certified reference material (TMDA-64 lake water.

  18. DETERMINATION OF CHLOROPHENOLS, NITROPHENOLS, AND METHYLPHENOLS IN GROUND-WATER SAMPLES USING HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

    Science.gov (United States)

    A high performance liquid chromatography (HPLC) method was developed to quantitatively determine phenolic compounds and their isomers in aqueous samples. The HPLC method can analyze a mixture of 15 contaminants in the same analytical run with an analysis time of 25 minutes. The...

  19. Dispersive liquid-liquid microextraction for metals enrichment: a useful strategy for improving sensitivity of laser-induced breakdown spectroscopy in liquid samples analysis.

    Science.gov (United States)

    Aguirre, M A; Selva, E J; Hidalgo, M; Canals, A

    2015-01-01

    A rapid and efficient Dispersive Liquid-Liquid Microextraction (DLLME) followed by Laser-Induced Breakdown Spectroscopy detection (LIBS) was evaluated for simultaneous determination of Cr, Cu, Mn, Ni and Zn in water samples. Metals in the samples were extracted with tetrachloromethane as pyrrolidinedithiocarbamate (APDC) complexes, using vortex agitation to achieve dispersion of the extractant solvent. Several DLLME experimental factors affecting extraction efficiency were optimized with a multivariate approach. Under optimum DLLME conditions, DLLME-LIBS method was found to be of about 4.0-5.5 times more sensitive than LIBS, achieving limits of detection of about 3.7-5.6 times lower. To assess accuracy of the proposed DLLME-LIBS procedure, a certified reference material of estuarine water was analyzed.

  20. Ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction combined with electrothermal atomic absorption spectrometry for a sensitive determination of cadmium in water samples

    Energy Technology Data Exchange (ETDEWEB)

    Li Shengqing [Department of Chemistry, College of Science, Huazhong Agricultural University, Wuhan 430070 (China); Supervision, Inspection and Testing Center of Microbial Products Quality (Wuhan), Ministry of Agriculture (China)], E-mail: sqingli@mail.hzau.edu.cn; Cai Shun; Hu Wei [Department of Chemistry, College of Science, Huazhong Agricultural University, Wuhan 430070 (China); Chen Hao [Department of Chemistry, College of Science, Huazhong Agricultural University, Wuhan 430070 (China)], E-mail: hchenhao@mail.hzau.edu.cn; Liu Hanlan [Department of Chemistry, College of Science, Huazhong Agricultural University, Wuhan 430070 (China)

    2009-07-15

    A new method was developed for the determination of cadmium in water samples using ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (IL-based USA-DLLME) followed by electrothermal atomic absorption spectrometry (ETAAS). The IL-based USA-DLLME procedure is free of volatile organic solvents, and there is no need for a dispersive solvent, in contrast to conventional DLLME. The ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate (HMIMPF{sub 6}), was quickly disrupted by an ultrasonic probe for 1 min and dispersed in water samples like a cloud. At this stage, a hydrophobic cadmium-DDTC complex was formed and extracted into the fine droplets of HMIMPF{sub 6}. After centrifugation, the concentration of the enriched cadmium in the sedimented phase was determined by ETAAS. Some effective parameters of the complex formation and microextraction, such as the concentration of the chelating agent, the pH, the volume of the extraction solvent, the extraction time, and the salt effect, have been optimized. Under optimal conditions, a high extraction efficiency and selectivity were reached for the extraction of 1.0 ng of cadmium in 10.0 mL of water solution employing 73 {mu}L of HMIMPF{sub 6} as the extraction solvent. The enrichment factor of the method is 67. The detection limit was 7.4 ng L{sup - 1}, and the characteristic mass (m{sub 0}, 0.0044 absorbance) of the proposed method was 0.02 pg for cadmium (Cd). The relative standard deviation (RSD) for 11 replicates of 50 ng L{sup - 1} Cd was 3.3%. The method was applied to the analysis of tap, well, river, and lake water samples and the Environmental Water Reference Material GSBZ 50009-88 (200921). The recoveries of spiked samples were in the range of 87.2-106%.

  1. Ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction combined with electrothermal atomic absorption spectrometry for a sensitive determination of cadmium in water samples

    Science.gov (United States)

    Li, Shengqing; Cai, Shun; Hu, Wei; Chen, Hao; Liu, Hanlan

    2009-07-01

    A new method was developed for the determination of cadmium in water samples using ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (IL-based USA-DLLME) followed by electrothermal atomic absorption spectrometry (ETAAS). The IL-based USA-DLLME procedure is free of volatile organic solvents, and there is no need for a dispersive solvent, in contrast to conventional DLLME. The ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate (HMIMPF 6), was quickly disrupted by an ultrasonic probe for 1 min and dispersed in water samples like a cloud. At this stage, a hydrophobic cadmium-DDTC complex was formed and extracted into the fine droplets of HMIMPF 6. After centrifugation, the concentration of the enriched cadmium in the sedimented phase was determined by ETAAS. Some effective parameters of the complex formation and microextraction, such as the concentration of the chelating agent, the pH, the volume of the extraction solvent, the extraction time, and the salt effect, have been optimized. Under optimal conditions, a high extraction efficiency and selectivity were reached for the extraction of 1.0 ng of cadmium in 10.0 mL of water solution employing 73 µL of HMIMPF 6 as the extraction solvent. The enrichment factor of the method is 67. The detection limit was 7.4 ng L - 1 , and the characteristic mass ( m0, 0.0044 absorbance) of the proposed method was 0.02 pg for cadmium (Cd). The relative standard deviation (RSD) for 11 replicates of 50 ng L - 1 Cd was 3.3%. The method was applied to the analysis of tap, well, river, and lake water samples and the Environmental Water Reference Material GSBZ 50009-88 (200921). The recoveries of spiked samples were in the range of 87.2-106%.

  2. Modified ionic liquid cold-induced aggregation dispersive liquid-liquid microextraction combined with spectrofluorimetry for trace determination of ofloxacin in pharmaceutical and biological samples

    Science.gov (United States)

    Zeeb, M.; Ganjali, M.R.; Norouzi, P.

    2011-01-01

    Background and the purpose of the study Ofloxacin is a quinolone synthetic antibiotic, which acts against resistant mutants of bacteria by inhibiting DNA gyrase. This antibacterial agent is widely used in the treatment of respiratory tract, urinary tract and tissue-based infections, which are caused by Gram-positive and Gram-negative bacteria. In this work, an efficient modified ionic liquid cold-induced aggregation dispersive liquid-liquid microextraction (M-IL-CIA-DLLME) was combined with spectrofluorimetry for trace determination of ofloxacin in real samples. Methods In this microextraction method, hydrophobic 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim] [PF6]) ionic liquid (IL) as a microextraction solvent was dispersed into a heated sample solution containing sodium hexafluorophosphate (NaPF6) (as a common ion) and the analyte of interest. Afterwards, the resultant solution was cooled in an ice-water bath and a cloudy condition was formed due to a considerable decrease of IL solubility. After centrifuging, the enriched phase was introduced to the spectrofluorimeter for the determination of ofloxacin. Results and major conclusion In this technique, the performance of the microextraction method was not influenced by variations in the ionic strength of the sample solution (up to 30% w/v). Furthermore, [Hmim][PF6] IL was chosen as a green microextraction phase and an alternative to traditional toxic organic solvents. Different parameters affecting the analytical performance were studied and optimized. At optimum conditions, a relatively broad linear dynamic range of 0.15-125 µg l-1 and a limit of detection (LOD) of 0.029 µg l-1 were obtained. The relative standard deviation (R.S.D.) obtained for the determination of five replicates of the 10 ml solution containing 50 µg l-1 ofloxacin was 2.7%. Finally, the combined methodology was successfully applied to ofloxacin determination in actual pharmaceutical formulations and biological samples. PMID

  3. Modified Ionic Liquid Cold-Induced Aggregation Dispersive Liquid-Liquid Microextraction Combined with Spectrofluorimetry for Trace Determination of Ofloxacin in Pharmaceutical and Biological Samples

    Directory of Open Access Journals (Sweden)

    P. Norouzi

    2011-12-01

    Full Text Available Background and the purpose of the study: Ofloxacin is a quinolone synthetic antibiotic, which acts against resistant mutants of bacteria by inhibiting DNA gyrase. This antibacterial agent is widely used in the treatment of respiratory tract, urinary tract and tissue-based infections, which are caused by Gram-positive and Gram-negative bacteria. In this work, an efficient modified ionic liquid cold-induced aggregation dispersive liquid-liquid microextraction (M-IL-CIA-DLLME was combined with spectrofluorimetry for trace determination of ofloxacin in real samples.Methods: In this microextraction method, hydrophobic 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim] [PF6] ionic liquid (IL as a microextraction solvent was dispersed into a heated sample solution containing sodium hexafluorophosphate (NaPF6 (as a common ion and the analyte of interest. Afterwards, the resultant solution was cooled in an ice-water bath and a cloudy condition was formed due to a considerable decrease of IL solubility. After centrifuging, the enriched phase was introduced to the spectrofluorimeter for the determination of ofloxacin.Results and major conclusion: In this technique, the performance of the microextraction method was not influenced by variations in the ionic strength of the sample solution (up to 30% w/v. Furthermore, [Hmim][PF6] IL was chosen as a green microextraction phase and an alternative to traditional toxic organic solvents. Different parameters affecting the analytical performance were studied and optimized. At optimum conditions, a relatively broad linear dynamic range of 0.15-125 μg l-1 and a limit of detection (LOD of 0.029 μg l-1 were obtained. The relative standard deviation (R.S.D. obtained for the determination of five replicates of the 10 ml solution containing 50 μg l-1 ofloxacin was 2.7%. Finally, the combined methodology was successfully applied to ofloxacin determination in actual pharmaceutical formulations and biological samples.

  4. Determination of metal ions in tea samples using task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction coupled to liquid chromatography with ultraviolet detection.

    Science.gov (United States)

    Werner, Justyna

    2016-04-01

    Task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction was used for the preconcentration of cadmium(II), cobalt(II), and lead(II) ions in tea samples, which were subsequently analyzed by liquid chromatography with UV detection. The proposed method of preconcentration is free of volatile organic compounds, which are often used as extractants and dispersing solvents in classic techniques of microextraction. A task-specific ionic liquid trioctylmethylammonium thiosalicylate was used as an extractant and a chelating agent. Ultrasound was used to disperse the ionic liquid. After microextraction, the phases were separated by centrifugation, and the ionic liquid phase was solubilized in methanol and directly injected into the liquid chromatograph. Selected microextraction parameters, such as the volume of ionic liquid, the pH of the sample, the duration of ultrasound treatment, the speed and time of centrifugation, and the effect of ionic strength, were optimized. Under optimal conditions an enrichment factor of 200 was obtained for each analyte. The limits of detection were 0.002 mg/kg for Cd(II), 0.009 mg/kg for Co(II), and 0.013 mg/kg for Pb(II). The accuracy of the proposed method was evaluated by an analysis of the Certified Reference Materials (INCT-TL-1, INCT-MPH-2) with the recovery values in the range of 90-104%.

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

    Science.gov (United States)

    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.

  6. Automated dispersive liquid-liquid microextraction coupled to high performance liquid chromatography - cold vapour atomic fluorescence spectroscopy for the determination of mercury species in natural water samples.

    Science.gov (United States)

    Liu, Yao-Min; Zhang, Feng-Ping; Jiao, Bao-Yu; Rao, Jin-Yu; Leng, Geng

    2017-04-14

    An automated, home-constructed, and low cost dispersive liquid-liquid microextraction (DLLME) device that directly coupled to a high performance liquid chromatography (HPLC) - cold vapour atomic fluorescence spectroscopy (CVAFS) system was designed and developed for the determination of trace concentrations of methylmercury (MeHg(+)), ethylmercury (EtHg(+)) and inorganic mercury (Hg(2+)) in natural waters. With a simple, miniaturized and efficient automated DLLME system, nanogram amounts of these mercury species were extracted from natural water samples and injected into a hyphenated HPLC-CVAFS for quantification. The complete analytical procedure, including chelation, extraction, phase separation, collection and injection of the extracts, as well as HPLC-CVAFS quantification, was automated. Key parameters, such as the type and volume of the chelation, extraction and dispersive solvent, aspiration speed, sample pH, salt effect and matrix effect, were thoroughly investigated. Under the optimum conditions, linear range was 10-1200ngL(-1) for EtHg(+) and 5-450ngL(-1) for MeHg(+) and Hg(2+). Limits of detection were 3.0ngL(-1) for EtHg(+) and 1.5ngL(-1) for MeHg(+) and Hg(2+). Reproducibility and recoveries were assessed by spiking three natural water samples with different Hg concentrations, giving recoveries from 88.4-96.1%, and relative standard deviations <5.1%.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jia Xiaoyu; Han Yi; Liu Xinli [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Duan Taicheng, E-mail: tcduan@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China); Chen Hangting, E-mail: htchen@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022 (China)

    2011-01-15

    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{sup +}) and mercury (Hg{sup 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{sup +} and Hg{sup 2+} were obtained from only 5.00 mL sample solution. The detection limits of the analytes (as Hg) were 0.0076 ng mL{sup -1} for MeHg{sup +} and 0.0014 ng mL{sup -1} for Hg{sup 2+}, respectively. The relative standard deviations for ten replicate measurements of 0.5 ng mL{sup -1} MeHg{sup +} and Hg{sup 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.

  8. Vortex-assisted low density solvent based demulsified dispersive liquid-liquid microextraction and high-performance liquid chromatography for the determination of organophosphorus pesticides in water samples.

    Science.gov (United States)

    Seebunrueng, Ketsarin; Santaladchaiyakit, Yanawath; Srijaranai, Supalax

    2014-05-01

    A simple, rapid, effective and eco-friendly preconcentration method, vortex-assisted low density solvent based solvent demulsified dispersive liquid-liquid microextraction (VLDS-SD-DLLME), followed by high performance liquid chromatography-diode array detector (HPLC-DAD) analysis, has been developed for the first time for the determination of four organophosphorus pesticides (OPPs) (e.g., azinphos-methyl, parathion-methyl, fenitrothion and diazinon) in environmental water samples. In this preconcentration procedure, an emulsion was obtained after the mixture of extraction solvent (1-dodecanol) and dispersive solvent (acetonitrile, ACN) was injected rapidly into 10 mL of the sample solution. The vortex agitator aided the dispersion of the extraction solvent into the sample solution. After the formation of an emulsion, the demulsifier (ACN) was added, resulting in the rapid separation of the mixture into two phases without centrifugation. Under optimal conditions, the proposed method provided high extraction efficiency (90-99%), good linearity range (0.5-500 ng mL(-1)), low limits of detection (0.25-1 ng mL(-1)) and good repeatability and recoveries were obtained.

  9. Rapid extraction and determination of amphetamines in human urine samples using dispersive liquid-liquid microextraction and solidification of floating organic drop followed by high performance liquid chromatography.

    Science.gov (United States)

    Ahmadi-Jouibari, Toraj; Fattahi, Nazir; Shamsipur, Mojtaba

    2014-06-01

    A novel, rapid, simple and sensitive dispersive liquid-liquid microextraction method based on the solidification of floating organic drop (DLLME-SFO) combined with high-performance liquid chromatography-ultraviolet detection (HPLC-UV) was used to determine amphetamine and methamphetamine in urine samples. The factors affecting the extraction efficiency of DLLME-SFO such as the kind and volume of the extraction and the disperser solvents, effect of concentration of K2CO3 and extraction time were investigated and the optimal extraction conditions were established. Under the optimum conditions (extraction solvent: 30.0μl 1-undecanol; disperser solvent: 300μl acetonitrile; buffer concentration: 2% (w/v) K2CO3 and extraction time: 1min), calibration curves are linear in the range of 10-3000μgl(-1) and limit of detections (LODs) are in the range of 2-8μgl(-1). The relative standard deviations (RSDs) for 100μgl(-1) of amphetamine and methamphetamine in diluted urine are in the range of 6.2-7.8% (n=7). The method was successfully applied for the determination of amphetamine and methamphetamine in the actual urine samples. The relative recoveries of urine samples spiked with amphetamine and methamphetamine are 87.8-113.2%. The obtained results show that DLLME-SFO combined with HPLC-UV is a fast and simple method for the determination of amphetamine and methamphetamine in urine.

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

    Directory of Open Access Journals (Sweden)

    Haiying Luo

    2014-01-01

    Full Text Available 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.

  11. A multiclass method for the analysis of endocrine disrupting chemicals in human urine samples. Sample treatment by dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Vela-Soria, F; Ballesteros, O; Zafra-Gómez, A; Ballesteros, L; Navalón, A

    2014-11-01

    The population is continuously exposed to endocrine disrupting chemicals (EDCs). This has influenced an increase in diseases and syndromes that are more frequent nowadays. Therefore, it is necessary to develop new analytical procedures to evaluate the exposure with the ultimate objective of establishing, in an accurate way, relationships between EDCs and harmful health effects. In the present work, a new method based on a sample treatment by dispersive liquid-liquid microextraction (DLLME) for the extraction of six parabens (methyl-, ethyl-, isopropyl-, propyl-, isobutyl and butylparaben), six benzophenones (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-6, benzophenone-8 and 4-hydroxybenzophenone) and two bisphenols (bisphenol A and bisphenol S) in human urine samples, followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis is proposed. An enzymatic treatment allows determining the total content of the target EDCs. The extraction parameters were accurately optimized using multivariate optimization strategies. Ethylparaben ring-(13)C6 and bisphenol A-d16 were used as surrogates. Found limits of quantification ranging from 0.2 to 0.5 ng mL(-1) and inter-day variability (evaluated as relative standard deviation) ranging from 2.0% to 14.9%. The method was validated using matrix-matched standard calibration followed by a recovery assay with spiked samples. Recovery rates ranged from 94% to 105%. A good linearity, for concentrations up to 300 ng mL(-1) for parabens and 40 ng mL(-1) for benzophenones and bisphenols, respectively, was obtained. The method was satisfactorily applied for the determination of target compounds in human urine samples from 20 randomly selected individuals.

  12. Newly developed liquid-based cytology. TACAS™: cytological appearance and HPV testing using liquid-based sample.

    Science.gov (United States)

    Kubushiro, Kaneyuki; Taoka, Hideki; Sakurai, Nobuyuki; Yamamoto, Yasuhiro; Kurasaki, Akiko; Asakawa, Yasuyuki; Iwahara, Minoru; Takahashi, Kei

    2011-09-01

    Cell profiles determined by the thin-layer advanced cytology assay system (TACAS™), a liquid-based cytology technique newly developed in Japan, were analyzed in this study. Hybrid capture 2 (HC-2) was also performed using the liquid-based samples prepared by TACAS to ascertain its ability to detect human papillomavirus (HPV). Cell collection samples from uterine cervix were obtained from 359 patients and examined cytologically. A HC-2 assay for HPV was carried out in the cell specimens. All specimens were found to show background factors such as leukocytes. After excluding the 5 unsatisfactory cases from the total 354 cases, 82 cases (23.2%) were positive and 272 cases (76.8%) were negative for HPV. Cell specimens from 30 HPV-positive cases and 166 HPV-negative cases were subjected to 4 weeks of preservation at room temperature. Then, when subsequently re-assayed, 28 cases (93.3%) in the former group were found to be HPV positive and 164 cases (98.8%) in the latter group were found to be HPV negative. These results supported the excellent reproducibility of TACAS for HPV testing. A reasonable inference from the foregoing analysis is that TACAS may be distinguished from other liquid-based cytological approaches, such as ThinPrep and SurePath, in that it can retain the cell backgrounds. Furthermore, this study raises the possibility that cell specimens prepared using TACAS could be preserved for at least 4 weeks prior to carrying out a HC-2 assay for HPV.

  13. A novel vortex-assisted liquid-liquid microextraction approach using auxiliary solvent: Determination of iodide in mineral water samples.

    Science.gov (United States)

    Zaruba, Serhii; Vishnikin, Andriy B; Andruch, Vasil

    2016-01-01

    A novel vortex-assisted liquid-liquid microextraction (VA-LLME) for determination of iodide was developed. The method includes the oxidation of iodide with iodate in the presence of hydrochloric acid followed by VA-LLME of the ion-pair formed between ICl2(-) and Astra Phloxine reagent (AP) and subsequent absorbance measurement at 555nm. The appropriate experimental conditions were investigated and found to be: 5mL of sample, 0.27molL(-)(1) HCl, 0.027mmolL(-1) KIO3 as the oxidation agent, 250μL of extraction mixture containing amyl acetate as the extraction solvent and carbon tetrachloride as the auxiliary solvent (1:1, v/v), 0.04mmolL(-1) AP reagent, vortex time: 20s at 3000rpm, centrifugation: 4min at 3000rpm. The calibration plot was linear in the range 16.9-169μg L(-1) of iodide, with a correlation coefficient (R(2)) of 0.996, and the relative standard deviation ranged from 1.9 to 5.7%. The limit of detection (LOD) and limit of quantification (LOQ) were 1.75 and 6.01μgL(-)(1) of iodide, respectively. The suggested procedure was applied for determination of iodide in real mineral water samples.

  14. Dispersive liquid-liquid microextraction for four phenolic environmental estrogens in water samples followed by determination using capillary electrophoresis.

    Science.gov (United States)

    Liu, Junying; Lu, Wenhui; Liu, Huitao; Wu, Xiaqing; Li, Jinhua; Chen, Lingxin

    2016-10-01

    Dispersive liquid-liquid microextraction (DLLME) coupled with CE was successfully developed for simultaneous determination of four types of phenolic environmental estrogens (PEEs), namely hexestrol (HS), bisphenol A (BPA), diethylstilbestrol (DES) and dienestrol (DS). Several parameters affecting DLLME and CE conditions were systematically investigated including the type and volume of extraction solvent and dispersive solvent, extraction time, salt, pH value, surfactant, buffer solution and so on. Under the optimal conditions, DLLME-CE exhibited strong enrichment ability, presenting high enrichment factors of 467, 241, 367 and 362 for HS, BPA, DES and DS, respectively, as well as low detection limits of 0.3, 0.6, 0.6 and 0.3 μg/L, respectively. Excellent linearity was achieved in the range of 2.0-150 μg/L for HS and DS, and 4.0-300 μg/L for BPA and DES, with correlation coefficients R>0.9983. Recoveries ranging from 70.4 to 108.1% were obtained with tap water, lake water and seawater samples spiked at three concentration levels and the relative standard deviations (RSDs, for n = 5) were 2.1-9.7%. This DLLME-CE method with high selectivity and sensitivity, high stability, simplicity, cost-effectiveness, eco-friendliness was proved potentially applicable for the rapid and simultaneous determination of PEEs in complicated water samples.

  15. Rapid spectrophotometric determination of trace amounts of palladium in water samples after dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Rahnama Kozani, Reyhaneh; Mofid-Nakhaei, Jamshid; Jamali, Mohammad Reza

    2013-08-01

    A simple, rapid, and efficient dispersive liquid-liquid microextraction method, followed by UV-Vis spectrophotometry was developed for the preconcentration and determination of Pd ions in water samples. Pd ions react with α-furildioxime (chelating agent) to form a hydrophobic complex. Various parameters were altered to study and optimize their effects on the extraction efficiency, such as pH, ligand concentration, the type and volume of extraction and dispersive solvents, extraction time, and salt concentration. Under optimized conditions, the method exhibited an enrichment factor (C org/C aq) of 25 and recovery more than 98 % within a very short extraction time. The linearity of the method ranged from 10 to 200 μg L(-1). The limit of detection was 1.1 μg L(-1). The relative standard deviation for the concentration of 100 μg L(-1) of Pd was 2.3 % (n = 10). Finally, the developed method was successfully applied to the extraction and determination of Pd in tap, river, mineral, and sea water samples.

  16. Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid-liquid microextraction and microvolume back-extraction for determination of mercury in water samples.

    Science.gov (United States)

    Fernández, Elena; Vidal, Lorena; Martín-Yerga, Daniel; Blanco, María del Carmen; Canals, Antonio; Costa-García, Agustín

    2015-04-01

    A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid-liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L(-1) was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L(-1), which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L(-1) and 1 µg L(-1), respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L(-1)) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Measurement of (90)Sr in environmental samples by cation-exchange and liquid scintillation counting.

    Science.gov (United States)

    Amano, H; Yanase, N

    1990-06-01

    A new method for the measurement of (90)Sr in environmental samples by cation-exchange and liquid scintillation counting is described. Strontium carbonate is purified by precipitation and ion-exchange, weighed for the determination of chemical yield, dissolved in hydrochloric acid and mixed with the liquid scintillator, Aquasol-2. Two channels of a low-background liquid scintillation counter are used to determine (90)Sr, (90)Y and (89)Sr, free from the effects of environmental tritium. The values of (90)Sr obtained by this method are in good agreement with those from ordinary (90)Y milking and the gas proportional counting method. The concentration of (90)Sr in the air at Tokai-mura in Japan has been measured by the new method.

  18. Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

    Institute of Scientific and Technical Information of China (English)

    Zhi Mei Liu; Xiao Huan Zang; Wei Hua Liu; Chun Wang; Zhi Wang

    2009-01-01

    A novel method for the determination of five carbamate pesticides(metolcarb,carbofuran,carbaryl,isoprocard and diethofencard)in water samples was developed by dispersive liquid-liquid microextraction(DLLME)coupled with high performance liquid chromatography-diode array detector(HPLC-DAD).Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results.Under the optimum conditions for the method,the calibration curve was linear in the concentration range from 5 to I000 ng mL-1 for all the five carbamate pesticides,with the correlation coefficients(r2)varying from 0.9984 to 0.9994.Good enrichment factors were achieved ranging from 80 to 177-fold,depending on the compound.The limits of detection(LODs)(S/N = 3)were ranged from 0.1 to 0.5 ng mL-1.The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

  19. Determination of six pyrethroid insecticides in fruit juice samples using dispersive liquid-liquid microextraction combined with high performance liquid chromatography.

    Science.gov (United States)

    Boonchiangma, Suthasinee; Ngeontae, Wittaya; Srijaranai, Supalax

    2012-01-15

    Dispersive liquid-liquid microextraction (DLLME) coupled to high performance liquid chromatography (HPLC) with UV detection was applied for the determination of six pyrethroids (tetramethrin, fenpropathrin, cypermethrin, deltamethrin, fenvalerate and permethrin) in various fruit juices including apple, red grape, orange, kiwi, passion fruit, pomegranate and guava juice. Six pyrethroids were separated within 30 min using a Waters Atlantis T3 column under an isocratic elution of acetonitrile-water (72:28). The parameters affecting extraction efficiency of the DLLME method such as type of disperser and extraction solvent, volume of disperser and extraction solvent and centrifugation time were investigated. Under the optimum conditions, 5.00 mL of sample solution, 300 μL of chloroform as extraction solvent and 1.25 mL of methanol as dispersive solvent gave high enrichment factor in the range of 62-84. Good linearity was obtained from 2 to 1,500 μg/L (r(2)>0.995). The mean recoveries of the pyrethroids evaluated by fortification of real samples were in the range of 84-94%. The limits of detection ranging from 2 to 5 μg/L are sufficient to analyze pyrethroid residues at the maximum residue limits (MRLs) established by the European Union (EU) in fruit juices. The proposed method can be applied to direct determination of pyrethroid residues in fruit juices.

  20. Automated dynamic hollow fiber liquid-liquid-liquid microextraction combined with capillary electrophoresis for speciation of mercury in biological and environmental samples.

    Science.gov (United States)

    Li, Pingjing; He, Man; Chen, Beibei; Hu, Bin

    2015-10-01

    A simple home-made automatic dynamic hollow fiber based liquid-liquid-liquid microextraction (AD-HF-LLLME) device was designed and constructed for the simultaneous extraction of organomercury and inorganic mercury species with the assistant of a programmable flow injection analyzer. With 18-crown-6 as the complexing reagent, mercury species including methyl-, ethyl-, phenyl- and inorganic mercury were extracted into the organic phase (chlorobenzene), and then back-extracted into the acceptor phase of 0.1% (m/v) 3-mercapto-1-propanesulfonic acid (MPS) aqueous solution. Compared with automatic static (AS)-HF-LLLME system, the extraction equilibrium of target mercury species was obtained in shorter time with higher extraction efficiency in AD-HF-LLLME system. Based on it, a new method of AD-HF-LLLME coupled with large volume sample stacking (LVSS)-capillary electrophoresis (CE)/UV detection was developed for the simultaneous analysis of methyl-, phenyl- and inorganic mercury species in biological samples and environmental water. Under the optimized conditions, AD-HF-LLLME provided high enrichment factors (EFs) of 149-253-fold within relatively short extraction equilibrium time (25min) and good precision with RSD between 3.8 and 8.1%. By combining AD-HF-LLLME with LVSS-CE/UV, EFs were magnified up to 2195-fold and the limits of detection (at S/N=3) for target mercury species were improved to be sub ppb level.

  1. Validation of method for determination of different classes of pesticides in aqueous samples by dispersive liquid-liquid microextraction with liquid chromatography-tandem mass spectrometric detection.

    Science.gov (United States)

    Caldas, Sergiane Souza; Costa, Fabiane Pinho; Primel, Ednei Gilberto

    2010-04-14

    In this study, a simple, rapid and efficient method has been developed for the extraction and preconcentration of different classes of pesticides, carbofuran (insecticide), clomazone (herbicide) and tebuconazole (fungicide) in aqueous samples by dispersive liquid-liquid microextraction (DLLME) coupled with liquid chromatography-tandem mass spectrometric detection. Some experimental parameters that influence the extraction efficiency, such as the type and volume of the disperser solvents and extraction solvents, extraction time, speed of centrifugation, pH and addition of salt were examined and optimized. Under the optimum conditions, the recoveries of pesticides in water at spiking levels between 0.02 and 2.0 microg L(-1) ranged from 62.7% to 120.0%. The relative standard deviations varied between 1.9% and 9.1% (n=3). The limits of quantification of the method considering a 50-fold preconcentration step were 0.02 microg L(-1). The linearity of the method ranged from 1.0 to 1000 microg L(-1) for all compounds, with correlation coefficients varying from 0.9982 to 0.9992. Results show that the method we propose can meet the requirements for the determination of pesticides in water samples. The comparison of this method with solid-phase extraction indicates that DLLME is a simple, fast, and low-cost method for the determination of pesticides in natural waters.

  2. A rapid ultrasound-assisted dispersive liquid-liquid microextraction followed by ultra-performance liquid chromatography for the simultaneous determination of seven benzodiazepines in human plasma samples.

    Science.gov (United States)

    Fernández, Purificación; González, Cristina; Pena, M Teresa; Carro, Antonia M; Lorenzo, Rosa A

    2013-03-12

    A simple and efficient ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) method has been developed for the determination of seven benzodiazepines (alprazolam, bromazepam, clonazepam, diazepam, lorazepam, lormetazepam and tetrazepam) in human plasma samples. Chloroform and methanol were used as extractant and disperser solvents, respectively. The influence of several variables (e.g., type and volume of dispersant and extraction solvents, pH, ultrasonic time and ionic strength) was carefully evaluated and optimized, using an asymmetric screening design 3(2)4(2)//16. Analysis of extracts was performed by ultra-performance liquid chromatography coupled with photodiode array detection (UPLC-PDA). Under the optimum conditions, two reversed-phases, Shield RP18 and C18 columns were successfully tested, obtaining good linearity in a range of 0.01-5μgmL(-1), with correlation coefficients r>0.996. Quantification limits ranged between 4.3-13.2ngmL(-1) and 4.0-14.8ngmL(-1), were obtained for C18 and Shield RP18 columns, respectively. The optimized method exhibited a good precision level, with relative standard deviation values lower than 8%. The recoveries studied at two spiked levels, ranged from 71 to 102% for all considered compounds. The proposed method was successfully applied to the analysis of seven benzodiazepines in real human plasma samples.

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

    Science.gov (United States)

    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 (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.

  4. NMR of bicelles: orientation and mosaic spread of the liquid-crystal director under sample rotation

    Energy Technology Data Exchange (ETDEWEB)

    Zandomeneghi, Giorgia; Tomaselli, Marco; Williamson, Philip T.F.; Meier, Beat H. [Physical Chemistry, ETH Zurich, ETH-Hoenggerberg (Switzerland)], E-mail: beme@ethz.ch

    2003-02-15

    Model-membrane systems composed of liquid-crystalline bicellar phases can be uniaxially oriented with respect to a magnetic field, thereby facilitating structural and dynamics studies of membrane-associated proteins. Here we quantitatively characterize a method that allows the manipulation of the direction of this uniaxial orientation. Bicelles formed from DMPC/DHPC are examined by {sup 31}P NMR under variable-angle sample-spinning (VAS) conditions, confirming that the orientation of the liquid-crystalline director can be influenced by sample spinning. The director is perpendicular to the rotation axis when {theta} (the angle between the sample-spinning axis and the magnetic field direction) is smaller than the magic angle, and is parallel to the rotation axis when {theta} is larger than the magic angle. The new {sup 31}P NMR VAS data presented are considerably more sensitive to the orientation of the bicelle than earlier {sup 2}H studies and the analysis of the sideband pattern allows the determination of the orientation of the liquid-crystal director and its variation over the sample, i.e., the mosaic spread. Under VAS, the mosaic spread is small if {theta} deviates significantly from the magic angle but becomes very large at the magic angle.

  5. Determination of extremely low (236)U/(238)U isotope ratios in environmental samples by sector-field inductively coupled plasma mass spectrometry using high-efficiency sample introduction.

    Science.gov (United States)

    Boulyga, Sergei F; Heumann, Klaus G

    2006-01-01

    A method by inductively coupled plasma mass spectrometry (ICP-MS) was developed which allows the measurement of (236)U at concentration ranges down to 3 x 10(-14)g g(-1) and extremely low (236)U/(238)U isotope ratios in soil samples of 10(-7). By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5,000 counts fg(-1) uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH(+)/U(+) down to a level of 10(-6). An abundance sensitivity of 3 x 10(-7) was observed for (236)U/(238)U isotope ratio measurements at mass resolution 4000. The detection limit for (236)U and the lowest detectable (236)U/(238)U isotope ratio were improved by more than two orders of magnitude compared with corresponding values by alpha spectrometry. Determination of uranium in soil samples collected in the vicinity of Chernobyl nuclear power plant (NPP) resulted in that the (236)U/(238)U isotope ratio is a much more sensitive and accurate marker for environmental contamination by spent uranium in comparison to the (235)U/(238)U isotope ratio. The ICP-MS technique allowed for the first time detection of irradiated uranium in soil samples even at distances more than 200 km to the north of Chernobyl NPP (Mogilev region). The concentration of (236)U in the upper 0-10 cm soil layers varied from 2 x 10(-9)g g(-1) within radioactive spots close to the Chernobyl NPP to 3 x 10(-13)g g(-1) on a sampling site located by >200 km from Chernobyl.

  6. Optimized measurement of radium-226 concentration in liquid samples with radon-222 emanation.

    Science.gov (United States)

    Perrier, Frédéric; Aupiais, Jean; Girault, Frédéric; Przylibski, Tadeusz A; Bouquerel, Hélène

    2016-06-01

    Measuring radium-226 concentration in liquid samples using radon-222 emanation remains competitive with techniques such as liquid scintillation, alpha or mass spectrometry. Indeed, we show that high-precision can be obtained without air circulation, using an optimal air to liquid volume ratio and moderate heating. Cost-effective and efficient measurement of radon concentration is achieved by scintillation flasks and sufficiently long counting times for signal and background. More than 400 such measurements were performed, including 39 dilution experiments, a successful blind measurement of six reference test solutions, and more than 110 repeated measurements. Under optimal conditions, uncertainties reach 5% for an activity concentration of 100 mBq L(-1) and 10% for 10 mBq L(-1). While the theoretical detection limit predicted by Monte Carlo simulation is around 3 mBq L(-1), a conservative experimental estimate is rather 5 mBq L(-1), corresponding to 0.14 fg g(-1). The method was applied to 47 natural waters, 51 commercial waters, and 17 wine samples, illustrating that it could be an option for liquids that cannot be easily measured by other methods. Counting of scintillation flasks can be done in remote locations in absence of electricity supply, using a solar panel. Thus, this portable method, which has demonstrated sufficient accuracy for numerous natural liquids, could be useful in geological and environmental problems, with the additional benefit that it can be applied in isolated locations and in circumstances when samples cannot be transported.

  7. Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products.

    Science.gov (United States)

    Boulyga, Sergei F; Heilmann, Jens; Heumann, Klaus G

    2005-08-01

    Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different 34S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured 34S/32S isotope ratio of the isotope-diluted sample remained constant-a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 microg g(-1) ('sulfur-free' premium gasoline) to 10.4 mg g(-1) (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 microg g(-1) and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level.

  8. Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, Sergei F.; Heilmann, Jens; Heumann, Klaus G. [Johannes Gutenberg-University Mainz (Germany). Institute of Inorganic Chemistry and Analytical Chemistry

    2005-08-01

    Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different {sup 34}S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured {sup 34}S/{sup 32}S isotope ratio of the isotope-diluted sample remained constant - a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 {mu}g g{sup -1} ('sulfur-free' premium gasoline) to 10.4 mg g{sup -1} (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 {mu}g g{sup -1} and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level. (orig.)

  9. Rapid determination of atrazine in environmental water samples by a novel liquid phase microextraction

    Institute of Scientific and Technical Information of China (English)

    Qing Xiang Zhou; Guo Hong Xie; Long Pang

    2008-01-01

    A novel method was described for the rapid determination of atrazine using dispersive liquid phase microextraction incombination with high performance liquid chromatography (HPLC). Possible impact parameters such as sample pH, extraction anddisperser solvents, salting-out effect, and extraction time were investigated. The experimental results indicated that proposedmethod possessed an excellent analytical performance. The linear range, detection limit, and precision (R.S.D.) were 0.1-50 ng mL-1 (R2 = 0.9955), 0.601 ng mL-1 and 6.4%, respectively. The proposed method was validated with the real water samples,and the spiked recoveries were in the range of 69.9-89.8%, respectively. These results indicated that the established method withhigh enrichment factor, short extraction time was an excellent alternative for the routine analysis of atrazine in environmentalsamples.

  10. A Hydrogel's Formation Device for Quick Analysis of Liquid Samples Using Laser-Induced Breakdown Spectroscopy

    Science.gov (United States)

    Guo, Guangmeng; Wang, Jie; Bian, Fang; Tian, Di; Fan, Qingwen

    2016-06-01

    The laser-induced breakdown spectroscopy technique has irreplaceable advantages in the field of detection due to its multi-phase specimen detection ability. The development of the LIBS technique for liquid analysis is obstructed by its inherent drawbacks like the surface ripples and extinction of emitted intensity, which make it unpractical. In this work, an in-situ hydrogel formation sampling device was designed and used the hydrogel as the detection phase of LIBS for Cu, Cr and Al in an aqueous solution. With the measured amount of resin placed in the device, the formed hydrogel could be obtained within 20 s after putting the device into water solution. The formed hydrogel could be directly analyzed by LIBS and reflect the elemental information of the water sample. The prominent performance made this hydrogel's formation device especially suitable for quick in-situ environmental liquid analysis using LIBS.

  11. Estrogens determination in wastewater samples by automatic in-syringe dispersive liquid-liquid microextraction prior silylation and gas chromatography.

    Science.gov (United States)

    González, Alba; Avivar, Jessica; Cerdà, Víctor

    2015-09-25

    A new procedure for the extraction, preconcentration and simultaneous determination of the estrogens most used in contraception pharmaceuticals (estrone, 17β-estradiol, estriol, and 17α-ethynylestradiol), cataloged as Contaminants of Emergent Concern by the Environmental Protection Agency of the United States (US-EPA), is proposed. The developed system performs an in-syringe magnetic stirring-assisted dispersive liquid-liquid microextraction (in-syringe-MSA-DLLME) prior derivatization and gas chromatography (GC-MS). Different extraction (carbon tetrachloride, ethyl acetate, chloroform and trichloroethylene) and disperser solvents (acetone, acetonitrile and methanol) were tested. Chloroform and acetone were chosen as extraction and disperser solvent, respectively, as they provided the best extraction efficiency. Then, a multivariate optimization of the extraction conditions was carried out. Derivatization conditions were also studied to ensure the conversion of the estrogens to their respective trimethylsilyl derivatives. Low LODs and LOQs were achieved, i.e. between 11 and 82ngL(-1), and 37 and 272ngL(-1), respectively. Good values for intra and inter-day precision were obtained (RSDs≤7.06% and RSD≤7.11%, respectively). The method was successfully applied to wastewater samples.

  12. Determination of artificial sweeteners in sewage sludge samples using pressurised liquid extraction and liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Ordoñez, Edgar Y; Quintana, José Benito; Rodil, Rosario; Cela, Rafael

    2013-12-13

    An analytical method for the determination of six artificial sweeteners in sewage sludge has been developed. The procedure is based on pressurised liquid extraction (PLE) with water followed by solid-phase extraction (SPE) and subsequent liquid chromatography-tandem mass spectrometry analysis. After optimisation of the different PLE parameters, extraction with aqueous 500mM formate buffer (pH 3.5) at 80°C during a single static cycle of 21min proved to be best conditions. After a subsequent SPE, quantification limits, referred to dry weight (dw) of sewage sludge, ranged from 0.3ng/g for acesulfame (ACE) to 16ng/g for saccharin (SAC) and neohespiridine dihydrochalcone. The trueness, expressed as recovery, ranged between 72% and 105% and the precision, expressed as relative standard deviation, was lower than 16%. Moreover, the method proved its linearity up to the 2μg/g range. Finally, the described method was applied to the determination of the artificial sweeteners in primary and secondary sewage sludge from urban wastewater treatment plants. Four of the six studied artificial sweeteners (ACE, cyclamate, SAC and sucralose) were found in the samples at concentrations ranging from 17 to 628ng/g dw.

  13. [Determination of four phenolic endocrine disruptors in environmental water samples by high performance liquid chromatography-fluorescence detection using dispersive liquid-liquid microextraction coupled with derivatization].

    Science.gov (United States)

    Wang, Xiaoyan; Qi, Weimei; Zhao, Xian'en; Lü, Tao; Wang, Xiya; Zheng, Longfang; Yan, Yehao; You, Jinmao

    2014-06-01

    To achieve accurate, fast and sensitive detection of phenolic endocrine disruptors in small volume of environmental water samples, a method of dispersive liquid-liquid microextraction (DLLME) coupled with fluorescent derivatization was developed for the determination of bisphenol A, nonylphenol, octylphenol and 4-tert-octylphenol in environmental water samples by high performance liquid chromatography-fluorescence detection (HPLC-FLD). The DLLME and derivatization conditions were investigated, and the optimized DLLME conditions for small volume of environmental water samples (pH 4.0) at room temperature were as follows: 70 microL chloroform as extraction solvent, 400 microL acetonitrile as dispersing solvent, vortex mixing for 3 min, and then high-speed centrifugation for 2 min. Using 2-[2-(7H-dibenzo [a, g] carbazol-7-yl)-ethoxy] ethyl chloroformate (DBCEC-Cl) as precolumn derivatization reagent, the stable derivatives of the four phenolic endocrine disruptors were obtained in pH 10.5 Na2CO3-NaHCO3 buffer/acetonitrile at 50 degrees C for 3 min, and then separated within 10 min by HPLC-FLD. The limits of detection (LODs) were in the range of 0.9-1.6 ng/L, and the limits of quantification (LOQs) were in the range of 3.8-7.1 ng/L. This method had perfect linearity, precision and recovery results, and showed obvious advantages and practicality comparing to the previously reported methods. It is a convenient and validated method for the routine analysis of phenolic endocrine disruptors in waste water of paper mill, lake water, domestic wastewater, tap water, etc.

  14. Combination of dispersive liquid-liquid microextraction and solid-phase microextraction: An efficient hyphenated sample preparation method.

    Science.gov (United States)

    Jafari, Mohammad T; Saraji, Mohammad; Mossaddegh, Mehdi

    2016-09-30

    Two well-known microextraction methods, dispersive liquid-liquid microextraction (DLLME) and solid-phase microextraction (SPME), were combined, resulting in as an encouraging method. The method, named DLLME-SPME, was performed based on total vaporization technique. For the DLLME step, 1,1,2,2-tetrachloroethane and acetonitrile were used as extraction and disperser solvents, respectively. Halloysite nanotubes-titanium dioxide was used as the fiber coating in the SPME step. The method was applied for the extraction of diazinon and parathion (as the test compounds) in environmental water samples and fruit juices, and gas chromatography-corona discharge ion mobility spectrometry was used as the determination apparatus. Desorption temperature and time, extraction temperature and time, and the volume of the extracting solvent in the DLLME step were optimized as the effective parameters on the extraction efficiency. The relative standard deviations (RSDs) of intra-day were found to be 4-7% and 6-8% for diazinon and parathion, respectively. Also, the RSDs of inter-day were 7-9% and 8-10% for diazinon and parathion, respectively. The limits of quantification and detection were obtained to be 0.015 and 0.005μgL(-1) for diazinon, and 0.020 and 0.007μgL(-1) for parathion. A good linearity range (r(2)˃0.993) was obtained in the range of 0.015-3.000 and 0.020-3.000μgL(-1) for diazinon and parathion, respectively. The high enrichment factors were obtained as 3150 and 2965 for diazinon and parathion, respectively. This method showed high sensitivity with good recovery values (between 87 and 99%) for the extraction of target analytes in the real samples. Overall, the results revealed that the developed DLLME-SPME method had better extraction efficiency than DLLME and SPME alone.

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

    Science.gov (United States)

    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%.

  16. Sensitive determination of melamine in milk and powdered infant formula samples by high-performance liquid chromatography using dabsyl chloride derivatization followed by dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Faraji, M; Adeli, M

    2017-04-15

    A new and sensitive pre-column derivatization with dabsyl chloride followed by dispersive liquid-liquid microextraction was developed for the analysis of melamine (MEL) in raw milk and powdered infant formula samples by high performance liquid chromatography (HPLC) with visible detection. Derivatization with dabsyl chloride leads to improving sensitivity and hydrophobicity of MEL. Under optimum conditions of derivatization and microextraction steps, the method yielded a linear calibration curve ranging from 1.0 to 500μgL(-1) with a determination coefficient (R(2)) of 0.9995. Limit of detection and limit of quantification were 0.1 and 0.3μgL(-1), respectively. The relative standard deviation (RSD%) for intra-day (repeatability) and inter-day (reproducibility) at 25 and 100μgL(-1) levels of MEL was less than 7.0% (n=6). Finally, the proposed method was successfully applied for the preconcentration and determination of MEL in different raw milk and powdered infant formula, and satisfactory results were obtained (relative recovery ⩾94%).

  17. Transformation zone sampling rate used as a performance indicator for cervical liquid-based cytology sample-takers.

    Science.gov (United States)

    Faraker, C A; Greenfield, J

    2013-08-01

    To investigate the sampling performance of individual cervical cytology practitioners using the transformation zone sampling rate (TZSR) as a performance indicator and to assess the impact of dedicated on site training for those identified with a low TZSR. The TZSR was calculated for all practitioners submitting ThinPrep(®) cervical cytology specimens to the Conquest laboratory between January 2010 and November 2011. After excluding those with less than 30 qualifying samples the 10th percentile of the TZSR was calculated. Practitioners with a TZSR below the 10th percentile were visited by a specialist cervical cytology screening facilitator after which the TZSR of these practitioners was closely monitored. After exclusions there were 175 practitioners who had collected 24 358 qualifying liquid-based cytology (LBC) samples. The average TZSR was 70% (range 12-96%). The 10th percentile was 44%; 18 scored below the 10th percentile. Failure to apply sufficient pressure when sampling was identified as the most common reason for a low TZSR. In some cases there was suspicion that the cervix was not always adequately visualized. Continuous monitoring after assessment identified improvement in the TZSRs of 13/18 practitioners. Identification of practitioners with low TZSRs compared with their peers allows these individuals to be selected for personalized observation and training by a specialist in cervical cytology which can lead to an improvement in TZSR. As previous studies show a significant correlation between the TZSR and the detection rate of cytological abnormality it is useful to investigate low TZSRs. © 2013 John Wiley & Sons Ltd.

  18. Experimental study on the type change of liquid flow in broken coal samples

    Institute of Scientific and Technical Information of China (English)

    Lu-zhen WANG; Zhan-qing CHEN; Hai-de SHEN

    2013-01-01

    A test system of the permeability of broken coal samples mainly consists of a CMT5305 electronic universal test machine,crushed rock compaction containing cylinder and a self-designed seepage circuit,which is composed of a gear pump,a reversing valve,a relief valve and other components.By using the steady penetration method,the permeability and non-Darcy flow β factor of broken coal samples under five different porosity levels were measured,the grain diameters of the coal samples were selected as 2.5-5 mm,5-10 mm,10-15 mm,15-20 mm,20-25 mm and 2.5-25 mm,respectively.After measuring the permeability under each porosity,the overfall pressure of the relief valve continuously increased until the coal sample was broken down.In this way,the flow type of liquid inside the broken coal samples changed from seepage to pipe flow.The correlation between breakdown pressure gradient (BPG) and porosity was analyzed,and the BPG was compared with the pressure gradient when seepage instability occurred.The results show that,① the non-Darcy flow β factor was negative before broken coal samples with six kinds of diameters were broken down; ② the BPG of coal samples with a grain size of 2.5-25 mm was lower than that of the others; ③ the BPG of coal samples with a single diameter under the same porosity increased as the grain size increased; ④ the BPG could be fitted by an exponential function with porosity,and the exponent decreased as the grain size increased for coal samples with a single diameter; ⑤ the BPG was slightly less than the seepage instability pressure gradient.The change in liquid flow type from seepage to pipe flow could be regarded as the performance of the seepage instability.

  19. Liquid Phase Micro-Extraction of Linear Alkylbenzene Sulfonate Anionic Surfactants in Aqueous Samples

    Directory of Open Access Journals (Sweden)

    Jan Åke Jönsson

    2011-10-01

    Full Text Available Hollow fiber liquid phase micro-extraction (LPME of linear alkylbenzene sulfonates (LAS from aqueous samples was studied. Ion pair extraction of C10, C11, C12 and C13 homologues was facilitated with trihexylamine as ion-pairing agent, using di-n-hexylether as solvent for the supported liquid membrane (SLM. Effects of extraction time, acceptor buffer concentration, stirring speed, sample volume, NaCl and humic acids were studied. At 10–50 µg L−1 linear R2-coefficients were 0.99 for C10 and C11 and 0.96 for C12. RSD was typically ~15%. Three observations were especially made. Firstly, LPME for these analytes was unusually slow with maximum enrichment observed after 15–24 h (depending on sample volume. Secondly, the enrichment depended on LAS sample concentration with 35–150 times enrichment below ~150 µg L−1 and 1850–4400 times enrichment at 1 mg L−1. Thirdly, lower homologues were enriched more than higher homologues at low sample concentrations, with reversed conditions at higher concentrations. These observations may be due to the fact that LAS and the amine counter ion themselves influence the mass transfer at the water-SLM interface. The observations on LPME of LAS may aid in LPME application to other compounds with surfactant properties or in surfactant enhanced membrane extraction of other compounds.

  20. Liquid phase micro-extraction of linear alkylbenzene sulfonate anionic surfactants in aqueous samples.

    Science.gov (United States)

    Larsson, Niklas; Otrembska, Paulina; Villar, Mercedes; Jönsson, Jan Åke

    2011-10-13

    Hollow fiber liquid phase micro-extraction (LPME) of linear alkylbenzene sulfonates (LAS) from aqueous samples was studied. Ion pair extraction of C10, C11, C12 and C13 homologues was facilitated with trihexylamine as ion-pairing agent, using di-n-hexylether as solvent for the supported liquid membrane (SLM). Effects of extraction time, acceptor buffer concentration, stirring speed, sample volume, NaCl and humic acids were studied. At 10-50 µg L-1 linear R2-coefficients were 0.99 for C10 and C11 and 0.96 for C12. RSD was typically ~15%. Three observations were especially made. Firstly, LPME for these analytes was unusually slow with maximum enrichment observed after 15-24 h (depending on sample volume). Secondly, the enrichment depended on LAS sample concentration with 35-150 times enrichment below ~150 µg L-1 and 1850-4400 times enrichment at 1 mg L-1. Thirdly, lower homologues were enriched more than higher homologues at low sample concentrations, with reversed conditions at higher concentrations. These observations may be due to the fact that LAS and the amine counter ion themselves influence the mass transfer at the water-SLM interface. The observations on LPME of LAS may aid in LPME application to other compounds with surfactant properties or in surfactant enhanced membrane extraction of other compounds.

  1. High-throughput droplet analysis and multiplex DNA detection in the microfluidic platform equipped with a robust sample-introduction technique.

    Science.gov (United States)

    Chen, Jinyang; Ji, Xinghu; He, Zhike

    2015-08-12

    In this work, a simple, flexible and low-cost sample-introduction technique was developed and integrated with droplet platform. The sample-introduction strategy was realized based on connecting the components of positive pressure input device, sample container and microfluidic chip through the tygon tubing with homemade polydimethylsiloxane (PDMS) adaptor, so the sample was delivered into the microchip from the sample container under the driving of positive pressure. This sample-introduction technique is so robust and compatible that could be integrated with T-junction, flow-focus or valve-assisted droplet microchips. By choosing the PDMS adaptor with proper dimension, the microchip could be flexibly equipped with various types of familiar sample containers, makes the sampling more straightforward without trivial sample transfer or loading. And the convenient sample changing was easily achieved by positioning the adaptor from one sample container to another. Benefiting from the proposed technique, the time-dependent concentration gradient was generated and applied for quantum dot (QD)-based fluorescence barcoding within droplet chip. High-throughput droplet screening was preliminarily demonstrated through the investigation of the quenching efficiency of ruthenium complex to the fluorescence of QD. More importantly, multiplex DNA assay was successfully carried out in the integrated system, which shows the practicability and potentials in high-throughput biosensing.

  2. Theoretically informed Monte Carlo simulation of liquid crystals by sampling of alignment-tensor fields.

    Energy Technology Data Exchange (ETDEWEB)

    Armas-Perez, Julio C.; Londono-Hurtado, Alejandro; Guzman, Orlando; Hernandez-Ortiz, Juan P.; de Pablo, Juan J.

    2015-07-27

    A theoretically informed coarse-grained Monte Carlo method is proposed for studying liquid crystals. The free energy functional of the system is described in the framework of the Landau-de Gennes formalism. The alignment field and its gradients are approximated by finite differences, and the free energy is minimized through a stochastic sampling technique. The validity of the proposed method is established by comparing the results of the proposed approach to those of traditional free energy minimization techniques. Its usefulness is illustrated in the context of three systems, namely, a nematic liquid crystal confined in a slit channel, a nematic liquid crystal droplet, and a chiral liquid crystal in the bulk. It is found that for systems that exhibit multiple metastable morphologies, the proposed Monte Carlo method is generally able to identify lower free energy states that are often missed by traditional approaches. Importantly, the Monte Carlo method identifies such states from random initial configurations, thereby obviating the need for educated initial guesses that can be difficult to formulate.

  3. Theoretically informed Monte Carlo simulation of liquid crystals by sampling of alignment-tensor fields

    Energy Technology Data Exchange (ETDEWEB)

    Armas-Pérez, Julio C.; Londono-Hurtado, Alejandro [Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637 (United States); Guzmán, Orlando [Departamento de Física, Universidad Autónoma Metropolitana, Iztapalapa, DF 09340, México (Mexico); Hernández-Ortiz, Juan P. [Departamento de Materiales y Minerales, Universidad Nacional de Colombia, Sede Medellín, Medellín (Colombia); Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637 (United States); Pablo, Juan J. de, E-mail: depablo@uchicago.edu [Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637 (United States); Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2015-07-28

    A theoretically informed coarse-grained Monte Carlo method is proposed for studying liquid crystals. The free energy functional of the system is described in the framework of the Landau-de Gennes formalism. The alignment field and its gradients are approximated by finite differences, and the free energy is minimized through a stochastic sampling technique. The validity of the proposed method is established by comparing the results of the proposed approach to those of traditional free energy minimization techniques. Its usefulness is illustrated in the context of three systems, namely, a nematic liquid crystal confined in a slit channel, a nematic liquid crystal droplet, and a chiral liquid crystal in the bulk. It is found that for systems that exhibit multiple metastable morphologies, the proposed Monte Carlo method is generally able to identify lower free energy states that are often missed by traditional approaches. Importantly, the Monte Carlo method identifies such states from random initial configurations, thereby obviating the need for educated initial guesses that can be difficult to formulate.

  4. Repeating cytological preparations on liquid-based cytology samples: A methodological advantage?

    Science.gov (United States)

    Pinto, Alvaro P; Maia, Henrique Felde; di Loretto, Celso; Krunn, Patrícia; Túlio, Siumara; Collaço, Luis Martins

    2007-10-01

    This study investigates the rule that repeating cytological preparations on liquid-based cytology improves sample adequacy, diagnosis, microbiological, and hormonal evaluations. We reviewed 156 cases of pap-stained preparations of exfoliated cervical cells in two slides processed by DNA-Cytoliq System. After sample repeat/dilution, limiting factors affecting sample adequacy were removed in nine cases and three unsatisfactory cases were reclassified as satisfactory. Diagnosis was altered in 24 cases. Of these, the original diagnosis in 15 was atypical squamous cells of undetermined significance; after the second slide examination, diagnosis in 5 of the 15 cases changed to low-grade squamous intraepithelial lesion, 3 to high-grade squamous intraepithelial lesion, and 7 to absence of lesion. Microbiological evaluation was altered, with Candida sp. detected in two repeated slides. Repeat slide preparation or dilution of residual samples enhances cytological diagnosis and decreases effects of limiting factors in manually processed DIGENE DCS LBC.

  5. High-throughput droplet analysis and multiplex DNA detection in the microfluidic platform equipped with a robust sample-introduction technique

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jinyang; Ji, Xinghu [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); He, Zhike, E-mail: zhkhe@whu.edu.cn [Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China); Suzhou Institute of Wuhan University, Suzhou 215123 (China)

    2015-08-12

    In this work, a simple, flexible and low-cost sample-introduction technique was developed and integrated with droplet platform. The sample-introduction strategy was realized based on connecting the components of positive pressure input device, sample container and microfluidic chip through the tygon tubing with homemade polydimethylsiloxane (PDMS) adaptor, so the sample was delivered into the microchip from the sample container under the driving of positive pressure. This sample-introduction technique is so robust and compatible that could be integrated with T-junction, flow-focus or valve-assisted droplet microchips. By choosing the PDMS adaptor with proper dimension, the microchip could be flexibly equipped with various types of familiar sample containers, makes the sampling more straightforward without trivial sample transfer or loading. And the convenient sample changing was easily achieved by positioning the adaptor from one sample container to another. Benefiting from the proposed technique, the time-dependent concentration gradient was generated and applied for quantum dot (QD)-based fluorescence barcoding within droplet chip. High-throughput droplet screening was preliminarily demonstrated through the investigation of the quenching efficiency of ruthenium complex to the fluorescence of QD. More importantly, multiplex DNA assay was successfully carried out in the integrated system, which shows the practicability and potentials in high-throughput biosensing. - Highlights: • A simple, robust and low-cost sample-introduction technique was developed. • Convenient and flexible sample changing was achieved in microfluidic system. • Novel strategy of concentration gradient generation was presented for barcoding. • High-throughput droplet screening could be realized in the integrated platform. • Multiplex DNA assay was successfully carried out in the droplet platform.

  6. Isolation and purification of heroin from heroin street samples by preparative high performance liquid chromatography.

    Science.gov (United States)

    Guo, Zhen; Zheng, Hui; Lu, Yanzhen; Wei, Yun

    2012-09-10

    The present study established a novel method using preparative high performance liquid chromatography to isolate and purify heroin·HCl from heroin street samples to be used as a reference standard. Different kinds of mobile phases and columns were used, ultimately the mobile phase consisting of hexane-isopropanol-methanol (65:28:7, v/v) and the SIL preparative column prepared in laboratory were selected as the final condition. Heroin was further purified by the drowning-out crystallization method using isopropanol-methanol (50:1, v/v) and hexane as drowning-out anti-solvents and salting-out agents, respectively. The purity was assessed by analytical high performance liquid chromatography and the confirmation of the chemical structure was performed by IR and NMR. About 110.7mg of heroin·HCl at a purity of over 99.52% was obtained from 180mg of heroin street samples which contained 156.15mg of heroin·HCl component by preparative high performance liquid chromatography. This method is suitable for preparing heroin standards in forensic science area.

  7. Comparison of dispersive liquid-liquid microextraction based on organic solvent and ionic liquid combined with high-performance liquid chromatography for the analysis of emodin and its metabolites in urine samples.

    Science.gov (United States)

    Tian, Jie; Chen, Xuan; Bai, Xiaohong

    2012-01-01

    In this paper, two methods based on organic solvent dispersive liquid-liquid microextraction (OS-DLLME) and ionic liquid dispersive liquid-liquid microextraction (IL-DLLME) coupled with high-performance liquid chromatography have been critically compared for analyzing emodin and its metabolites (aloe-emodin, anthraquinone-2-carboxylic acid, rhein, danthron, chrysophanol and physcion) in urine samples. Several important parameters influencing the extraction recoveries of DLLME were carefully optimized. Under optimal conditions, the enrichment factors (EFs) for emodin and its metabolites by OS-DLLME and IL-DLLME were within the range of 90-295 and 63-192 respectively; the relative standard deviations (RSDs, n=3) for intra-day and inter-day precision were lower than 7.2 and 8.7% by OS-DLLME, and lower than 5.7 and 6.4% by IL-DLLME; the recoveries of emodin and its metabolites were from 87.1 to 105% for OS-DLLME and from 94.8 to 103% for IL-DLLME, respectively. There were no significant deviations between the two methods for the determination of emodin and its metabolites. From the results of HPLC/UV of urine sample after DLLME, the metabolites aloe-emodin, rhein, chrysophanol and physcion were identified by comparing the retention times with the standards. From the results of HPLC/MS, anthraquinone-2-carboxylic acid and danthron as unreported metabolites of emodin were found.

  8. New high temperature plasmas and sample introduction systems for analytical atomic emission and mass spectrometry. Progress report, January 1, 1990--December 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Montaser, A.

    1992-09-01

    New high temperature plasmas and new sample introduction systems are explored for rapid elemental and isotopic analysis of gases, solutions, and solids using mass spectrometry and atomic emission spectrometry. Emphasis was placed on atmospheric pressure He inductively coupled plasmas (ICP) suitable for atomization, excitation, and ionization of elements; simulation and computer modeling of plasma sources with potential for use in spectrochemical analysis; spectroscopic imaging and diagnostic studies of high temperature plasmas, particularly He ICP discharges; and development of new, low-cost sample introduction systems, and examination of techniques for probing the aerosols over a wide range. Refs., 14 figs. (DLC)

  9. Separation-preconcentration of nickel and lead in food samples by a combination of solid-liquid-solid dispersive extraction using SiO2 nanoparticles, ionic liquid-based dispersive liquid-liquid micro-extraction.

    Science.gov (United States)

    Jalbani, Nusrat; Soylak, Mustafa

    2015-01-01

    A microextraction method for the determination of nickel and lead using solid-liquid-solid dispersive extraction followed by ionic liquid-based dispersive liquid-liquid microextraction (SLSDE-ILDLLME) was presented. It was applied to the extraction of nickel and lead from food samples. Ammonium pyrrolidine dithiocarbamate (APDC) as complexing agent, [C4MIM][PF6] as ionic liquid, SiO2 as nanoparticles and 2 mol L(-1) HNO3 as eluent were used. Several important parameters such as amount of IL, extraction time, pH and volume of the complexing agent were investigated. The quantitative recoveries were obtained at pH 7.0 for analytes. Under the optimum conditions, the limits of detection (LODs) calculated using 3(Sd)blank/m were 0.17 for Ni(II) and 0.79 µg L(-1) for Pb(II) for aqueous solutions with 125 enrichment factor (EF). The limit of detections of the analyte ions (3(Sd)blank/m) for solid samples were 0.09 µg g(-1) (Ni) and 0.40 µg g(-1) (Pb). The accuracy of the proposed method was confirmed by the analysis of standard reference material (1577c bovine liver) and spiked recovery test. The proposed method was applied to determine nickel and lead levels in chicken, fish and meat samples.

  10. Analysis of bromate in drinking water using liquid chromatography-tandem mass spectrometry without sample pretreatment.

    Science.gov (United States)

    Kosaka, Koji; Asami, Mari; Takei, Kanako; Akiba, Michihiro

    2011-01-01

    An analytical method for determining bromate in drinking water was developed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The (18)O-enriched bromate was used as an internal standard. The limit of quantification (LOQ) of bromate was 0.2 µg/L. The peak of bromate was separated from those of coexisting ions (i.e., chloride, nitrate and sulfate). The relative and absolute recoveries of bromate in two drinking water samples and in a synthesized ion solution (100 mg/L chloride, 10 mg N/L nitrate, and 100 mg/L sulfate) were 99-105 and 94-105%, respectively. Bromate concentrations in 11 drinking water samples determined by LC-MS/MS were water without sample pretreatment.

  11. 210Pb and 210Po determination in environmental samples using liquid scintillation counting and alpha spectrometry

    Science.gov (United States)

    Pérez Sánchez, D.; Martin Sánchez, A.; Jurado Vargas, M.

    2003-01-01

    A simple radiochemical procedure has been developed to determine 210Pb and 210Po in environmental samples from the same matrix. Sediment samples are decomposed by leaching with mineral acids or by microwave digestion, while water samples are pre-concentrated. One part of the resulting solution, spiked with 209Po, is used for 210Po determination by spontaneous deposition onto nickel disks (α-spectrometry). The other part is assayed for 210Pb, separating the Pb either by anion-exchange (sediment samples), or by solvent extraction (water samples). The 210Pb source is finally prepared by precipitation as oxalate and the chemical recovery determined by gravimetry. The 210Pb activity concentration is determined by liquid scintillation. A standard sediment sample supplied by IAEA and spiked water samples were analysed to check the procedure. The 210Pb and 210Po measurements agreed well with the certifications, deviations being less than 10%. The mean recoveries for Pb and Po were (70±12)% and (77±8%) for sediments, and (70±10)% and (81±7)% for waters, respectively.

  12. Morphometric analysis of endometrial cells in liquid-based cervical cytology samples.

    Science.gov (United States)

    Gupta, P; Gupta, N; Dey, P

    2017-04-01

    Exfoliated endometrial cells can be seen in cervical smears in association with a wide variety of conditions ranging from normal proliferative endometrium to endometrial malignancies. It is often difficult to differentiate between benign, atypical and malignant endometrial cells using cytomorphology alone. This study was conducted to evaluate if morphometric analysis of endometrial nuclei on liquid-based cervical samples could be of help in differentiating between these endometrial cells. Three groups of cervical samples with histopathological correlation were selected: Group A: showing benign endometrial cells; Group B: showing atypical endometrial cells and Group C: showing malignant endometrial cells. There were 30 cases each in Group A and B and 39 cases in Group C. Image J, NIH, USA was used for selecting the endometrial nuclei and performing the morphometric measurements. MANOVA was used for statistical analysis. The mean nuclear area and nuclear perimeter were significantly different between the three groups of endometrial cells with a P-value liquid-based cervical cytology samples. © 2016 John Wiley & Sons Ltd.

  13. Extraction and enrichment of natural pigments from solid samples using ionic liquids and chitosan nanoparticles.

    Science.gov (United States)

    Xu, Jing-Jing; Li, Qin; Cao, Jun; Warner, Elisa; An, Mingrui; Tan, Zhijing; Wang, Shu-Ling; Peng, Li-Qing; Liu, Xun-Gao

    2016-09-09

    A green and economical method for the extraction and preconcentration of natural pigments (curcumin, demethoxycurcumin and bisdemethoxycurcumin) was developed using ultrasound-assisted extraction combined with dispersive micro solid-phase extraction. In this work, Ionic liquids (ILs) were used for the pre-extraction of natural pigments. The pure chitosan nanoparticles (CS NPs) were then used as a sorbent for the microextraction mode. The method involves the use of ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry. Operating parameters influencing the performance of extraction steps such as type and concentration of ILs, concentration of CS NPs, type of elution solvent, agitation time and pH of sample-extracting solution were investigated. Under the optimum conditions, the proposed method exhibited a low detection limit in the range of 0.11-0.36ng/mL at S/N=3, and good linearities with coefficients of determination (R(2)) higher than 0.9990. The recoveries of turmeric samples were ranging from 90.45% to 105.04% for the three studied curcuminoids with SD of 3.27-6.58. The experimental results indicated that the ILs and CS NPs were the promising materials for the extraction and enrichment of target curcuminoids from complex solid samples.

  14. Comparative Performance of PLZT and PVDF Pyroelectric Sensors Used to the Thermal Characterization of Liquid Samples

    Directory of Open Access Journals (Sweden)

    Gemima Lara Hernandez

    2013-01-01

    Full Text Available Among the photothermal methods, the photopyroelectric (PPE technique is a suitable method to determine thermal properties of different kinds of samples ranging from solids to liquids and gases. Polyvinylidene difluoride (PVDF is one of the most frequently used pyroelectric sensors in PPE technique but has the disadvantage that it can be easily deformed by the sample weight. This deformation could add a piezoelectric effect to the thermal parameters assessment; also PVDF has a narrow temperature operation range when compared with ceramic pyroelectric sensors. In order to minimize possible piezoelectric effects due to sensor deformation, a ceramic of lanthanum modified lead zirconate (PLZT was used as pyroelectric sensor in the PPE technique. Then, thermal diffusivity of some liquid samples was measured, by using the PPE configuration that denominated the thermal wave resonator cavity (TWRC, with a PLZT ceramic as pyroelectric detector. The performance obtained with the proposed ceramic in the TWRC configuration was compared with that obtained with PVDF by using the same configuration.

  15. Determination of tetracycline antibiotics in fatty food samples by selective pressurized liquid extraction coupled with high-performance liquid chromatography and tandem mass spectrometry.

    Science.gov (United States)

    Jiao, Zhe; Zhang, Suling; Chen, Hongwei

    2015-01-01

    For the determination of trace residues of tetracycline antibiotics in fatty food samples, selective pressurized liquid extraction coupled with high-performance liquid chromatography and tandem mass spectrometry was applied in this study. Copper(II) isonicotinate was first used as online cleanup adsorbent in the selective pressurized liquid extraction process. The adsorbent to sample ratio, extraction temperature, extraction time, and recycle times, etc. were optimized. The tetracyclines in food samples of pork, chicken meat, and clam meat were detected by liquid chromatography with tandem mass spectrometry. Tetracycline was found at levels of 0.32 and 0.53 μg/g and oxytetracycline was found at 0.14 and 0.21 μg/g in chicken meat and clam meat, respectively, while chlorotetracycline and deoxytetracycline were below the detection limit. The detection limit (S/N = 3) for these four tetracyclines were from 0.2 to 3.3 ng/g, the recoveries were from 75.8 to 110.5%, and relative standard deviations were from 5.5 to 13.6%. Copper(II) isonicotinate showed a higher purification capacity than other cleanup adsorbents for extraction of antibiotics in fatty food and the recovery showed predominance compared with a pressurized liquid extraction method without adsorbent. The study demonstrated that copper(II) isonicotinate would be a promising cleanup adsorbent in pressurized liquid extraction for the analysis of trace organic pollutants in complicated samples.

  16. Means of introducing an analyte into liquid sampling atmospheric pressure glow discharge

    Energy Technology Data Exchange (ETDEWEB)

    Marcus, R. Kenneth; Quarles, Jr., Charles Derrick; Russo, Richard E.; Koppenaal, David W.; Barinaga, Charles J.; Carado, Anthony J.

    2017-01-03

    A liquid sampling, atmospheric pressure, glow discharge (LS-APGD) device as well as systems that incorporate the device and methods for using the device and systems are described. The LS-APGD includes a hollow capillary for delivering an electrolyte solution to a glow discharge space. The device also includes a counter electrode in the form of a second hollow capillary that can deliver the analyte into the glow discharge space. A voltage across the electrolyte solution and the counter electrode creates the microplasma within the glow discharge space that interacts with the analyte to move it to a higher energy state (vaporization, excitation, and/or ionization of the analyte).

  17. Direct Trace Element Analysis of Liquid Blood Samples by In-Air Ion Beam Analytical Techniques (PIXE-PIGE).

    Science.gov (United States)

    Huszank, Robert; Csedreki, László; Török, Zsófia

    2017-02-07

    There are various liquid materials whose elemental composition is of interest in various fields of science and technology. In many cases, sample preparation or the extraction can be complicated, or it would destroy the original environment before the analysis (for example, in the case of biological samples). However, multielement direct analysis of liquid samples can be realized by an external PIXE-PIGE measurement system. Particle-induced X-ray and gamma-ray emission spectroscopy (PIXE, PIGE) techniques were applied in external (in-air) microbeam configuration for the trace and main element determination of liquid samples. The direct analysis of standard solutions of several metal salts and human blood samples (whole blood, blood serum, blood plasma, and formed elements) was realized. From the blood samples, Na, P, S, Cl, K, Ca, Fe, Cu, Zn, and Br elemental concentrations were determined. The focused and scanned ion beam creates an opportunity to analyze very small volume samples (∼10 μL). As the sample matrix consists of light elements, the analysis is possible at ppm level. Using this external beam setup, it was found that it is possible to determine elemental composition of small-volume liquid samples routinely, while the liquid samples do not require any preparation processes, and thus, they can be analyzed directly. In the case of lower concentrations, the method is also suitable for the analysis (down to even ∼1 ppm level) but with less accuracy and longer measurement times.

  18. Determination of nickel in food samples by flame atomic absorption spectroscopy after preconcentration and microextraction based ionic liquids using full factorial and central composite design.

    Science.gov (United States)

    Zarei, Zohre; Shemirani, Farzaneh

    2012-12-01

    In this research, a microextraction technique based on ionic liquids (ILs) termed in situ solvent formation microextraction (ISFME) was used for determination of nickel in solutions. 1-(2-pyridylazo)-2-naphtol (PAN) was chosen as a complexing agent. After preconcentration, the settled IL-phase was dissolved in 50 μL of ethanol and aspirated into the flame atomic absorption spectrometer (FAAS) using a home-made microsample introduction system. Injection of 50 μL volumes of analyte into an air-acetylene flame provided very sensitive spike-like and reproducible signals. ISFME is based on phase separation phenomenon of ionic liquids in aqueous solutions. This method is simple and rapid for extraction and preconcentration of metal ions from food samples and can be applied for the sample solutions containing very high concentrations of salt. Furthermore, this technique is much safer in comparison with the organic solvent extraction because of using ionic liquid. The effective parameters such as amount of IL, salt effect, concentration of the chelating agent and ion pairing agent were inspected by a full factorial design to identify important parameters and their interactions. Next, a central composite design was applied to obtain optimum point of the important parameters. Under the optimum conditions, the calibration graph was linear over the range of 2 to 80 ng/mL. The limit of detection and relative standard deviation (n= 6) were 0.6 ng/mL and 2%, respectively.

  19. Ionic liquid-based dispersive liquid-liquid microextraction combined with high performance liquid chromatography-UV detection for simultaneous preconcentration and determination of Ni, Co, Cu and Zn in water samples

    Directory of Open Access Journals (Sweden)

    Asghari Alireza

    2014-01-01

    Full Text Available Ionic liquid-based dispersive liquid-liquid microextraction (IL-DLLME coupled with high performance liquid chromatography (HPLC-UV detection was developed for simultaneous extraction and determination of nickel, cobalt, copper and zinc ions. In the proposed approach, salophen (N,N'-bis(salisyliden-1,2-phenylenediamine was used as a chelating agent; the ionic liquid, 1-hexeyl-3-methylimidazolium hexafluorophosphate, and acetone were selected as extracting and dispersive solvents, respectively. After extraction, phase separation was performed by centrifugation and the sedimented phase (ionic liquid was solubilized in acetonitrile and directly injected into the HPLC for subsequent analysis. Baseline separation of metal ion complexes was achieved on a RP-C18 column using a gradient elution of the mixtures of methanol-acetonitrile-water as the mobile phase at a flow rate of 1.0 mL min-1. The influence of variables such as sample pH, concentration of the chelating agent, amount of ionic liquid (extraction solvent, disperser solvent volume, extraction time, salt effect and centrifugation speed were studied and optimized. Under the optimum conditions, the enrichment factor of 222 was obtained. The detection limits for Ni, Co, Cu and Zn were 0.8, 1.6, 1.9 and 2.8 μg L−1, respectively. The relative standard deviations (RSDs were in the range of 3.6-5.0 % for all of the investigated metal ions. The proposed procedure was successfully applied to the determination of the studied metal ions in water samples.

  20. The Determination of Polyethylene Glycol in Untreated Urine Samples by High Performance Liquid Chromatography for Intestinal Permeability Studies

    DEFF Research Database (Denmark)

    Larsen, Elfinn; Pedersen, Walther Batsberg; Philipsen, E.

    1985-01-01

    Polyethylene glycol in urine samples has been investigated by high performance liquid chromatography. The molecular weights ranged from 634 to 1338. The urine samples were applied to the chromatographic system without any pre-treatment. For samples with a concentration of 0.2% polyethylene glycol...

  1. Elastic anisotropy effects on the electrical responses of a thin sample of nematic liquid crystal

    Science.gov (United States)

    Gomes, O. A.; Yednak, C. A. R.; Ribeiro de Almeida, R. R.; Teixeira-Souza, R. T.; Evangelista, L. R.

    2017-03-01

    The electrical responses of a nematic liquid crystal cell are investigated by means of the elastic continuum theory. The nematic medium is considered as a parallel circuit of a resistance and a capacitance and the electric current profile across the sample is determined as a function of the elastic constants. In the reorientation process of the nematic director, the resistance and capacitance of the sample are determined by taking into account the elastic anisotropy. A nonmonotonic profile for the current is observed in which a minimum value of the current may be used to estimate the elastic constants values. This scenario suggests a theoretical method to determine the values of the bulk elastic constants in a single planar aligned cell just by changing the direction of applied electrical field and measuring the resulting electrical current.

  2. Development of high performance liquid chromatography method for miconazole analysis in powder sample

    Science.gov (United States)

    Hermawan, D.; Suwandri; Sulaeman, U.; Istiqomah, A.; Aboul-Enein, H. Y.

    2017-02-01

    A simple high performance liquid chromatography (HPLC) method has been developed in this study for the analysis of miconazole, an antifungal drug, in powder sample. The optimized HPLC system using C8 column was achieved using mobile phase composition containing methanol:water (85:15, v/v), a flow rate of 0.8 mL/min, and UV detection at 220 nm. The calibration graph was linear in the range from 10 to 50 mg/L with r 2 of 0.9983. The limit of detection (LOD) and limit of quantitation (LOQ) obtained were 2.24 mg/L and 7.47 mg/L, respectively. The present HPLC method is applicable for the determination of miconazole in the powder sample with a recovery of 101.28 % (RSD = 0.96%, n = 3). The developed HPLC method provides short analysis time, high reproducibility and high sensitivity.

  3. Co marker determination in rumen liquid sample by energy dispersive X-ray fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Almeida, Eduardo de; Nascimento Filho, Virgilio F.; Massoni, Paulo R. [Centro de Energia Nuclear na Agricultura (CENA), Piracicaba, SP (Brazil). Lab. de Instrumentacao Nuclear (LIN)]. E-mail: edualm@usp.br; Leite, Laudi C.; Lanna, Dante P.D. [Escola Superior de Agricultura ' Luiz de Queiroz' (ESALQ/USP), Piracicaba, SP (Brazil). Dept. de Zootecnia. Lab. de Anatomia e Fisiologia Animal (LAFA)]. E-mail: lcleite@ciagri.usp.br

    2007-07-01

    The Co element is used in nutritional studies as marker. This paper describes an analytical methodology for Co determination in rumen liquid sample using energy dispersive X-ray spectrometry (EDXRF). 200 {mu}L of the sample were dried at 60 deg C on 6.35 {mu}m Mylar film. Ga was used as internal standard. The excitation was carried out utilizing Mo target X-ray tube (Zr filter) at 30 kV / 20 mA. The acquisition time was 200 s. The accuracy of this methodology was assessed through standard addition method, the recovery obtained was 98.7 % for Co. The detection limit was 0.15 mg / L for this element. (author)

  4. Rapid analysis of aflatoxins B1, B2, and ochratoxin A in rice samples using dispersive liquid-liquid microextraction combined with HPLC.

    Science.gov (United States)

    Lai, Xian-Wen; Sun, Dai-Li; Ruan, Chun-Qiang; Zhang, He; Liu, Cheng-Lan

    2014-01-01

    A novel, simple, and rapid method is presented for the analysis of aflatoxin B1, aflatoxin B2, and ochratoxin A in rice samples by dispersive liquid-liquid microextraction combined with LC and fluorescence detection. After extraction of the rice samples with a mixture of acetonitrile/water/acetic acid, mycotoxins were rapidly partitioned into a small volume of organic solvent (chloroform) by dispersive liquid-liquid microextraction. The three mycotoxins were simultaneously determined by LC with fluorescence detection after precolumn derivatization for aflatoxin B1 and B2. Parameters affecting both extraction and dispersive liquid-liquid microextraction procedures, including the extraction solvent, the type and volume of extractant, the volume of dispersive solvent, the addition of salt, the pH and the extraction time, were optimized. The optimized protocol provided an enrichment factor of approximately 1.25 and with detection of limits (0.06-0.5 μg/kg) below the maximum levels imposed by current regulations for aflatoxins and ochratoxin A. The mean recovery of three mycotoxins ranged from 82.9-112%, with a RSD less than 7.9% in all cases. The method was successfully applied to measure mycotoxins in commercial rice samples collected from local supermarkets in China.

  5. Liquid chromatography-mass spectrometric determination of rufinamide in low volume plasma samples.

    Science.gov (United States)

    Gáll, Zsolt; Vancea, Szende; Dogaru, Maria T; Szilágyi, Tibor

    2013-12-01

    Quantification of rufinamide in plasma was achieved using a selective and sensitive liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method. The chromatographic separation was achieved on a reversed phase column (Zorbax SB-C18 100mm×3mm, 3.5μm) under isocratic conditions. The mobile phase consisted of a mixture of water containing 0.1% formic acid and methanol (50:50, v/v). The mass spectrometric detection of the analyte was in multiple reaction monitoring mode (MRM) using an electrospray positive ionization (ESI positive). The monitored ions were 127m/z derived from 239m/z rufinamide and 108m/z derived from 251m/z the internal standard (lacosamide). Protein precipitation with methanol was applied for sample preparation using only 50μl aliquots. The concentration range was 40-2000ng/ml for rufinamide in plasma. The limit of detection was 1.25ng/ml and the lower limit of quantification was established at 5ng/ml rufinamide concentration. Selectivity and matrix effect was verified using individual human, rat and rabbit plasma samples. Short-term, post-preparative and freeze-thaw stability was also investigated. The proposed method provides accuracy, precision and high-throughput (short runtime 4.5min) for quantitative determination of rufinamide in plasma. This is the first reported liquid chromatography-tandem mass spectrometric (LC-MS/MS) method for analysis of rufinamide from low volume plasma samples. The LC-MS/MS method was validated according to the current official guidelines and can be applied to accurately measure rufinamide level of large number of plasma samples from clinical studies or therapeutic drug monitoring.

  6. Sampling frequency, response times and embedded signal filtration in fast, high efficiency liquid chromatography: A tutorial.

    Science.gov (United States)

    Wahab, M Farooq; Dasgupta, Purnendu K; Kadjo, Akinde F; Armstrong, Daniel W

    2016-02-11

    With increasingly efficient columns, eluite peaks are increasingly narrower. To take full advantage of this, choice of the detector response time and the data acquisition rate a.k.a. detector sampling frequency, have become increasingly important. In this work, we revisit the concept of data sampling from the theorem variously attributed to Whittaker, Nyquist, Kotelnikov, and Shannon. Focusing on time scales relevant to the current practice of high performance liquid chromatography (HPLC) and optical absorbance detection (the most commonly used method), even for very narrow simulated peaks Fourier transformation shows that theoretical minimum sampling frequency is still relatively low (fast chromatography on a state-of-the-art column (38,000 plates), we evaluate the responses produced by different present generation instruments, each with their unique black box digital filters. We show that the common wisdom of sampling 20 points per peak can be inadequate for high efficiency columns and that the sampling frequency and response choices do affect the peak shape. If the sampling frequency is too low or response time is too large, the observed peak shapes will not remain as narrow as they really are - this is especially true for high efficiency and high speed separations. It is shown that both sampling frequency and digital filtering affect the retention time, noise amplitude, peak shape and width in a complex fashion. We show how a square-wave driven light emitting diode source can reveal the nature of the embedded filter. We discuss time uncertainties related to the choice of sampling frequency. Finally, we suggest steps to obtain optimum results from a given system.

  7. Simultaneous determination of the Cd and Zn total body burden of individual, nearly microscopic, nanoliter-volume aquatic organisms (Hyalella azteca) by rhenium-cup in-torch vaporization (ITV) sample introduction and axially viewed ICP-AES

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Andrea T.; Badiei, Hamid R.; Karanassios, Vassili [University of Waterloo, Department of Chemistry, Waterloo, ON (Canada); Evans, J. Catherine [University of Waterloo, Department of Biology, Waterloo, ON (Canada)

    2004-09-01

    The Cd and Zn total body burden of individual, up to 7-day-old aquatic organisms (Hyalella aztecabenthic amphipod) with an average volume of approximately 100 nL was determined simultaneously by using rhenium-cup (Re-cup) in-torch vaporization (ITV) sample introduction and an axially viewed inductively coupled plasma atomic emission spectrometry (ICP-AES) system. The direct elemental analysis capabilities of this system (i.e., no sample digestion) reduced sample preparation time, eliminated contamination concerns from the digestion reagent and, owing to its detection limits (e.g., in the low pg range for Cd and Zn), vit enabled simultaneous determinations of Cd and Zn in individual, neonate and young juvenile specimens barely visible to the unaided eye (e.g., nearly microscopic). As for calibration, liquid standards and the standard additions method were tested. Both methods gave comparable results, thus indicating that in this case liquid standards can be employed for calibration, and in the process making use of the standard additions method unnecessary. Overall, the ITV-ICP-AES approach by-passed the time-consuming acid digestions, eliminated the potential for contamination from the digestion reagents, improved considerably the speed of acquisition of analytical information and enabled simultaneous determinations of two elements using individual biological specimens. (orig.)

  8. Determination of ten pyrethroids in various fruit juices: comparison of dispersive liquid-liquid microextraction sample preparation and QuEChERS method combined with dispersive liquid-liquid microextraction.

    Science.gov (United States)

    Zhang, Yaohai; Zhang, Xuelian; Jiao, Bining

    2014-09-15

    Dispersive liquid-liquid microextraction (DLLME) sample preparation and the quick, easy, cheap, effective, rugged and safe (QuEChERS) method combined with DLLME were developed and compared for the analysis of ten pyrethroids in various fruit juices using gas chromatography-electron capture detection (GC-ECD). QuEChERS-DLLME method has found its widespread applications to all the fruit juices including those samples with more complex matrices (orange, lemon, kiwi and mango) while DLLME was confined to the fruit juices with simpler matrices (apple, pear, grape and peach). The two methods provided acceptable recoveries and repeatability. In addition, the applicabilities of two methods were demonstrated with the real samples and further confirmed by gas chromatography-mass spectrometry (GC-MS).

  9. Liquid-solid extraction coupled with magnetic solid-phase extraction for determination of pyrethroid residues in vegetable samples by ultra fast liquid chromatography.

    Science.gov (United States)

    Jiang, Chunzhu; Sun, Ying; Yu, Xi; Gao, Yan; Zhang, Lei; Wang, Yuanpeng; Zhang, Hanqi; Song, Daqian

    2013-09-30

    In this study, liquid-solid extraction coupled with magnetic solid-phase extraction was successfully developed for the extraction of pyrethroid residues in vegetable samples. The analytes were determined by ultra fast liquid chromatography. The pyrethroids were extracted by liquid-solid extraction and then adsorbed onto magnetic adsorbent. Magnetic adsorbent, C18-functionalized ultrafine magnetic silica nanoparticles, was synthesized by chemical coprecipitation, silanization and alkylation. The analytes adsorbed onto the magnetic adsorbent can be simply and rapidly isolated from sample solution with a strong magnet on the bottom of the extraction vessel. The extraction parameters, such as liquid-solid extraction solvent, liquid-solid extraction time, the amount of magnetic adsorbent, magnetic solid-phase extraction time and magnetic solid-phase extraction desorption solvent, were optimized to improve the extraction efficiency. The analytical performances of this method, including linear range, detection limit, precision, and recovery were evaluated. The limits of detection for pyrethroid were between 0.63 and 1.2 ng g(-1). Recoveries obtained by analyzing the four spiked vegetable samples were between 76.0% and 99.5%. The results showed that the present method was a simple, accurate and high efficient approach for the determination of pyrethroids in the vegetable samples.

  10. Boiling Heat Transfer Enhancement in a Vertical Annulus by Introduction of Air in Liquid Flow%内加热垂直环隙中引入惰性气体时的沸腾传热

    Institute of Scientific and Technical Information of China (English)

    王军; 苗君; 刘芸; 沈自求

    2004-01-01

    In this paper, boiling heat transfer in a vertical annulus with inner side heated with and without air introduction is experimentally studied. Results show that boiling heat transfer is significantly enhanced by the introduction of air. When air is introduced into the liquid with a temperature below boiling point, the enhancement of heat transfer is also detected. It is concluded from the study that the heat transfer enhanced by introduction of inert gas is due to the liquid vaporization at the gas-liquid interface near the wall, which removes a large amount of latent heat and lowers the interfacial temperature considerably. Thus the gas-liquid interface acts as a "heat sink"and the heat transfer is augmented significantly.

  11. Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction for determination of mercury in water samples

    OpenAIRE

    Fernández Martínez, Elena; Vidal Martínez, Lorena; Martín-Yerga, Daniel; Blanco, María del Carmen; Canals Hernández, Antonio; Costa-García, Agustín

    2015-01-01

    A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid–liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbam...

  12. Multielement determination of heavy metals in water samples by continuous powder introduction microwave-induced plasma atomic emission spectrometry after preconcentration on activated carbon

    Science.gov (United States)

    Jankowski, Krzysztof; Yao, Jun; Kasiura, Krzysztof; Jackowska, Adrianna; Sieradzka, Anna

    2005-03-01

    A novel continuous powder introduction microwave-induced plasma atomic emission spectrometry method (CPI-MIP-AES) has been developed for trace determination of metals in ground and tap water samples after preconcentration on activated carbon. The experimental setup consisted of integrated rectangular cavity TE 101 and vertically positioned plasma torch. The technical arrangement of the sample introduction system has been designed based on the fluidized bed concept. The satisfactory signal stability required for sequential analysis was attained owing to the vertical plasma configuration, as well as the plasma gas flow rate compatibility with sample introduction flow rate. The elements of interest (Cd, Cu, Cr, Fe, Mn, Pb, Zn) were preconcentrated in a batch procedure at pH 8-8.5 after addition of activated carbon and then, after filtering and drying of the activated carbon suspension, introduced to the MIP by the CPI system. An enrichment factor of about 1000-fold for a sample volume of 1 l was obtained. The detection limit values for the proposed method were 17-250 ng l -1. The proposed method was validated by analyzing the certified reference materials: SRW "Warta" Synthetic River Water and BCR CRM 399 major elements in freshwater. The method was successfully applied to the determination of the heavy metals in tap water samples.

  13. Multielement determination of heavy metals in water samples by continuous powder introduction microwave-induced plasma atomic emission spectrometry after preconcentration on activated carbon

    Energy Technology Data Exchange (ETDEWEB)

    Jankowski, Krzysztof [Warsaw University of Technology, Faculty of Chemistry, Department of Analytical Chemistry, 00-664 Warsaw, ul. Noakowskiego 3 (Poland)]. E-mail: kj@ch.pw.edu.pl; Yao Jun [College of Chemistry and Chemical Engineering, Jishou University, 120 Renmin South Road, Jishou 416000 (China); Kasiura, Krzysztof [Warsaw University of Technology, Faculty of Chemistry, Department of Analytical Chemistry, 00-664 Warsaw, ul. Noakowskiego 3 (Poland); Jackowska, Adrianna [Warsaw University of Technology, Faculty of Chemistry, Department of Analytical Chemistry, 00-664 Warsaw, ul. Noakowskiego 3 (Poland); Sieradzka, Anna [Warsaw University of Technology, Faculty of Chemistry, Department of Analytical Chemistry, 00-664 Warsaw, ul. Noakowskiego 3 (Poland)

    2005-03-31

    A novel continuous powder introduction microwave-induced plasma atomic emission spectrometry method (CPI-MIP-AES) has been developed for trace determination of metals in ground and tap water samples after preconcentration on activated carbon. The experimental setup consisted of integrated rectangular cavity TE{sub 101} and vertically positioned plasma torch. The technical arrangement of the sample introduction system has been designed based on the fluidized bed concept. The satisfactory signal stability required for sequential analysis was attained owing to the vertical plasma configuration, as well as the plasma gas flow rate compatibility with sample introduction flow rate. The elements of interest (Cd, Cu, Cr, Fe, Mn, Pb, Zn) were preconcentrated in a batch procedure at pH 8-8.5 after addition of activated carbon and then, after filtering and drying of the activated carbon suspension, introduced to the MIP by the CPI system. An enrichment factor of about 1000-fold for a sample volume of 1 l was obtained. The detection limit values for the proposed method were 17-250 ng l{sup -1}. The proposed method was validated by analyzing the certified reference materials: SRW 'Warta' Synthetic River Water and BCR CRM 399 major elements in freshwater. The method was successfully applied to the determination of the heavy metals in tap water samples.

  14. Study of adsorption Ag and Pb in liquid sample using Berea sandstone by commercial laser-induced breakdown spectroscopy (LIBS)

    Science.gov (United States)

    Suyanto, H.; Wendri, N.; Agustiningrum, U.; Manurung, M.

    2016-11-01

    Qualitative and quantitative analysis of Pb and Ag elements in liquid samples had been done by commercial laser-induced breakdown spectroscopy (LIBS) using adsorption method on a Berea Sandstone. The aim of this study is to identify the thickness of the Berea Sandstone for adsorbing Pb and Ag elements in liquid. The experiment was started with characterizing the Berea Sandstone that contains Si, Na, H, Li, K, Ca, O, N, Be, Ti, Al, Mg and Ba. Some of these elements have ability to adsorb Pb and Ag elements in the liquid. To prove this phenomenon, it is required to look for the experiment parameter optimum conditions such as laser energy, adsorption time and sample temperature. The experiment was conducted by dropping 2 ml standard liquid containing 1000 ppm of Pb and Ag to the Berea Sandstone surface. The result showed that the parameter optimum conditions for analyzing Pb and Ag elements in liquid sample with adsorption method were adsorption delay-time of 15 minutes, laser energy of 120 mJ and sample heating of 80 °C. The next experiment was focused on the number of adsorption as a function of depth. The data showed that Pb and Ag elements in liquid sample of 2 ml, 1000 ppm were fully adsorbed by the Berea Sandstone until the depth of 0.372 mm and 10.40 mm from the surface, respectively. The data also showed that the limit of detection predicted to about 22.76 ppm.

  15. Comparison of air-agitated liquid-liquid microextraction technique and conventional dispersive liquid-liquid micro-extraction for determination of triazole pesticides in aqueous samples by gas chromatography with flame ionization detection.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Mogaddam, Mohammad Reza Afshar; Aghdam, Abdollah Abdollahi

    2013-07-26

    Two micro-extraction methods, air-agitated liquid-liquid microextraction (AALLME) and dispersive liquid-liquid microextraction (DLLME), have been compared with each other by applying them for the analysis of five triazole pesticides (penconazole, hexaconazole, diniconazole, tebuconazole and triticonazole) in aqueous samples by gas chromatography with flame ionization detection (GC-FID). In the AALLME method, which excludes any disperser solvent, much less volume of organic solvent is used. In order to form fine and dispersed organic droplets in the aqueous phase, the mixture of aqueous sample solution and extraction solvent is repeatedly aspirated and dispensed with a syringe. In the DLLME method, an appropriate mixture of extraction solvent and disperser solvent is rapidly injected by a syringe into the aqueous sample. Effect of the pertinent experimental factors on DLLME (i.e. identity and volume of the extraction and disperser solvents and ionic strength) and on AALLME (identity and volume of the extraction solvent, number of agitations, and ionic strength) were investigated. Under optimal conditions, limits of detection for the five target pesticides obtained by AALLME-GC-FID and DLLME-GC-FID ranged from 0.20 to 1.1ngmL(-1) and 1.9 to 5.9ngmL(-1), respectively. The relative standard deviations (RSDs, n=5) were in the range of 1-4% and 3-5% with the enrichment factors of 449-504 and 79-143 for AALLME-GC-FID and DLLME-GC-FID, respectively. Both of the compared methods are simple, fast, efficient, inexpensive and can be applied to the analysis of the five pesticides in different aqueous samples in which penconazole and hexaconazole were found. For spiked samples, the recoveries were in the ranges of 92-105%, and 92-104% for AALLME and DLLME, respectively.

  16. Liquid-liquid-solid microextraction based on membrane-protected molecularly imprinted polymer fiber for trace analysis of triazines in complex aqueous samples.

    Science.gov (United States)

    Hu, Yuling; Wang, Yangyang; Hu, Yufei; Li, Gongke

    2009-11-20

    A novel liquid-liquid-solid microextraction (LLSME) technique based on porous membrane-protected molecularly imprinted polymer (MIP)-coated silica fiber has been developed. In this technique, a MIP-coated silica fiber was protected with a length of porous polypropylene hollow fiber membrane which was filled with water-immiscible organic phase. Subsequently the whole device was immersed into aqueous sample for extraction. The LLSME technique was a three-phase microextraction approach. The target analytes were firstly extracted from the aqueous sample through a few microliters of organic phase residing in the pores and lumen of the membrane, and were then finally extracted onto the MIP fiber. A terbutylazine MIP-coated silica fiber was adopted as an example to demonstrate the feasibility of the novel LLSME method. The extraction parameters such as the organic solvent, extraction and desorption time were investigated. Comparison of the LLSME technique was made with molecularly imprinted polymer based solid-phase microextraction (MIP-SPME) and hollow fiber membrane-based liquid-phase microextraction (HF-LPME), respectively. The LLSME, integrating the advantages of high selectivity of MIP-SPME and enrichment and sample cleanup capability of the HF-LPME into a single device, is a promising sample preparation method for complex samples. Moreover, the new technique overcomes the problem of disturbance from water when the MIP-SPME fiber was exposed directly to aqueous samples. Applications to analysis of triazine herbicides in sludge water, watermelon, milk and urine samples were evaluated to access the real sample application of the LLSME method by coupling with high-performance liquid chromatography (HPLC). Low limits of detection (0.006-0.02 microg L(-1)), satisfactory recoveries and good repeatability for real sample (RSD 1.2-9.6%, n = 5) were obtained. The method was demonstrated to be a fast, selective and sensitive pretreatment method for trace analysis of triazines

  17. Development of sample preparation method for eleutheroside B and E analysis in Acanthopanax senticosus by ionic liquids-ultrasound based extraction and high-performance liquid chromatography detection.

    Science.gov (United States)

    Yang, Lei; Ge, Hongshuang; Wang, Wenjie; Zu, Yuangang; Yang, Fengjian; Zhao, Chunjian; Zhang, Lin; Zhang, Ying

    2013-12-01

    An ionic liquids-based ultrasonic-assisted extraction (ILUAE) method was successfully developed for extracting eleutheroside B and E from Radix Acanthopanax senticosus. Thirteen 1-alkyl-3-methylimidazolium ionic liquids with different cations and anions were investigated and 1-butyl-3-methylimidazolium bromide ([C4mim]Br) solution was selected as the solvent. The conditions for ILUAE, including the ionic liquid concentration, soaking time, ultrasonic power, ultrasonic time, solid-liquid ratio and number of extraction cycles, were optimized. With the proposed method, the energy consumption time was reduced to 30 min, whereas conventional method requires about 4h. The proposed method had good recovery (97.96-103.39%) and reproducibility (RSD, n=5; 3.3% for eleutheroside B, 4.6% for eleutheroside E). ILUAE was an efficient, rapid and simple sample preparation technique that showed high reproducibility and was environmental friendly.

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

    Science.gov (United States)

    Tsai, Wan-Chun; Huang, Shang-Da

    2009-07-03

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

  19. Ionic liquid-based ultrasound-assisted emulsification microextraction coupled with high performance liquid chromatography for the determination of four fungicides in environmental water samples.

    Science.gov (United States)

    Liang, Pei; Wang, Fang; Wan, Qin

    2013-02-15

    A highly efficient and environmentally friendly sample preparation method termed ionic liquid-based ultrasound-assisted emulsification microextraction (IL-USAEME) combined with high performance liquid chromatography has been developed for the determination of four fungicides (azoxystrobin, diethofencarb, pyrimethanil and kresoxim-methyl) in water samples. In this novel approach, ionic liquid (IL) was used as extraction solvent in place of the organic solvent used in conventional USAEME assay, and there is no need for using organic dispersive solvent which is typically required in the common dispersive liquid-liquid microextraction method. Various parameters that affect the extraction efficiency, such as the kind and volume of IL, ultrasound emulsification time, extraction temperature and salt addition were investigated and optimized. Under the optimum extraction condition, the linearities of calibration curves were in the range from 3 to 5000 ng mL(-1) for target analytes with the correlation coefficient higher than 0.9992. The enrichment factors and the limits of detection were in the range of 88-137 and 0.73-2.2 ng mL(-1), depending on the analytes. The environmental water samples were successfully analyzed using the proposed method, and the relative recoveries at fortified levels of 50 and 100 ng mL(-1) were in the range of 83.9%-116.2%.

  20. Clinical Introduction of a Novel Liquid Fiducial Marker for Breathing Adapted Radiotherapy of Non-Small Cell Lung Cancer

    DEFF Research Database (Denmark)

    Rydhog, Jonas Scherman

    , possible dose perturbation and volumetric changes. We found that the liquid fiducial marker was an excellent alternative to solid fiducial markers. It showed small dose perturbations in proton therapy, was volumetrically stable during several weeks of radiotherapy and functioned well as a surrogate...

  1. Sampling and analysis of radioactive liquid wastes and sludges in the Melton Valley and evaporator facility storage tanks at ORNL

    Energy Technology Data Exchange (ETDEWEB)

    Sears, M.B.; Botts, J.L.; Ceo, R.N.; Ferrada, J.J.; Griest, W.H.; Keller, J.M.; Schenley, R.L.

    1990-09-01

    The sampling and analysis of the radioactive liquid wastes and sludges in the Melton Valley Storage Tanks (MVSTs), as well as two of the evaporator service facility storage tanks at ORNL, are described. Aqueous samples of the supernatant liquid and composite samples of the sludges were analyzed for major constituents, radionuclides, total organic carbon, and metals listed as hazardous under the Resource Conservation and Recovery Act (RCRA). Liquid samples from five tanks and sludge samples from three tanks were analyzed for organic compounds on the Environmental Protection Agency (EPA) Target Compound List. Estimates were made of the inventory of liquid and sludge phases in the tanks. Descriptions of the sampling and analytical activities and tabulations of the results are included. The report provides data in support of the design of the proposed Waste Handling and Packaging Plant, the Liquid Low-Level Waste Solidification Project, and research and development activities (R D) activities in developing waste management alternatives. 7 refs., 8 figs., 16 tabs.

  2. Comprehensive sample analysis using high performance liquid chromatography with multi-detection

    Energy Technology Data Exchange (ETDEWEB)

    Pravadali, Sercan [Australian Centre for Research on Separation Sciences (ACROSS), School of Science and Health, University of Western Sydney (Parramatta), NSW 1797 (Australia); Bassanese, Danielle N.; Conlan, Xavier A.; Francis, Paul S.; Smith, Zoe M.; Terry, Jessica M. [Centre for Chemistry and Biotechnology, School of Life and Environmental Sciences, Deakin University, Victoria 3216 (Australia); Shalliker, R. Andrew, E-mail: R.Shalliker@uws.edu.au [Australian Centre for Research on Separation Sciences (ACROSS), School of Science and Health, University of Western Sydney (Parramatta), NSW 1797 (Australia)

    2013-11-25

    Graphical abstract: -- Highlights: •Detection selectivity was assessed with 6 detection modes. •Natural samples show great diversity in detection selectivity. •Complex samples require evaluation using a multifaceted approach to detection. •23/30 known compounds (detected by MS) detected by chemiluminescence, DPPH and UV. -- Abstract: Herein we assess the separation space offered by a liquid chromatography system with an optimised uni-dimensional separation for the determination of the key chemical entities in the highly complex matrix of a tobacco leaf extract. Multiple modes of detection, including UV–visible absorbance, chemiluminescence (acidic potassium permanganate, manganese(IV), and tris(2,2′-bipyridine)ruthenium(III)), mass spectrometry and DPPH radical scavenging were used in an attempt to systematically reduce the data complexity of the sample whilst obtaining a greater degree of molecule-specific information. A large amount of chemical data was obtained, but several limitations in the ability to assign detector responses to particular compounds, even with the aid of complementary detection systems, were observed. Thirty-three compounds were detected via MS on the tobacco extract and 12 out of 32 compounds gave a peak height ratio (PHR) greater than 0.33 on one or more detectors. This paper serves as a case study of these limitations, illustrating why multidimensional chromatography is an important consideration when developing a comprehensive chemical detection system.

  3. Minimizing tip-sample forces in jumping mode atomic force microscopy in liquid

    Energy Technology Data Exchange (ETDEWEB)

    Ortega-Esteban, A. [Departamento de Fisica de la Materia Condensada, C-3, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Horcas, I. [Nanotec Electronica S.L., Centro Empresarial Euronova 3, Ronda de Poniente 12, 28760 Tres Cantos, Madrid (Spain); Hernando-Perez, M. [Departamento de Fisica de la Materia Condensada, C-3, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Ares, P. [Nanotec Electronica S.L., Centro Empresarial Euronova 3, Ronda de Poniente 12, 28760 Tres Cantos, Madrid (Spain); Perez-Berna, A.J.; San Martin, C.; Carrascosa, J.L. [Centro Nacional de Biotecnologia (CNB-CSIC), Darwin 3, 28049 Madrid (Spain); Pablo, P.J. de [Departamento de Fisica de la Materia Condensada, C-3, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Gomez-Herrero, J., E-mail: julio.gomez@uam.es [Departamento de Fisica de la Materia Condensada, C-3, Universidad Autonoma de Madrid, Cantoblanco, 28049 Madrid (Spain)

    2012-03-15

    Control and minimization of tip-sample interaction forces are imperative tasks to maximize the performance of atomic force microscopy. In particular, when imaging soft biological matter in liquids, the cantilever dragging force prevents identification of the tip-sample mechanical contact, resulting in deleterious interaction with the specimen. In this work we present an improved jumping mode procedure that allows detecting the tip-sample contact with high accuracy, thus minimizing the scanning forces ({approx}100 pN) during the approach cycles. To illustrate this method we report images of human adenovirus and T7 bacteriophage particles which are prone to uncontrolled modifications when using conventional jumping mode. -- Highlights: Black-Right-Pointing-Pointer Improvement in atomic force microscopy in buffer solution. Black-Right-Pointing-Pointer Peak force detection. Black-Right-Pointing-Pointer Subtracting the cantilever dragging force. Black-Right-Pointing-Pointer Forces in the 100 pN range. Black-Right-Pointing-Pointer Imaging of delicate viruses with atomic force microscopy.

  4. Determination of 10 sulfonamide residues in meat samples by liquid chromatography with ultraviolet detection.

    Science.gov (United States)

    Di Sabatino, Marcello; Di Pietra, Anna Maria; Benfenati, Luigi; Di Simone, Bruno

    2007-01-01

    A liquid chromatography (LC) method is described for the simultaneous determination of 10 commonly used sulfonamide drug residues in meat. The 10 sulfonamide drugs of interest were sulfadiazine, sulfathiazole, sulfamerazine, sulfadimidine, sulfamethizole, sulfamonomethoxine, sulfachloropyridazine, sulfadoxine, sulfadimethoxine, and sulfaquinoxaline. The residues were extracted with acetone-chloroform (1 + 1). Sulfonamides were quantitatively retained in the extracting solution and afterwards eluted from a cation-exchanger solid-phase extraction cartridge with a solution of methanol-aqueous ammonia. The solution was dried, reconstituted with 5 mL methanol and filtered before analysis by LC-ultraviolet using a C18 column with a mobile phase gradient of potassium dihydrogen phosphate buffer, pH 2.5, and methanol-acetonitrile (30 + 70, v/v). The method was applied to cattle, swine, chicken, and sheep muscle tissues. The validation was performed with a fortified cattle meat sample at level of 100 ppb, which is the administrative maximum residue limit for sulfonamides in the European Union. The limit of quantitation for all sulfonamides was between 3 and 14 ppb. Recovery was evaluated for different meat matrixes. The mean recovery values were between 66.3% for pork meat samples and 71.5% for cattle meat samples.

  5. Determination by high-performance liquid chromatography of phenylbutazone in samples of plasma from fighting bulls.

    Science.gov (United States)

    Marti, M I González; Sánchez, González C I; Jiménez, Hernández; Cachán, García; Castro, de Cabo M J; Cuadrado, A L Garzón

    2002-03-25

    The purpose of this study was to investigate the possible presence of phenylbutazone in plasma samples from fighting bulls killed in 2nd and 3rd category bullrings in the province of Salamanca (Spain) in 1998, 1999 and 2000. For quantitative and qualitative determination, a high-performance liquid chromatograph was used, equipped with a photodiode-array detector and setting wavelengths at 240, 254 and 284 nm. The mobile phase optimized for the simultaneous detection of dexamethasone, betamethasone, flunixin and phenylbutazone, was 0.01 M acetic acid pH 3 in methanol (35:65 v/v) at a flow rate of 1 ml/min. Plasma samples were deproteinized with 400 microl of acetonitrile and 20 microl of the supernatant were injected directly into the chromatographic system equipped with a Lichrospher 60 RP select B column and guard column. For the quantitative analysis, standard calibration curves were made in a concentration range between 0.25 and 30 microg/ml, using betamethasone as internal standard. The retention time of phenylbutazone was 8.7 +/- 0.2 min and recovery was 83%. The detection and quantification limits were 0.016 and 0.029, respectively for A=240 nm. The study results show that 17 of the 74 samples analyzed in 1998, 18 of those from 1999 and 10 of those from 2000 were positive for phenylbutazone.

  6. Method for determination of uranium isotopes in environmental samples by liquid-liquid extraction with triisooctylamine/xylene in hydrochloric media and alpha spectrometry.

    Science.gov (United States)

    Popov, L

    2012-10-01

    Alternative method for determination of uranium isotopes in various environmental samples is presented. The method is based on total decomposition of the solid materials and preconcentration of liquid samples. The separation of uranium from interfering radionuclides and stable matrix elements is attained by liquid-liquid extraction with triisooctylamine/xylene in hydrochloric media. After the additional removal of stable iron by extraction with diisopropyl ether, purified uranium is electrodeposited on stainless steel disks and measured by alpha spectrometry. The analytical method has been successfully applied to the determination of uranium isotopes in water and bottom sediments from the rivers Danube, Ogosta and Tzibritza in Northwestern Bulgaria. The analytical quality was checked by analyzing reference materials with different matrices.

  7. Vortex-assisted magnetic β-cyclodextrin/attapulgite-linked ionic liquid dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the fast determination of four fungicides in water samples.

    Science.gov (United States)

    Yang, Miyi; Xi, Xuefei; Wu, Xiaoling; Lu, Runhua; Zhou, Wenfeng; Zhang, Sanbing; Gao, Haixiang

    2015-02-13

    A novel microextraction technique combining magnetic solid-phase microextraction (MSPME) with ionic liquid dispersive liquid-liquid microextraction (IL-DLLME) to determine four fungicides is presented in this work for the first time. The main factors affecting the extraction efficiency were optimized by the one-factor-at-a-time approach and the impacts of these factors were studied by an orthogonal design. Without tedious clean-up procedure, analytes were extracted from the sample to the adsorbent and organic solvent and then desorbed in acetonitrile prior to chromatographic analysis. Under the optimum conditions, good linearity and high enrichment factors were obtained for all analytes, with correlation coefficients ranging from 0.9998 to 1.0000 and enrichment factors ranging 135 and 159 folds. The recoveries for proposed approach were between 98% and 115%, the limits of detection were between 0.02 and 0.04 μg L(-1) and the RSDs changed from 2.96 to 4.16. The method was successfully applied in the analysis of four fungicides (azoxystrobin, chlorothalonil, cyprodinil and trifloxystrobin) in environmental water samples. The recoveries for the real water samples ranged between 81% and 109%. The procedure proved to be a time-saving, environmentally friendly, and efficient analytical technique.

  8. European guidelines for quality assurance in cervical cancer screening: recommendations for collecting samples for conventional and liquid-based cytology.

    NARCIS (Netherlands)

    Arbyn, M.; Herbert, A.; Schenck, U.; Nieminen, P.; Jordan, J.; Mcgoogan, E.; Patnick, J.; Bergeron, C.; Baldauf, J.J.; Klinkhamer, P.; Bulten, J.; Martin-Hirsch, P.

    2007-01-01

    The current paper presents an annex in the second edition of the European Guidelines for Quality Assurance in Cervical Cancer Screening. It provides guidance on how to make a satisfactory conventional Pap smear or a liquid-based cytology (LBC) sample. Practitioners taking samples for cytology should

  9. European guidelines for quality assurance in cervical cancer screening: recommendations for collecting samples for conventional and liquid-based cytology.

    NARCIS (Netherlands)

    Arbyn, M.; Herbert, A.; Schenck, U.; Nieminen, P.; Jordan, J.; Mcgoogan, E.; Patnick, J.; Bergeron, C.; Baldauf, J.J.; Klinkhamer, P.; Bulten, J.; Martin-Hirsch, P.

    2007-01-01

    The current paper presents an annex in the second edition of the European Guidelines for Quality Assurance in Cervical Cancer Screening. It provides guidance on how to make a satisfactory conventional Pap smear or a liquid-based cytology (LBC) sample. Practitioners taking samples for cytology should

  10. Dispersive liquid–liquid microextraction for metals enrichment: A useful strategy for improving sensitivity of laser-induced breakdown spectroscopy in liquid samples analysis

    OpenAIRE

    Aguirre Pastor, Miguel Ángel; Selva, E.J.; Hidalgo, Montserrat; Canals, Antonio

    2015-01-01

    A rapid and efficient Dispersive Liquid–Liquid Microextraction (DLLME) followed by Laser-Induced Breakdown Spectroscopy detection (LIBS) was evaluated for simultaneous determination of Cr, Cu, Mn, Ni and Zn in water samples. Metals in the samples were extracted with tetrachloromethane as pyrrolidinedithiocarbamate (APDC) complexes, using vortex agitation to achieve dispersion of the extractant solvent. Several DLLME experimental factors affecting extraction efficiency were optimized with a mu...

  11. Salting-out assisted liquid-liquid extraction combined with capillary HPLC for the determination of sulfonylurea herbicides in environmental water and banana juice samples.

    Science.gov (United States)

    Gure, Abera; Lara, Francisco J; Moreno-González, David; Megersa, Negussie; del Olmo-Iruela, Monsalud; García-Campaña, Ana M

    2014-09-01

    A salting-out assisted liquid-liquid extraction (SALLE) combined with capillary high performance liquid chromatography with diode array detector (capillary HPLC-DAD) was proposed for extraction and determination of residues of nine sulfonylurea herbicides (SUHs) in environmental water and banana juice samples. Various parameters affecting the extraction process such as the type and volume of the organic solvent, sample volume, type and amount of salt, pH of the sample and vortex time were optimized. Under optimum conditions, matrix matched calibration curves were established using river water and banana juice samples. Good linear relationships as well as low limits of detection, LODs (0.4-1.3 and 3-13 µg/L) and quantification, LOQs (1.3-4.3 and 10-43 µg/L) were obtained in water and banana juice samples, respectively. The precision (intra- and inter-day) of the peak areas expressed as relative standard deviations (%, RSD), at two concentration levels were below 10 % in both matrices. Recoveries obtained from spiked environmental waters (river water and groundwater) and banana juice samples, at two concentration levels, ranged from 72 to 115%. The results of the analysis revealed that the proposed SALLE-capillary HPLC method is simple, rapid, cheap and environmentally friendly, being successfully applicable for the determination of SUH residues in waters and banana juices.

  12. Arsenic speciation in clinical samples: urine analysis using fast micro-liquid chromatography ICP-MS.

    Science.gov (United States)

    Morton, Jackie; Leese, Elizabeth

    2011-02-01

    Arsenic speciation is a subject that is developing all the time both from improvements in analytical techniques and from increases in toxicological understanding. Despite speciation methods being widely developed, arsenic speciation is not routinely offered as an analysis in clinical laboratory. The work in this paper describes a simple routine method for arsenic speciation that could be easily implemented in clinical laboratories. The method described, a new, fast analytical method for arsenic speciation, is reported using micro-liquid chromatography hyphenated to an inductively coupled plasma mass spectrometer (μLC-ICP-MS). The method uses a low-pressure delivery six-port valve with a 5 cm anion exchange column, which allows a fully resolved separation of five arsenic species (arsenobetaine [AB], arsenite [As(3+)], arsenate [As(5+)], mono-methylarsonic acid [MMA(5+)] and dimethylarsinic acid [DMA(5+)]) in urine in just 6 min. This fast analytical method offers an arsenic speciation method that is feasible for a laboratory that does not have the capability for a dedicated arsenic speciation LC-ICP-MS instrument. The micro-LC system is small, easy to install and is fully integrated with the ICP-MS software. The results reported here are from urine samples from 65 workers in a semiconductor work providing a sample for their routine biological monitoring to assess workplace exposure. Control samples from 20 unexposed people were also determined. Results show that the semiconductor workers exhibit very low levels of arsenic in their urine samples, similar to the levels in the controls, and thus are not significantly exposed to arsenic. Care must be taken when interpreting urinary arsenic species results because it is not always possible to differentiate between dietary and other external sources of exposure.

  13. Aqueous two phase system based on ionic liquid for isolation of quinine from human plasma sample.

    Science.gov (United States)

    Flieger, J; Czajkowska-Żelazko, A

    2015-01-01

    Aqueous two phase system was applied for selective extraction of quinine from human plasma. Bi-phase was constructed from ionic liquid: butyl-methyl-imidazolium chloride after addition kosmotropic salts K₃PO₄ or KH₂PO₄. Quinine was determined in plasma samples after drinking of tonic containing quinine. Determination was performed by HPLC on 5-μm Zorbax SB-CN column and eluent containing 40% acetonitrile (v/v), 20 mM phosphate buffer at pH 3 and 40 mM NaPF₆ using external standard method. The spectrophotometric detection was set λ=214 nm. Selective fluorescence detection was performed at excitation of 325 nm and emission of 375 nm. Proposed strategy provides suitable sample purification and gives extraction yields in the range of 89-106%. The determination coefficient (R(2)) has a value ≥0.997 in the range of 50-800 ng/ml quinine concentration. The limit of quantification was set at 27.9 ng/ml and the detection limit was found to be 8.4 ng/ml under fluorescence detection.

  14. Determination of Capsaicin and Dihydrocapsaicin in Capsicum Fruit Samples using High Performance Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    Ayman Abdel Ghafar

    2011-10-01

    Full Text Available The aim of the present study was to determine the content of capsaicin and dihydrocapsaicin in Capsicum samples collected from city markets in Riyadh (Saudi Arabia, calculate their pungency in Scoville heat units (SHU and evaluate the average daily intake of capsaicin for the population of Riyadh. The investigated samples consisted of hot chillies, red chillies, green chillies, green peppers, red peppers and yellow peppers. Extraction of capsaicinoids was done using ethanol as solvent, while high performance liquid chromatography (HPLC was used for separation, identification and quantitation of the components. The limit of detection (LOD of the method was 0.09 and 0.10 µg/g for capsaicin and dihydrocapsaicin, respectively, while the limit of quantification (LOQ was 0.30 and 0.36 µg/g for capsaicin and dihydrocapsaicin, respectively. Hot chillies showed the highest concentration of capsaicin (4249.0 ± 190.3 µg/g and the highest pungency level (67984.60 SHU, whereas green peppers had the lowest detected concentration (1.0 ± 0.9 µg/g; green peppers, red peppers and yellow peppers were non pungent. The mean consumption of peppers for Riyadh city population was determined to be 15.5 g/person/day while the daily capsaicin intake was 7.584 mg/person/day.

  15. Analysis of Fluconazole in Human Urine Sample by High Performance Liquid Chromatography Method

    Science.gov (United States)

    Hermawan, D.; Ali, N. A. Md; Ibrahim, W. A. Wan; Sanagi, M. M.

    2013-04-01

    A method for determination of fluconazole, antifungal drug in human urine by using reversed-phased high performance liquid chromatography (RP-HPLC) with ultraviolet (UV) detector was developed. Optimization HPLC conditions were carried out by changing the flow rate and composition of mobile phase. The optimum separation conditions at a flow rate 0.85 mL/min with a composition of mobile phase containing methanol:water (70:30, v/v) with UV detection at a wavelength 254 nm was able to analyze fluconazole within 3 min. The excellent linearity was obtained in the range of concentration 1 to 10 μg/mL with r2 = 0.998. The limit of detection (LOD) and limit of quantitation (LOQ) were 0.39 μg/mL and 1.28 μg/mL, respectively. Solid phase extraction (SPE) method using octadecylsilane (C18) as a sorbent was used to clean-up and pre-concentrated of the urine sample prior to HPLC analysis. The average recoveries of fluconazole in spiked urine sample was 72.4% with RSD of 3.21% (n=3).

  16. Design and dynamic analysis of a piezoelectric linear stage for pipetting liquid samples

    Science.gov (United States)

    Yu-Jen, Wang; Chien, Lee; Yi-Bin, Jiang; Kuo-Chieh, Fu

    2017-06-01

    Piezoelectric actuators have been widely used in positioning stages because of their compact size, stepping controllability, and holding force. This study proposes a piezoelectric-driven stage composed of a bi-electrode piezoelectric slab, capacitive position sensor, and capillary filling detector for filling liquid samples into nanopipettes using capillary flow. This automatic sample-filling device is suitable for transmission electron microscopy image-based quantitative analysis of aqueous products with added nanoparticles. The step length of the actuator is adjusted by a pulse width modulation signal that depends on the stage position; the actuator stops moving once the capillary filling has been detected. A novel dynamic model of the piezoelectric-driven stage based on collision interactions between the piezoelectric actuator and the sliding clipper is presented. Unknown model parameters are derived from the steady state solution of the equivalent steady phase angle. The output force of the piezoelectric actuator is formulated using the impulse and momentum principle. Considering the applied forces and related velocity between the sliding clipper and the piezoelectric slab, the stage dynamic response is confirmed with the experimental results. Moreover, the model can be used to explain the in-phase slanted trajectories of piezoelectric slab to drive sliders, but not elliptical trajectories. The maximum velocity and minimum step length of the piezoelectric-driven stage are 130 mm s-1 and 1 μm respectively.

  17. Determination of capsaicin and dihydrocapsaicin in Capsicum fruit samples using high performance liquid chromatography.

    Science.gov (United States)

    Al Othman, Zeid Abdullah; Ahmed, Yacine Badjah Hadj; Habila, Mohamed Abdelaty; Ghafar, Ayman Abdel

    2011-10-24

    The aim of the present study was to determine the content of capsaicin and dihydrocapsaicin in Capsicum samples collected from city markets in Riyadh (Saudi Arabia), calculate their pungency in Scoville heat units (SHU) and evaluate the average daily intake of capsaicin for the population of Riyadh. The investigated samples consisted of hot chillies, red chillies, green chillies, green peppers, red peppers and yellow peppers. Extraction of capsaicinoids was done using ethanol as solvent, while high performance liquid chromatography (HPLC) was used for separation, identification and quantitation of the components. The limit of detection (LOD) of the method was 0.09 and 0.10 µg/g for capsaicin and dihydrocapsaicin, respectively, while the limit of quantification (LOQ) was 0.30 and 0.36 µg/g for capsaicin and dihydrocapsaicin, respectively. Hot chillies showed the highest concentration of capsaicin (4249.0 ± 190.3 µg/g) and the highest pungency level (67984.60 SHU), whereas green peppers had the lowest detected concentration (1.0 ± 0.9 µg/g); green peppers, red peppers and yellow peppers were non pungent. The mean consumption of peppers for Riyadh city population was determined to be 15.5 g/person/day while the daily capsaicin intake was 7.584 mg/person/day.

  18. Determination of {sup 226}Ra and {sup 224}Ra in sediments samples by liquid scintillation counting

    Energy Technology Data Exchange (ETDEWEB)

    Villa, M. [Facultad de Fisica. Av. Reina Mercedes s/n, apdo 1065, Departamento de Fisica Atomica, Molecular y Nuclear, Universidad de Sevilla, 41080-Sevilla (Spain)]. E-mail: mvilla@us.es; Moreno, H.P. [E.T.S. Arquitectura. Av. Reina Mercedes, 2, Departamento de Fisica Aplicada II, Universidad de Sevilla, 41012-Sevilla (Spain); Manjon, G. [E.T.S. Arquitectura. Av. Reina Mercedes, 2, Departamento de Fisica Aplicada II, Universidad de Sevilla, 41012-Sevilla (Spain)

    2005-10-01

    An experimental procedure has been developed for a rapid determination of the activity concentration of {sup 226}Ra and {sup 224}Ra in sediments by liquid scintillation counting. The importance of the method lies in its application to the measurement of sediments where the Ra-isotopes activity concentration has been increased due to an anthropomorphic enhancement based on releases of naturally occurring radioactive material (NORM). A sample pre-treatment, including a digestion with aqua regia and a precipitation of hydroxides, was applied to samples before the radium extraction, which was made by co-precipitation with barium. Measurements were done in a low background scintillation spectrometer Quantulus 1220, which can separate and detect simultaneously {alpha} and {beta} particles. Additionally, some improvements are suggested for a better {alpha} and {beta} interference correction of the results. The obtaining of radiochemical yields is also improved using {sup 133}Ba as tracer, which decays by emission of conversion electrons and {gamma}-rays; the wide range of radiochemical yields obtained confirms the need of this analyses. The procedure has been applied to the measurement of riverbed sediments from an estuary in the south-west of Spain, affected in the past by direct and indirect phosphogypsum discharges.

  19. Rapid pretreatment and determination of bisphenol A in water samples based on vortex-assisted liquid-liquid microextraction followed by high-performance liquid chromatography with fluorescence detection.

    Science.gov (United States)

    Yang, Xiao; Diao, Chun-Peng; Sun, Ai-Ling; Liu, Ren-Min

    2014-10-01

    A method for the rapid pretreatment and determination of bisphenol A in water samples based on vortex-assisted liquid-liquid microextraction followed by high-performance liquid chromatography with fluorescence detection was proposed in this paper. A simple apparatus consisting of a test tube and a cut-glass dropper was designed and applied to collect the floating extraction drop in liquid-liquid microextraction when low-density organic solvent was used as the extraction solvent. Solidification and melting steps that were tedious but necessary once the low-density organic solvent used as extraction solvent could be avoided by using this apparatus. Bisphenol A was selected as model pollutant and vortex-assisted liquid-liquid microextraction was employed to investigate the usefulness of the apparatus. High-performance liquid chromatography with fluorescence detection was selected as the analytical tool for the detection of bisphenol A. The linear dynamic range was from 0.10 to 100 μg/L for bisphenol A, with good squared regression coefficient (r(2) = 0.9990). The relative standard deviation (n = 7) was 4.7% and the limit of detection was 0.02 μg/L. The proposed method had been applied to the determination of bisphenol A in natural water samples and was shown to be economical, fast, and convenient.

  20. Respondent-Driven Sampling with Hard-to-Reach Emerging Adults: An Introduction and Case Study with Rural African Americans

    Science.gov (United States)

    Kogan, Steven M.; Wejnert, Cyprian; Chen, Yi-fu; Brody, Gene H.; Slater, LaTrina M.

    2011-01-01

    Obtaining representative samples from populations of emerging adults who do not attend college is challenging for researchers. This article introduces respondent-driven sampling (RDS), a method for obtaining representative samples of hard-to-reach but socially interconnected populations. RDS combines a prescribed method for chain referral with a…

  1. Prediction efficiency by near-infrared spectroscopy of immunoglobulin G in liquid and dried bovine colostrum samples.

    Science.gov (United States)

    Rivero, M Jordana; Alomar, Daniel; Valderrama, Ximena; Le Cozler, Yannick; Velásquez, Alejandro; Haines, Deborah

    2016-08-01

    The objective of this study was to compare the prediction efficiency of IgG concentration in bovine colostrum by NIRS, using liquid and dried (Dry-Extract Spectroscopy for Infrared Reflectance, DESIR) samples by transflectance and reflectance modes, respectively. Colostrum samples (157), obtained from 2 commercial Holstein dairy farms, were collected within the first hour after calving and kept at -20 °C until analysis. After thawing and homogenisation, a subsample of 500 mg of liquid colostrum was placed in an aluminium mirror transflectance cell (0·1 mm path length), in duplicate, to collect the spectrum. A glass fiber filter disc was infused with another subsample of 500 mg of colostrum, in duplicate, and dried in a forced-air oven at 60 °C for 20 min. The samples were placed in cells for dry samples to collect the spectra. The spectra in the VIS-NIR region (400-2500 nm) were obtained with a NIRSystems 6500 monochromator. Mathematical treatments, scatter correction treatments and number of cross-validation groups were tested to obtain prediction equations for both techniques. Reference analysis for IgG content was performed by radial immunodiffusion. The DESIR technique showed a higher variation in the spectral regions associated with water absorption bands, compared with liquid samples. The best equation for transflectance method (liquid samples) obtained a higher coefficient of determination for calibration (0·95 vs. 0·94, respectively) and cross validation (0·94 vs. 0·91, respectively), and a lower error of cross validation (9·03 vs. 11·5, respectively) than the best equation for reflectance method (DESIR samples). In final, both methods showed excellent capacity for quantitative analysis, with residual predictive deviations above 3. It is concluded that, regarding accuracy of prediction and time for obtaining results of IgG from bovine colostrum, NIRS analysis of liquid samples (transflectance) is recommended over dried samples (DESIR technique by

  2. Comparison of the performance of conventional, temperature-controlled, and ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction combined with high-performance liquid chromatography in analyzing pyrethroid pesticides in honey samples.

    Science.gov (United States)

    Zhang, Jiaheng; Gao, Haixiang; Peng, Bing; Li, Songqing; Zhou, Zhiqiang

    2011-09-23

    This research paper presents a comparative study of the performance of conventional, ultrasound-assisted (UA), and temperature-controlled (TC) ionic liquid (IL) dispersive liquid-phase microextraction (IL-DLLME). Various parameters that affect extraction efficiency, such as type and volume of extraction and disperser solvent, centrifugation time, salt addition, effect of temperature on TC-IL-DLLME, and effect of sonication time on UA-IL-DLLME, were evaluated. UA-IL-DLLME was found to provide the best extraction efficiency. Under optimized conditions, great enrichment factors (506-515) and good recoveries (101.2-103.0%) were obtained by analyte extraction in real samples. The limit of detections (LODs) ranged from 0.21 to 0.38 μg L(-1). Good linearity was obtained in the range of 0.5-200 μg L(-1) for ethofenprox and tetramethrin, and 1-200 μg L(-1) for meperfluthrin and alpha-cypermethrin. Based on optimized conditions, the UA-IL-DLLME method was applied and combined with high-performance liquid chromatography with diode array detection (HPLC-DAD) to determine the presence of ethofenprox, tetramethrin, meperfluthrin, and alpha-cypermethrin in honey samples.

  3. Determination of sunset yellow and tartrazine in food samples by combining ionic liquid-based aqueous two-phase system with high performance liquid chromatography.

    Science.gov (United States)

    Sha, Ou; Zhu, Xiashi; Feng, Yanli; Ma, Weixing

    2014-01-01

    We proposed a simple and effective method, by coupling ionic liquid-based aqueous two-phase systems (IL-ATPSs) with high performance liquid chromatography (HPLC), for the analysis of determining tartrazine and sunset yellow in food samples. Under the optimized conditions, IL-ATPSs generated an extraction efficiency of 99% for both analytes, which could then be directly analyzed by HPLC without further treatment. Calibration plots were linear in the range of 0.01-50.0 μg/mL for both Ta and SY. The limits of detection were 5.2 ng/mL for Ta and 6.9 ng/mL for SY. This method proves successful for the separation/analysis of tartrazine and sunset yellow in soft drink sample, candy sample, and instant powder drink and leads to consistent results as obtained from the Chinese national standard method.

  4. Determination of Sunset Yellow and Tartrazine in Food Samples by Combining Ionic Liquid-Based Aqueous Two-Phase System with High Performance Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    Ou Sha

    2014-01-01

    Full Text Available We proposed a simple and effective method, by coupling ionic liquid-based aqueous two-phase systems (IL-ATPSs with high performance liquid chromatography (HPLC, for the analysis of determining tartrazine and sunset yellow in food samples. Under the optimized conditions, IL-ATPSs generated an extraction efficiency of 99% for both analytes, which could then be directly analyzed by HPLC without further treatment. Calibration plots were linear in the range of 0.01–50.0 μg/mL for both Ta and SY. The limits of detection were 5.2 ng/mL for Ta and 6.9 ng/mL for SY. This method proves successful for the separation/analysis of tartrazine and sunset yellow in soft drink sample, candy sample, and instant powder drink and leads to consistent results as obtained from the Chinese national standard method.

  5. Application of In-Syringe Dispersive Liquid-Liquid Microextraction and Narrow-Bore Tube Dispersive Liquid-Liquid Microextraction for the Determination of Trace Amounts of BTEX in Water Samples.

    Science.gov (United States)

    Rahmani, Mashaallah; Kaykhaii, Massoud; Ghasemi, Elham; Tahernejad, Mohadeseh

    2015-08-01

    Two new simple and effective methods based on dispersive liquid-liquid microextraction (DLLME) procedure, termed "in-syringe DLLME (IS-DLLME)" and "narrow-bore tube DLLME (NB-DLLME)", were developed and applied for rapid and simultaneous separation and preconcentration of trace amounts of benzene, toluene, ethylbenzene and xylene isomers in water samples followed by gas chromatographic analysis. Different parameters influencing the extraction efficiency of both methods such as type and volume of the extraction solvent and the disperser solvent; pH, temperature and volume of sample solution and ionic strength of samples were investigated and optimized. Under optimal condition, the limits of detection ranged from 1.7 to 2.4 µg L(-1) for IS-DLLME and 1.5 to 2.2 µg L(-1) for NB-DLLME. Precision (as relative standard deviation) of the two techniques was between 2.1 and 4.6% for IS-DLLME and between 1.5 and 4.5% for NB-DLLME. The enrichment factors found to be between 20-29 and 31-73 for IS- and NB-DLLME, respectively. The applicability of the proposed methods was investigated by analyzing real water samples.

  6. Ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet for determination of three antifungal drugs in water and biological samples.

    Science.gov (United States)

    Ezoddin, Maryam; Shojaie, Mehran; Abdi, Khosrou; Karimi, Mohammad Ali

    2017-03-01

    A novel ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet (UAAD-LLM-SFO) followed by HPLC-UV detection was developed for the analysis of three antifungal drugs in water and biological samples. In this method, 1-dodecanol was used as the extraction solvent. The emulsion was rapidly formed by pulling in and pushing out the mixture of sample solution and extraction solvent for 5 times repeatedly using a 10-mL glass syringe while sonication was performed. Therefore, an organic dispersive solvent required in common microextraction methods was not used in the proposed method. After dispersing, an aliquot of acetonitrile was introduced as a demulsifier solvent into the sample solution to separate two phases. Therefore, some additional steps, such as the centrifugation, ultrasonication, or agitation of the sample solution, are not needed. Parameters influencing the extraction recovery were investigated. The proposed method showed a good linearity for the three antifungal drugs studied with the correlation coefficients (R (2) > 0.9995). The limits of detection (LODs) and the limits of the quantification (LOQs) were between 0.01-0.03 μg L(-1) and 0.03-0.08 μg L(-1), respectively. The preconcentration factors (PFs) were in the range of 107-116, respectively. The precisions, as the relative standard deviations (RSDs) (n = 5), for inter-day and intra-day analysis were in the range of 2.1-4.5% and 6.5-8.5%, respectively. This method was successfully applied to determine the three antifungal drugs in tap water and biological samples. The recoveries of antifungal drugs in these samples were 92.4-98.5%. Graphical abstract Ultrasound-air-assisted demulsified liquid-liquid microextraction by solidification of a floating organic droplet for the analysis of three antifungal drugs prior HPLC-UV.

  7. Effective indirect enrichment and determination of nitrite ion in water and biological samples using ionic liquid-dispersive liquid-liquid microextraction combined with high-performance liquid chromatography.

    Science.gov (United States)

    He, Lijun; Zhang, Kaige; Wang, Caijuan; Luo, Xianli; Zhang, Shusheng

    2011-06-10

    An ionic liquid dispersive liquid-liquid microextraction high-performance liquid chromatography (IL-DLLME-HPLC) method for effective enrichment and determination of nitrite ion in water and biological samples was developed. The method was based on the reaction of nitrite ion with p-nitroaniline in the presence of diphenylamine in acid media and IL-DLLME of azo product. The optimization of reaction and extraction conditions, such as kind and concentration of acid, reaction time, volume of reaction solvent, temperature, kind of extraction and dispersive solvent, volume of extraction and dispersive solvent, addition of salt, extraction and centrifugal time were studied. Under the optimal conditions, 1-octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide IL-DLLME procedure provided high enrichment factor of 430 and good extraction recovery of 91.7% for nitrite ion. The linearity was observed in the range of 0.4-500.0 μg L⁻¹ with good correlation coefficient (r²=0.9996). The relative standard deviations (RSDs) for five replicate measurements varied between 1.5% and 4.8%. The limit of detection of the method (S/N=3) was 0.05 μg L⁻¹. The interference effect of some anions and cations was also tested. The developed method allowed achieving an excellent enrichment factor, yielding a lower LOD in comparison with other methods. Moreover, the proposed method was able to analyze nitrite ion in water and biological samples with satisfactory recovery ranged from 96.5% to 107.3%.

  8. Measuring Black Carbon Concentrations in Liquid Samples Using the Single Particle Soot Photometer: Addressing Black Carbon Losses During Sample Storage and Nebulization

    Science.gov (United States)

    Menking, J. A.; Kaspari, S.; Jenkins, M.

    2011-12-01

    Black Carbon (BC), an aerosol created from the incomplete combustion of fossil and bio-fuels, is the second largest contributor to global warming next to CO2. BC deposited on snow and ice reduces the surface albedo, accelerating seasonal snowmelt and glacier retreat and influencing the regional water cycle and climate (Hansen and Nazarenko, 2004). BC emissions and its post-depositional spatial distribution in snow and ice are a large uncertainty in climate change analyses, thus measurements of global BC concentrations in liquid samples of snow and ice are desirable. The Single Particle Soot Photometer (SP2) is a relatively new method for measuring BC concentrations in liquid samples with promising advantages over other commonly used methods, namely that measurements require smaller sample volumes and are not affected by the presence of other absorbing particles. Despite potential advantages over traditional methods, total BC in liquid samples cannot be quantified because of methodological uncertainties. Preliminary tests show BC losses related to (1) nebulization and (2) changes to the sample during storage. BC in storage may adhere to the vial walls, resulting in BC losses. Particles containing BC may also agglomerate to form large particles with sizes outside of the SP2 detection range (80-650nm). Further losses are indicated in a comparison of polydisperse Aquadag (BC standard) particle size distributions between the ultrasonic nebulizer and a collision-type atomizer, which shows a loss of particles > ~500nm associated with the Cetac U-5000AT+ ultrasonic nebulizer. Larger particles may not be nebulized because of inefficiencies related to the ultrasonic transducer plate, and/or highly charged particles may adhere to the glass within the nebulizer, also resulting in BC losses. The purpose of this study was to determine the methods of storage and nebulization that maximize the amount of BC delivered to the SP2 inlet. Storage and sample parameters tested include

  9. Selective extraction of triazine herbicides from food samples based on a combination of a liquid membrane and molecularly imprinted polymers.

    Science.gov (United States)

    Mhaka, Byron; Cukrowska, Ewa; Bui, Bernadette Tse Sum; Ramström, Olof; Haupt, Karsten; Tutu, Hlanganani; Chimuka, Luke

    2009-10-02

    A selective extraction technique based on the combination of liquid membrane (microporous membrane liquid-liquid extraction) and molecularly imprinted polymers (MIP) was applied to triazines herbicides in food samples. Simazine, atrazine and propazine were extracted from aqueous food samples through the hydrophobic porous membrane that was impregnated with toluene, which also formed part of the acceptor phase. In the acceptor phase, the compounds were re-extracted onto MIP particles. The extraction technique was optimised for the amount of molecularly imprinted polymers particles in the organic acceptor phase, extraction time, and type of organic acceptor solvent and desorption solvent. An extraction time of 90 min and 50mg of MIP were found to be optimum parameters. Toluene as the acceptor phase was found to give higher triazines binding onto MIP particles compared to hexane and combinations of diethyl ether and hexane. 90% methanol in water was found to be the best desorption solvent compared to acetonitrile, methanol and water. The selectivity of the technique was demonstrated by extracting spiked lettuce and apple extracts where clean chromatograms were obtained compared to liquid membrane extraction alone or to the microporous membrane liquid-liquid extraction - non-imprinted polymer combination. The MIP showed a certain degree of group specificity and the extraction efficiency in lettuce extract was 79% (0.72) for simazine, 98% (1.55) for atrazine and 86% (3.08) for propazine.

  10. Centrifuge-less dispersive liquid-liquid microextraction base on the solidification of switchable solvent for rapid on-site extraction of four pyrethroid insecticides in water samples.

    Science.gov (United States)

    Hu, Lu; Wang, Huazi; Qian, Heng; Liu, Chaoran; Lu, Runhua; Zhang, Sanbing; Zhou, Wenfeng; Gao, Haixiang; Xu, Donghui

    2016-11-11

    An on-site dispersive liquid liquid microextraction base on the solidification of switchable solvent has been developed as a simple, rapid and eco-friendly sample extraction method for the fast determination of pyrethroid insecticides in aqueous samples using high-performance liquid chromatography with ultraviolet detection. In this extraction method, medium-chain saturated fatty acids (n≥10), which can rapidly solidify at low temperatures (insecticides were obtained in the concentration ranges of 1-500μg/L, with coefficients of determination greater than 0.9993. The recoveries of the four pyrethroid insecticides ranged from 84.7 to 95.3%, with relative standard deviations ranging from 1.6 to 4.6%. The limits of detection based on a signal-to-noise ratio of 3 were in the range of 0.24-0.68μg/L, and the enrichment factors were in the range of 121-136. The results demonstrate that this method was successfully applied to determine pyrethroid insecticides in real water samples. No centrifugation or any special apparatus are required, make this a promising method for rapid field-sampling procedures. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. A New Liquid Chromatography-Tandem Mass Spectrometry Method for Determination of Bisoprolol in Human Plasma Samples

    Directory of Open Access Journals (Sweden)

    Gabriela Peste

    2009-01-01

    Full Text Available Liquid chromatography (LC coupled with mass spectrometry (MS detection is one of the most powerful analytical tools for organic compound analysis. The advantages of using LC/MS methods over HPLC methods include: selectivity, chromatographic integrity, peak assignment, structural information, and rapid method development. In this paper, a new liquid chromatography-tandem mass spectrometry (LC-MS/MS method has been developed and validated for the determination of bisoprolol in human plasma samples, using metoprolol as internal standard and liquid-liquid extraction procedure. The assay has proven to be sensitive, specific and reproducible, suitable to determine the bisoprolol concentration, following a single oral administration of a 10 mg bisoprolol tablet in 22 healthy volunteers, in the bioequivalence study of Bisoprolol 10 mg coated tablets, produced by Antibiotice S.A. versus Concor 10 mg, produced by Merck.

  12. Development of counter current salting-out homogenous liquid-liquid extraction for isolation and preconcentration of some pesticides from aqueous samples.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Feriduni, Behruz; Afshar Mogaddam, Mohammad Reza

    2015-07-23

    In this paper, a new version of salting-out homogenous liquid-liquid extraction based on counter current mode combined with dispersive liquid-liquid microextraction has been developed for the extraction and preconcentration of some pesticides from aqueous samples and their determination by gas chromatography-flame ionization detection. In order to perform the method, aqueous solution of the analytes containing acetonitrile and 1,2-dibromoethane is transferred into a narrow bore tube which is filled partially with NaCl. During passing the solution through the tube, fine droplets of the organic phase are produced at the interface of solution and salt which go up through the tube and form a separated layer on the aqueous phase. The collected organic phase is removed and injected into de-ionized water for more enrichment of the analytes. Under the optimum extraction conditions, the method shows broad linear ranges for the target analytes. Enrichment factors and limits of detection for the selected pesticides are obtained in the ranges of 3480-3800 and 0.1-5μgL(-1), respectively. Relative standard deviations are in the range of 2-7% (n=6, C=50 or 100μgL(-1), each analyte). Finally, some aqueous samples were successfully analyzed using the developed method.

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

    Science.gov (United States)

    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.

  14. Clinical Introduction of a Novel Liquid Fiducial Marker for Breathing Adapted Radiotherapy of Non-Small Cell Lung Cancer

    DEFF Research Database (Denmark)

    Rydhog, Jonas Scherman

    .g. the heart and the lungs. Breathing adaptation and fiducial markers are tools which can increase precision in lung cancer radiotherapy. The primary aim of this thesis was to evaluate a novel liquid fiducial marker in both a pre-clinical and a clinical setting. The marker was tested rigorously for visibility...... delivery, e.g. breathing related tumour motion and anatomical changes during treatment. To ensure dose delivery to the target, a safety margin is added to the tumour. A large treatment volume, however, can be problematic due to the proximity of vital anatomical structures in the chest region, e...... for the tumour position in lung cancer patients. Furthermore, we evaluated the potential benefit of a breathing adaptation technique, where patients hold their breath during treatment delivery. We found that this technique reduced both tumour motion and doses to risk organs. Finally, we investigated...

  15. Coupling of homogeneous liquid-liquid extraction and dispersive liquid-liquid microextraction for the extraction and preconcentration of polycyclic aromatic hydrocarbons from aqueous samples followed by GC with flame ionization detection.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Khiavi, Elahe Behboudi; Khorram, Parisa; Mogaddam, Mohammad Reza Afshar

    2017-01-01

    In the present study, a simple and rapid method for the extraction and preconcentration of some polycyclic aromatic hydrocarbons in water samples has been developed. In this method, two sample preparation methods were combined to obtain high extraction recoveries and enrichment factors for sensitive analysis of the selected analytes. In the first stage of the method, a homogeneous solution containing an aqueous solution and cyclohexyl amine is broken by the addition of a salt. After centrifugation, the upper collected phase containing the extracted analytes is subjected to the following dispersive liquid-liquid microextraction method. Rapid injection of the mixture of cyclohexyl amine resulted from the first stage and 1,1,2-trichloroethane (as an extraction solvent) into an acetic acid solution is led to form a cloudy solution. After centrifuging, the fine droplets of the extraction solvent are settled down in the bottom of the test tube, and an aliquot of it is analyzed by gas chromatography. Under the optimum extraction conditions, enrichment factors and limits of detection for the studied analytes were obtained in the ranges of 616-752 and 0.08-0.20 μg/L, respectively. The simplicity, high extraction efficiency, short sample preparation time, low cost, and safety demonstrated the efficiency of this method relative to other approaches.

  16. Analysis of antibiotics from liquid sample using electrospray ionization-ion mobility spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Li Shu; Jia Jian; Gao Xiaoguang; He Xiuli [State Key Laboratory of Transducer Technology, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190 (China); Li Jianping, E-mail: jpli@mail.ie.ac.cn [State Key Laboratory of Transducer Technology, Institute of Electronics, Chinese Academy of Sciences, Beijing 100190 (China)

    2012-03-30

    Highlights: Black-Right-Pointing-Pointer The reduced mobilities of 18 antibiotics are determined. Black-Right-Pointing-Pointer Establishing antibiotic mass-mobility correlation using (12,4) potential model. Black-Right-Pointing-Pointer Multi-component characteristics of antibiotics can be revealed using ESI-IMS. Black-Right-Pointing-Pointer Most mixtures of antibiotics can be analyzed using ESI-IMS. Black-Right-Pointing-Pointer The detection limit of amoxicillin is 70 pg. - Abstract: The recent findings of antibiotic residues in aquatic environment at trace level have gained much concern for the detrimental effect on ecological and human health due to bacterial resistance. Here, the feasibility of using electrospray ionization ion mobility spectrometry (ESI-IMS) for analysis antibiotics in liquid sample is demonstrated. Reduced mobilities and collision cross sections of 18 antibiotics are experimentally measured and compared with theoretical values according to mass-mobility correlation. Gentamicin is used as an example to investigate the capability of ESI-IMS for multi-component analysis of antibiotics. Mixtures of antibiotics at different concentrations are analyzed. The estimated detection limit for amoxicillin is 0.7 mg L{sup -1} (70 pg) and the linear range of response maintains over two orders. This method will be a potential technique for the analysis of antibiotics in aquatic environment.

  17. Liquid-based versus conventional cytology of oral brush biopsies: a split-sample pilot study.

    Science.gov (United States)

    Remmerbach, T W; Pomjanski, N; Bauer, U; Neumann, H

    2017-01-11

    The aim of this prospective split sample study was to evaluate the applicability of liquid-based cytology (LBC) of oral brush biopsies for detection of oral cancer. Two different preparation techniques were investigated: the conventional transfer procedure to glass slides and the LBC preparation method. The obtainments of epithelial cells were performed five times with a nylon brush and transferred onto five glass slides. Additionally, the brushes, which were normally discarded, were stored in a fixative solution. Conventional slides and respective thin layers from a total of 113 cases were reviewed with both techniques. Thin layers showed excellent morphology on a clear background, which allowed an accurate diagnosis. In contrast, the conventional glass slides showed significantly more blood contamination and cell overlapping. The sensitivity of conventional cytological diagnosis was 96.3%, the specificity archived 90.6%, the positive predictive value was 96.3% and the negative predictive value scored 90.6%. The sensitivity of the cytological diagnosis using thin layers archived 97.5%, the specificity was 68.8%, the positive predictive value revealed 88.76% and negative predictive value was 91.7%. Our findings indicate that in oral cytology, LBC may replace other types of wet-fixed preparations using the full amount of collected cells, resulting in enhanced specimen quality archiving comparable values of diagnostic accuracy. LBC facilitates the cell collection due to simpler handling and less transfer errors by dentists and may improve the overall diagnostic accuracy of oral brush biopsies in future.

  18. Merits of online electrochemistry liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS).

    Science.gov (United States)

    Looi, Wen Donq; Brown, Blake; Chamand, Laura; Brajter-Toth, Anna

    2016-03-01

    A new online electrochemistry/liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS) system with a simple electrochemical thin-layer flow-through cell was developed and tested using N,N-dimethyl-p-phenylenediamine (DMPA) as a model probe. Although oxidation of DMPA is observed as a result of ionization of LS in positive ion mode LS DESI, application of voltage to the online electrochemical (EC) cell in EC/LS DESI MS increases yields of oxidation products. An advantage of LS DESI MS is its sensitivity in aqueous electrolyte solutions, which improves efficiency of electrochemical reactions in EC/LS DESI MS. In highly conductive low pH aqueous buffer solutions, oxidation efficiency is close to 100%. EC/ESI MS typically requires mixed aqueous/organic solvents and low electrolyte concentrations for efficient ionization in MS, limiting efficiency of electrochemistry online with MS. Independently, the results verify higher electrochemical oxidation efficiency during positive mode ESI than during LS DESI.

  19. Liquid Chromatographic Determination of Pioglitazone in Pharmaceuticals, Serum and Urine Samples

    Directory of Open Access Journals (Sweden)

    Shahnaz Perveen

    2011-12-01

    Full Text Available A rapid and reliable analytical method based on high-performance liquid chromatography (HPLC with UV detection (221nm has been developed for the determination of the anti-hyperglycemic agent Pioglitazone in pharmaceutical formulations and biological fluids (serum and urine after clean-up with solid-phase extraction. Chromatographic separation was achieved with a Chromolith® Performance RP-18e (100×4.6mm column using mobile phase composition of acetonitrile: mixed phosphate buffer (pH 2.5; 10mM (30:70, v/v with a flow rate of 2.0mL/min. The total run time was 2 min. under optimized conditions. The calibration curve was found to be linear in the range of 1-10 µg mL-1 with regression coefficient of 0.9996, and the lower limit of detection 72 ng/20µL injection. The method has been validated for the system suitability, linearity, precision and accuracy, limits of detection, specificity, stability and robustness. The %recovery of Pioglitazone in pharmaceutical formulations was found to be 104.7%. The assay has been applied successfully to the pharmaceutical Tablet samples and biological fluids (serum and urine of healthy volunteers.

  20. Influence of the operating parameters and of the sample introduction system on time correlation of line intensities using an axially viewed CCD-based ICP-AES system

    Energy Technology Data Exchange (ETDEWEB)

    Grotti, Marco, E-mail: grotti@chimica.unige.i [Dipartimento di Chimica e Chimica Industriale, Via Dodecaneso 31, 16146 Genova (Italy); Todoli, Jose Luis [Departamento de Quimica Analitica, Nutricion y Bromatologia, Universidad de Alicante, 03080, Alicante (Spain); Mermet, Jean Michel [Spectroscopy Forever, 01390 Tramoyes (France)

    2010-02-15

    The influence of the acquisition and operating parameters on time correlation between emission line intensities was investigated using axially viewed inductively coupled plasma-multichannel-based emission spectrometry and various sample introduction systems. It was found that to obtain flicker-noise limited signals, necessary to compensate for time-correlated signal fluctuations by internal standardization, the flicker-noise magnitude of the sample introduction system, the integration time and the emission line intensity had to be considered. The highest correlation between lines was observed for ultrasonic nebulization with desolvatation, the noisiest system among those considered, for which the contribution of the uncorrelated shot-noise was negligible. In contrast, for sample introduction systems characterized by lower flicker-noise levels, shot-noise led to high, non-correlated RSD values, making the internal standard method to be much less efficient. To minimize shot-noise, time correlation was improved by increasing the emission line intensities and the integration time. Improvement in repeatability did not depend only on time correlation, but also on the ratio between the relative standard deviations of the analytical and reference lines. The best signal compensation was obtained when RSD values of the reference and analytical lines were similar, which is usually obtained when the system is flicker-noise limited, while departure from similarity can lead to a degradation of repeatability when using the internal standard method. Moreover, the use of so-called robust plasma conditions, i.e. a high power (1500 W) along with a low carrier gas flow rate (0.8 L/min) improved also the compensation. Finally, high correlation and consequent improvement in repeatability by internal standardization was observed also in the presence of complex matrices (sediment and soil samples), although a matrix-induced degradation of the correlation between lines was generally

  1. Application of Cold-Induced Aggregation Microextraction Based on Ionic Liquid for Determination of Trace Amount of Cadmium and Lead in Powder Milk Samples

    Directory of Open Access Journals (Sweden)

    Mostafa Delavar

    2014-06-01

    Full Text Available Background: cold-induced aggregation micro extraction based (CIAME based on ionic liquid was used as a rapid and simple method for determination trace amounts of cadmium and lead in milk powder by analysis with flame atomic absorption spectrometry (FAAS. Methods: Sample solution containing of Cd2+ and Pb2+ in dynamic range, phosphate buffer (pH = 9, 3 ml, diethyl dithiocarbamate (complexing agent, Triton X-100, NaPF6 ,[HMIM][PF6] (extraction solvent were transferred into conical bottom glass tube. Sample was kept in a thermostated bath and then ice bath; a cloudy solution was formed. Two phases separated by centrifugation. After removing of aqueous phase, IL-phase was dissolved in methanol and diluted was injected to the FAAS by microsampler introduction. Results: ILs, containing imidazoliumcation and hexafluoro phosphate anion, [HMIM][PF6](70mg, 200 mg NaPF6 ,0.01 mol.L-1 DDTC, 0.015% of Triton X-100 obtained, pH 9 and centrifuge time; 5 min (4000 rmp was chosen. Detection limit were obtained 0.12 µgL-1, 1.61µgL-1, RSD 0.95%, 2.2% and enrichment factor of 70, 67 for Cd and Pb, respectively. Conclusion: CIAME allows determination of cadmium and lead in real samples in a simple, rapid and safe method with only a small amount of ionic liquid was used. In comparison with the organic solvent extraction, CIAME is much safer and the determination of species in high ionic strength samples is possible.

  2. Analysis of epinephrine, norepinephrine, and dopamine in urine samples of hospital patients by micellar liquid chromatography.

    Science.gov (United States)

    García Ferrer, Daniel; García García, Aurelio; Peris-Vicente, Juan; Gimeno-Adelantado, José Vicente; Esteve-Romero, Josep

    2015-12-01

    An analytical method based on micellar liquid chromatography was developed to determine the concentration of three catecholamines (epinephrine, norepinephrine, and dopamine) in urine. The detection of these compounds in urine can be useful to diagnose several diseases, related to stress and sympathoadrenal system dysfunction, using a non-invasive collection procedure. The sample pretreatment was a simple dilution in a micellar solution, filtration, and direct injection, thus avoiding time-consuming and tedious extraction steps. Therefore, there is no need to use an internal standard. The three catecholamines were eluted using a C18 column and a mobile phase of 0.055 M sodium dodecyl sulfate-1.5% methanol buffered at pH 3.8 running at 1.5 mL/min under isocratic mode in less than 25 min. The detection was performed by amperometry applying a constant potential of +0.5 V. The procedure was validated following the guidelines of the European Medicines Agency in terms of the following: calibration range (0.09-5 μg/mL), linearity (r(2) > 0.9995), limit of detection (0.02 μg/mL), within- and between-run accuracy (-6.5 to +8.4%) and precision (<10.2%), dilution integrity, matrix effect, robustness (<8.4), and stability. The obtained values were below those required by the guide. The method was rapid, easy-to-handle, eco-friendly, and safe and provides reliable quantitative data, and is thus useful for routine analysis. The procedure was applied to the analysis of epinephrine, norepinephrine, and dopamine in urine samples from patients of a local hospital.

  3. High performance liquid chromatography--atomic fluorescence spectrometric determination of arsenic species in beer samples

    Energy Technology Data Exchange (ETDEWEB)

    Melo Coelho, N.M.; Parrilla, Carmen; Cervera, M.L.; Pastor, A.; Guardia, M. de la

    2003-04-10

    A method has been developed for the direct determination of As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and As(V) in beers by hydride generation--atomic fluorescence spectrometry after separation of arsenic species by high performance liquid chromatography. Compounds were separated by anion-exchange chromatography with isocratic elution using KH{sub 2}PO{sub 4}/K{sub 2}HPO{sub 4} as mobile phase with elution times of 1.67, 2.08, 6.52 and 10.72 min for As(III), DMA, MMA and As(V), respectively. Parameters affecting the hydride generation of all arsenic species were studied and the best conditions were established as a reaction coil of 150 cm, for a sample injected volume of 100 {mu}l, a 4.0% (m/v) solution of sodium tetrahydroborate and 2.0 mol l{sup -1} hydrochloric acid with flow rates of 2.7 and 1.7 ml min{sup -1}, respectively and a flow rate of 500 ml min{sup -1} for the argon carrier gas. Under the best experimental conditions, the detection limit was found to be 0.12, 0.20, 0.27 and 0.39 {mu}g l{sup -1} for As(III), DMA, MMA and As(V), respectively. The relative standard deviation for eight independent determinations varied from 3.9 till 8.9% for species considered at a concentration level of 10.0 {mu}g l{sup -1}. Recovery and comparative studies evidenced that the method is suitable for the accurate determination of arsenic species in water and beer samples.

  4. Application of elevated temperature-dispersive liquid-liquid microextraction for determination of organophosphorus pesticides residues in aqueous samples followed by gas chromatography-flame ionization detection.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Afshar Mogaddam, Mohammad Reza; Rezaee Aghdam, Samaneh; Nouri, Nina; Bamorrowat, Mahdi

    2016-12-01

    In the present study, an elevated temperature, dispersive, liquid-liquid microextraction/gas chromatography-flame ionization detection was investigated for the determination, pre-concentration, and extraction of six organophosphorus pesticides (malathion, phosalone, dichlorvos, diazinon, profenofos, and chlorpyrifos) residues in fruit juice and aqueous samples. A mixture of 1,2-dibromoethane (extraction solvent) and dimethyl sulfoxide (disperser solvent) was injected rapidly into the sample solution heated at an elevated temperature. Analytical parameters, including enrichment factors (1600-2075), linearity (r>0.994), limits of detection (0.82-2.72ngmL(-1)) and quantification (2.60-7.36ngmL(-1)), relative standard deviations (<7%) and extraction recoveries (64-83%), showed the high efficiency of the method developed for analysis of the target analytes. The proposed procedure was used effectively to analyse selected analytes in river water and fruit juice, and diazinon was found at ngmL(-1) concentrations in apple juice.

  5. Extraction of carbamate pesticides in fruit samples by graphene reinforced hollow fibre liquid microextraction followed by high performance liquid chromatographic detection.

    Science.gov (United States)

    Ma, Xiaoxing; Wang, Juntao; Wu, Qiuhua; Wang, Chun; Wang, Zhi

    2014-08-15

    Graphene reinforced hollow fibre liquid phase microextraction combined with high performance liquid chromatography-diode array detection was developed for the determination of some carbamate pesticides (metolcarb, carbaryl, isoprocarb, and diethofencarb) in fruit samples. The main parameters that affect the extraction efficiency for the carbamates were investigated. Under the optimum conditions, a good linearity was observed in the range of 1.0-100.0 ng g(-1) for carbaryl and 3.0-100.0 ng g(-1) for the other three analytes, with the correlation coefficients (r) of 0.9965-0.9993. The limits of detection of the method ranged from 0.2 to 1.0 ng g(-1). The relative standard deviations were in the range from 6.2% to 7.8%. The results indicated that the developed method is sensitive and efficient for the determination of the carbamate pesticides in fruit samples. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. A solution for an inverse problem in liquid AFM: calculation of three-dimensional solvation structure on a sample surface

    CERN Document Server

    Amano, Ken-ich

    2013-01-01

    Recent frequency-modulated atomic force microscopy (FM-AFM) can measure three-dimensional force distribution between a probe and a sample surface in liquid. The force distribution is, in the present circumstances, assumed to be solvation structure on the sample surface, because the force distribution and solvation structure have somewhat similar shape. However, the force distribution is exactly not the solvation structure. If we would like to obtain the solvation structure by using the liquid AFM, a method for transforming the force distribution into the solvation structure is necessary. Therefore, in this letter, we present the transforming method in a brief style. We call this method as a solution for an inverse problem, because the solvation structure is obtained at first and the force distribution is obtained next in general calculation processes. The method is formulated (mainly) by statistical mechanics of liquid.

  7. Analysis of s-triazine herbicides in model systems and samples of groundwater by gas and liquid chromatography

    Directory of Open Access Journals (Sweden)

    Kostadinović Ljiljana

    2010-01-01

    Full Text Available In this paper, residues of s-triazine herbicides (Simazine, Atrazine, Amethrine, Promethrine and Azyprothrine have been determined in samples of model systems and real groundwater samples by gas-chromatography and high performance liquid chromatography. S-triazine herbicides were isolated from water samples by chloroform-methanol mixture (1:1, followed by purification of extract on the Al2O3 column. Gas-chromatographic determination the residues of s-triazines is performed on parallel capilar columns ULTRA I and ULTRA II, using specific NP detector. Liquid-chromatographic determination the s-triazines was performed on the column TSK ODS-120 A 5 mm 'LKB', using the mobile phase methanol-water (60:40. Total concentration of s-triazines in samples of Danube water was 3.54 mg dm-3. .

  8. Hyphenation of optimized microfluidic sample preparation with nano liquid chromatography for faster and greener alkaloid analysis

    NARCIS (Netherlands)

    Shen, Y.; Beek, van T.A.; Zuilhof, H.; Chen, B.

    2013-01-01

    A glass liquid–liquid extraction (LLE) microchip with three parallel 3.5 cm long and 100 µm wide interconnecting channels was optimized in terms of more environmentally friendly (greener) solvents and extraction efficiency. In addition, the optimized chip was successfully hyphenated with nano-liquid

  9. Hyphenation of optimized microfluidic sample preparation with nano liquid chromatography for faster and greener alkaloid analysis

    NARCIS (Netherlands)

    Shen, Y.; Beek, van T.A.; Zuilhof, H.; Chen, B.

    2013-01-01

    A glass liquid–liquid extraction (LLE) microchip with three parallel 3.5 cm long and 100 µm wide interconnecting channels was optimized in terms of more environmentally friendly (greener) solvents and extraction efficiency. In addition, the optimized chip was successfully hyphenated with nano-liquid

  10. High performance liquid chromatographic determination of ultra traces of two tricyclic antidepressant drugs imipramine and trimipramine in urine samples after their dispersive liquid-liquid microextraction coupled with response surface optimization.

    Science.gov (United States)

    Shamsipur, Mojtaba; Mirmohammadi, Mehrosadat

    2014-11-01

    Dispersive liquid-liquid microextraction (DLLME) coupled with high performance liquid chromatography by ultraviolet detection (HPLC-UV) as a fast and inexpensive technique was applied to the determination of imipramine and trimipramine in urine samples. Response surface methodology (RSM) was used for multivariate optimization of the effects of seven different parameters influencing the extraction efficiency of the proposed method. Under optimized experimental conditions, the enrichment factors and extraction recoveries were between 161.7-186.7 and 97-112%, respectively. The linear range and limit of detection for both analytes found to be 5-100ng mL(-1) and 0.6ng mL(-1), respectively. The relative standard deviations for 5ng mL(-1) of the drugs in urine samples were in the range of 5.1-6.1 (n=5). The developed method was successfully applied to real urine sample analyses.

  11. Estimation of the sensitivity of environmental sampling for detection of Salmonella in commercial layer flocks post-introduction of national control programmes.

    Science.gov (United States)

    Arnold, M E; Martelli, F; McLaren, I; Davies, R H

    2014-05-01

    A key element of national control programmes (NCPs) for Salmonella in commercial laying flocks, introduced across the European Union, is the identification of infected flocks and holdings through statutory sampling. It is therefore important to know the sensitivity of the sampling methods, in order to design effective and efficient surveillance for Salmonella. However, improved Salmonella control in response to the NCP may have influenced key factors that determine the sensitivity of the sampling methods used to detect Salmonella in NCPs. Therefore the aim of this study was to compare estimates of the sensitivity of the sampling methods using data collected before and after the introduction of the NCP, using Bayesian methods. There was a large reduction in the sensitivity of dust in non-cage flocks between the pre-NCP studies (81% of samples positive in positive flocks) and post-NCP studies (10% of samples positive in positive flocks), leading to the conclusion that sampling dust is not recommended for detection of Salmonella in non-cage flocks. However, cage dust (43% of samples positive in positive flocks) was found to be more sensitive than cage faeces (29% of samples positive in positive flocks). To have a high probability of detection, several NCP-style samples need to be used. For confirmation of Salmonella, five NCP faecal samples for cage flocks, and three NCP faecal boot swab samples for non-cage flocks would be required to have the equivalent sensitivity of the EU baseline survey method, which was estimated to have an 87% and 75% sensitivity to detect Salmonella at a 5% within-flock prevalence in cage and non-cage flocks, respectively.

  12. Sampling considerations when analyzing micrometric-sized particles in a liquid jet using laser induced breakdown spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Faye, C.B.; Amodeo, T.; Fréjafon, E. [Institut National de l' Environnement Industriel et des Risques (INERIS/DRC/CARA/NOVA), Parc Technologique Alata, BP 2, 60550 Verneuil-En-Halatte (France); Delepine-Gilon, N. [Institut des Sciences Analytiques, 5 rue de la Doua, 69100 Villeurbanne (France); Dutouquet, C., E-mail: christophe.dutouquet@ineris.fr [Institut National de l' Environnement Industriel et des Risques (INERIS/DRC/CARA/NOVA), Parc Technologique Alata, BP 2, 60550 Verneuil-En-Halatte (France)

    2014-01-01

    Pollution of water is a matter of concern all over the earth. Particles are known to play an important role in the transportation of pollutants in this medium. In addition, the emergence of new materials such as NOAA (Nano-Objects, their Aggregates and their Agglomerates) emphasizes the need to develop adapted instruments for their detection. Surveillance of pollutants in particulate form in waste waters in industries involved in nanoparticle manufacturing and processing is a telling example of possible applications of such instrumental development. The LIBS (laser-induced breakdown spectroscopy) technique coupled with the liquid jet as sampling mode for suspensions was deemed as a potential candidate for on-line and real time monitoring. With the final aim in view to obtain the best detection limits, the interaction of nanosecond laser pulses with the liquid jet was examined. The evolution of the volume sampled by laser pulses was estimated as a function of the laser energy applying conditional analysis when analyzing a suspension of micrometric-sized particles of borosilicate glass. An estimation of the sampled depth was made. Along with the estimation of the sampled volume, the evolution of the SNR (signal to noise ratio) as a function of the laser energy was investigated as well. Eventually, the laser energy and the corresponding fluence optimizing both the sampling volume and the SNR were determined. The obtained results highlight intrinsic limitations of the liquid jet sampling mode when using 532 nm nanosecond laser pulses with suspensions. - Highlights: • Micrometric-sized particles in suspensions are analyzed using LIBS and a liquid jet. • The evolution of the sampling volume is estimated as a function of laser energy. • The sampling volume happens to saturate beyond a certain laser fluence. • Its value was found much lower than the beam diameter times the jet thickness. • Particles proved not to be entirely vaporized.

  13. Liquid-based cytology versus conventional cytology for evaluation of cervical Pap smears: Experience from the first 1000 split samples

    OpenAIRE

    Vikrant Bhar Singh; Nalini Gupta; Raje Nijhawan; Radhika Srinivasan; Vanita Suri; Arvind Rajwanshi

    2015-01-01

    Context and Aim: Screening programs using conventional cytology conventional Pap smear (CPS) have successfully reduced cervical cancer, but newer tests like liquid-based cytology (LBC) and human papillomavirus testing might enhance screening. The main aim of the present study was to assess the diagnostic accuracy of LBC versus CPS using "split samples." Materials and Methods: This was a prospective study comprising of 1000 consecutive cervical "split samples" over a period of 1 year. Split sa...

  14. In situ metathesis reaction combined with liquid-phase microextraction based on the solidification of sedimentary ionic liquids for the determination of pyrethroid insecticides in water samples.

    Science.gov (United States)

    Hu, Lu; Zhang, Panjie; Shan, Wanyu; Wang, Xuan; Li, Songqing; Zhou, Wenfeng; Gao, Haixiang

    2015-11-01

    A novel dispersion liquid-liquid microextraction method based on the solidification of sedimentary ionic liquids (SSIL-DLLME), in which an in situ metathesis reaction forms an ionic liquid (IL) extraction phase, was developed to determine four pyrethroid insecticides (i.e., permethrin, cyhalothrin, fenpropathrin, and transfluthrin) in water followed by separation using high-performance liquid chromatography. In the developed method, in situ DLLME was used to enhance the extraction efficiency and yield. After centrifugation, the extraction solvent, tributyldodecylphosphonium hexafluorophosphate ([P44412][PF6]), was easily collected by solidification in the bottom of the tube. The effects of various experimental parameters, the quantity of tributyldodecylphosphonium bromide ([P44412]Br), the molar ratio of [P44412]Br to potassium hexafluorophosphate (KPF6), the ionic strength, the temperature of the sample solution, and the centrifugation time, were optimized using a Plackett-Burman design to identify the significant factors that affected the extraction efficiency. These significant factors were then optimized using a central composite design. Under the optimized conditions, the recoveries of the four pyrethroid insecticides at four spiked levels ranged from 87.1% to 101.7%, with relative standard deviations (RSDs) ranging from 0.1% to 5.5%. At concentration levels between 1 and 500 µg/L, good linearity was obtained, with coefficients of determination greater than 0.9995. The limits of detection (LODs) for the four pyrethroid insecticides were in the range of 0.71-1.54 µg/L. The developed method was then successfully used for the determination of pyrethroid insecticides in environmental samples. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Aqueous two-phase based on ionic liquid liquid-liquid microextraction for simultaneous determination of five synthetic food colourants in different food samples by high-performance liquid chromatography.

    Science.gov (United States)

    Sha, Ou; Zhu, Xiashi; Feng, Yanli; Ma, Weixing

    2015-05-01

    A rapid and effective method of aqueous two-phase systems based on ionic liquid microextraction for the simultaneous determination of five synthetic food colourants (tartrazine, sunset yellow, amaranth, ponceau 4R and brilliant blue) in food samples was established. High-performance liquid chromatography coupled with an ultraviolet detector of variable wavelength was used for the determinations. 1-alkyl-3-methylimidazolium bromide was selected as the extraction reagent. The extraction efficiency of the five colourants in the proposed system is influenced by the types of salts, concentrations of salt and [CnMIM]Br, as well as the extracting time. Under the optimal conditions, the extraction efficiencies for these five colourants were above 95%. The phase behaviours of aqueous two-phase system and extraction mechanism were investigated by UV-vis spectroscopy. This method was applied to the analysis of the five colourants in real food samples with the detection limit of 0.051-0.074 ng/mL. Good spiked recoveries from 93.2% to 98.9% were obtained.

  16. A novel method for simultaneous determination of selected elements in dolomite and magnesia by Inductively Coupled Plasma Atomic Emission Spectroscopy with slurry sample introduction

    Science.gov (United States)

    Bok-Badura, Joanna; Jakóbik-Kolon, Agata; Turek, Marian; Szczerba, Jacek; Lemanowicz, Marcin; Karoń, Krzysztof

    2015-11-01

    The slurry nebulization ICP-AES method for simultaneous determination of selected elements in dolomite and magnesia was proposed. Based on the investigation results the optimal conditions for this analysis were as follows: particle size CRM 782-1 and High Purity Magnesia BCS-CRM 389/1 were analyzed. Student's t-test proved that there were no statistically significant differences between determined values and the certified ones. This proves that the slurry sample introduction into plasma in ICP-AES technique can be applied for simultaneous determination of elements in dolomite and magnesia.

  17. Flame AAS/flame AES for trace determination in fresh and used lubricating oils with sample introduction by hydraulic high-pressure nebulization.

    Science.gov (United States)

    Berndt, H; Schaldach, G; Kägler, S H

    1996-04-01

    In hydraulic high-pressure nebulization (HHPN) an aerosol is produced by means of an HPLC-pump and a special nebulization nozzle, applying a pressure of about 200 bar. This spray technique has been employed for sample introduction of mineral oil samples in flame atomic absorption/flame emission spectrometry. The determination of the trace elements Al, Cr, Cu, Fe, K, Na, Ni, Pb, Si and V has been investigated. Viscosity hardly acts upon the sensitivity of the determination, thereby avoiding a time consuming dilution of oil samples. By means of two interconnecting sampling valves a calibration method based on the standard addition technique can be performed which is both simple and easy to carry out. In samples of used oils, results for Cu and Pb equalled those of XRF-analysis. Regarding Fe traces, data obtained from AAS and XRF measurement correlate. In comparison with sample uptake by pneumatic nebulization, which is restricted to diluted oil samples, detection limits decrease by a factor of 2 to 4, indicating the dilution required in pneumatic nebulization.

  18. Development of liquid chromatography-tandem mass spectrometry method for analysis of polyphenolic compounds in liquid samples of grape juice, green tea and coffee.

    Science.gov (United States)

    Sapozhnikova, Yelena

    2014-05-01

    A simple and fast method for the analysis of a wide range of polyphenolic compounds in juice, tea, and coffee samples was developed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The method was based on a simple sample preparation "dilute and shoot" approach, and LC-MS/MS quantification using genistein-d4 as an internal standard. The performance of six different syringeless filter devices was tested for sample preparation. The method was evaluated for recoveries of polyphenols at three spiking levels in juice, tea, and coffee samples. The recoveries of the majority of polyphenols were satisfactory (70-120%), but some varied significantly (20-138%) depending on the matrix. NIST Standard Reference Materials (SRM) 3257 Catechin Calibration Solutions and 3255 Camellia sinensis (Green Tea) Extract with certified concentrations of catechin and epicatechin were used for method validation. The measurement accuracy in two SRMs was 71-113%. The method was successfully applied to the analysis of liquid samples of grape juice, green tea, and coffee.

  19. Particle transport in a He-microchip plasma atomic emission system with an ultrasonic nebulizer for aqueous sample introduction

    Science.gov (United States)

    Oh, Joosuck; Lim, H. B.

    2008-11-01

    The transport efficiency of dried particles generated from an ultrasonic nebulizer (USN) was studied to improve the analytical performance of a lab-made, He-microchip plasma system, in which a quartz tube (~ 1 mm i.d.) was positioned inside the central channel of a poly(dimethylsiloxane) (PDMS) polymer chip. The polymer microchip plasma has the advantages of low cost, small size, easy handling and design, and self-ignition with long stabilization (> 24 h). However, direct introduction of aqueous solution into the microplasma for the detection of metals remains problematic due to plasma instability. In addition, the much smaller size of the system can cause signal suppression due to low transport efficiency. Therefore, knowledge of particle transport efficiency in this microplasma system is required to enhance the sensitivity and stability. The weight of transported particles in the range of 0.02 to 10 mg m - 3 was measured using a piezobalance with a precision of 0.4-17.8%, depending on the operating conditions. The significant effects of the USN operating conditions and the physical properties of the tubing, namely, length, inner diameter and surface characteristics, on the number of particles transported from the nebulizer to the microplasma were studied. When selected metals, such as Na, Mg and Pb, at a concentration of 5 mg L - 1 were nebulized, transported particles were obtained with a mass range of 0.5-5 mg m - 3 , depending on atomic weights. For application of the He-rf-microplasma, the atomic emission system was optimized by changing both the radio frequency (rf) power (60-200 W) and cooling temperature of the USN (- 12-9 °C). The limits of detection obtained for K, Na and Cu were 0.26, 0.22, and 0.28 mg L - 1 , respectively. These results confirmed the suitable stability and sensitivity of the He-rf-PDMS microchip plasma for application as an atomization source.

  20. Density-viscosity product of small-volume ionic liquid samples using quartz crystal impedance analysis.

    Science.gov (United States)

    McHale, Glen; Hardacre, Chris; Ge, Rile; Doy, Nicola; Allen, Ray W K; MacInnes, Jordan M; Bown, Mark R; Newton, Michael I

    2008-08-01

    Quartz crystal impedance analysis has been developed as a technique to assess whether room-temperature ionic liquids are Newtonian fluids and as a small-volume method for determining the values of their viscosity-density product, rho eta. Changes in the impedance spectrum of a 5-MHz fundamental frequency quartz crystal induced by a water-miscible room-temperature ionic liquid, 1-butyl-3-methylimiclazolium trifluoromethylsulfonate ([C4mim][OTf]), were measured. From coupled frequency shift and bandwidth changes as the concentration was varied from 0 to 100% ionic liquid, it was determined that this liquid provided a Newtonian response. A second water-immiscible ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4mim][NTf2], with concentration varied using methanol, was tested and also found to provide a Newtonian response. In both cases, the values of the square root of the viscosity-density product deduced from the small-volume quartz crystal technique were consistent with those measured using a viscometer and density meter. The third harmonic of the crystal was found to provide the closest agreement between the two measurement methods; the pure ionic liquids had the largest difference of approximately 10%. In addition, 18 pure ionic liquids were tested, and for 11 of these, good-quality frequency shift and bandwidth data were obtained; these 12 all had a Newtonian response. The frequency shift of the third harmonic was found to vary linearly with square root of viscosity-density product of the pure ionic liquids up to a value of square root(rho eta) approximately 18 kg m(-2) s(-1/2), but with a slope 10% smaller than that predicted by the Kanazawa and Gordon equation. It is envisaged that the quartz crystal technique could be used in a high-throughput microfluidic system for characterizing ionic liquids.

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

    Science.gov (United States)

    Zhang, Yufeng; Lee, Hian Kee

    2012-08-03

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

  2. Optimization of Sample Preparation for the Identification and Quantification of Saxitoxin in Proficiency Test Mussel Sample using Liquid Chromatography-Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Kirsi Harju

    2015-11-01

    Full Text Available Saxitoxin (STX and some selected paralytic shellfish poisoning (PSP analogues in mussel samples were identified and quantified with liquid chromatography-tandem mass spectrometry (LC-MS/MS. Sample extraction and purification methods of mussel sample were optimized for LC-MS/MS analysis. The developed method was applied to the analysis of the homogenized mussel samples in the proficiency test (PT within the EQuATox project (Establishment of Quality Assurance for the Detection of Biological Toxins of Potential Bioterrorism Risk. Ten laboratories from eight countries participated in the STX PT. Identification of PSP toxins in naturally contaminated mussel samples was performed by comparison of product ion spectra and retention times with those of reference standards. The quantitative results were obtained with LC-MS/MS by spiking reference standards in toxic mussel extracts. The results were within the z-score of ±1 when compared to the results measured with the official AOAC (Association of Official Analytical Chemists method 2005.06, pre-column oxidation high-performance liquid chromatography with fluorescence detection (HPLC-FLD.

  3. Entropic Description of Gas Hydrate Ice-Liquid Equilibrium via Enhanced Sampling of Coexisting Phases.

    Science.gov (United States)

    Małolepsza, Edyta; Kim, Jaegil; Keyes, Tom

    2015-05-01

    Metastable β ice holds small guest molecules in stable gas hydrates, so its solid-liquid equilibrium is of interest. However, aqueous crystal-liquid transitions are very difficult to simulate. A new molecular dynamics algorithm generates trajectories in a generalized NPT ensemble and equilibrates states of coexisting phases with a selectable enthalpy. With replicas spanning the range between β ice and liquid water, we find the statistical temperature from the enthalpy histograms and characterize the transition by the entropy, introducing a general computational procedure for first-order transitions.

  4. Development of one-step hollow fiber supported liquid phase sampling technique for occupational workplace air analysis using high performance liquid chromatography with ultra-violet detector.

    Science.gov (United States)

    Yan, Cheing-Tong; Chien, Hai-Ying

    2012-07-13

    In this study, a simple and novel one-step hollow-fiber supported liquid-phase sampling (HF-LPS) technique was developed for enriched sampling of gaseous toxic species prior to chemical analysis for workplace air monitoring. A lab-made apparatus designed with a gaseous sample generator and a microdialysis sampling cavity (for HF-LPS) was utilized and evaluated to simulate gaseous contaminant air for occupational workplace analysis. Gaseous phenol was selected as the model toxic species. A polyethersulfone hollow fiber dialysis module filled with ethylene glycol in the shell-side was applied as the absorption solvent to collect phenol from a gas flow through the tube-side, based on the concentration distribution of phenol between the absorption solvent and the gas flow. After sampling, 20 μL of the extractant was analyzed by high performance liquid chromatography with ultraviolet detection (HPLC-UV). Factors that influence the generation of gaseous standards and the HF-LPS were studied thoroughly. Results indicated that at 25 °C the phenol (2000 μg/mL) standard solution injected at 15-μL/min can be vaporized into sampling cavity under nitrogen flow at 780 mL/min, to generate gaseous phenol with concentration approximate to twice the permissible exposure limit. Sampling at 37.3 mL/min for 30 min can meet the requirement of the workplace air monitoring. The phenol in air ranged between 0.7 and 10 cm³/m³ (shows excellent linearity) with recovery between 98.1 and 104.1%. The proposed method was identified as a one-step sampling for workplace monitoring with advantages of convenience, rapidity, sensitivity, and usage of less-toxic solvent. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. High-frequency isotopic analysis of liquid water samples in the field - initial results from continuous water sampling and cavity ring-down spectroscopy

    Science.gov (United States)

    von Freyberg, Jana; Studer, Bjørn; Kirchner, James

    2016-04-01

    Studying rapidly changing hydrochemical signals in catchments can help to improve our mechanistic understanding of their water flow pathways and travel times. For these purposes, stable water isotopes (18O and 2H) are commonly used as natural tracers. However, high-frequency isotopic analyses of liquid water samples are challenging. One must capture highly dynamic behavior with high precision and accuracy, but the lab workload (and sample storage artifacts) involved in collecting and analyzing thousands of bottled samples should also be avoided. Therefore, we have tested Picarro, Inc.'s newly developed Continuous Water Sampler Module (CoWS), which is coupled to their L2130-i Cavity Ring-Down Spectrometer to enable real-time on-line measurements of 18O and 2H in liquid water samples. We coupled this isotope analysis system to a dual-channel ion chomatograph (Metrohm AG, Herisau, Switzerland) for analysis of major cations and anions, as well as a UV-Vis spectroscopy system (s::can Messtechnik GmbH, Vienna, Austria) and electrochemical probes for characterization of basic water quality parameters. The system was run unattended for up to a week at a time in the laboratory and at a small catchment. At the field site, stream-water and precipitation samples were analyzed, alternating at sub-hourly intervals. We observed that measured isotope ratios were highly sensitive to the liquid water flow rate in the CoWS, and thus to the hydraulic head difference between the CoWS and the samples from which water was drawn. We used a programmable high-precision dosing pump to control the injection flow rate and eliminate this flow-rate artifact. Our experiments showed that the precision of the CoWS-L2130-i-system for 2-minute average values was typically better than 0.06‰ for δ18O and 0.16‰ for δ2H. Carryover effects were 1% or less between isotopically contrasting water samples for 30-minute sampling intervals. Instrument drift could be minimized through periodic analysis of

  6. Particle transport in a He-microchip plasma atomic emission system with an ultrasonic nebulizer for aqueous sample introduction

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Joosuck [Department of Chemistry, Dankook University, 126 Jukjeon-dong, Suji-gu, Yongin-si, Gyeonggi-do, 448-701 (Korea, Republic of); Lim, H.B. [Department of Chemistry, Dankook University, 126 Jukjeon-dong, Suji-gu, Yongin-si, Gyeonggi-do, 448-701 (Korea, Republic of)], E-mail: plasma@dankook.ac.kr

    2008-11-15

    The transport efficiency of dried particles generated from an ultrasonic nebulizer (USN) was studied to improve the analytical performance of a lab-made, He-microchip plasma system, in which a quartz tube ({approx} 1 mm i.d.) was positioned inside the central channel of a poly(dimethylsiloxane) (PDMS) polymer chip. The polymer microchip plasma has the advantages of low cost, small size, easy handling and design, and self-ignition with long stabilization (> 24 h). However, direct introduction of aqueous solution into the microplasma for the detection of metals remains problematic due to plasma instability. In addition, the much smaller size of the system can cause signal suppression due to low transport efficiency. Therefore, knowledge of particle transport efficiency in this microplasma system is required to enhance the sensitivity and stability. The weight of transported particles in the range of 0.02 to 10 mg m{sup -3} was measured using a piezobalance with a precision of 0.4-17.8%, depending on the operating conditions. The significant effects of the USN operating conditions and the physical properties of the tubing, namely, length, inner diameter and surface characteristics, on the number of particles transported from the nebulizer to the microplasma were studied. When selected metals, such as Na, Mg and Pb, at a concentration of 5 mg L{sup -1} were nebulized, transported particles were obtained with a mass range of 0.5-5 mg m{sup -3}, depending on atomic weights. For application of the He-rf-microplasma, the atomic emission system was optimized by changing both the radio frequency (rf) power (60-200 W) and cooling temperature of the USN (- 12-9 deg. C). The limits of detection obtained for K, Na and Cu were 0.26, 0.22, and 0.28 mg L{sup -1}, respectively. These results confirmed the suitable stability and sensitivity of the He-rf-PDMS microchip plasma for application as an atomization source.

  7. Overview of nongynecological samples prepared with liquid-based cytology medium.

    Science.gov (United States)

    Ren, Shuyue; Solomides, Charalambos; Draganova-Tacheva, Rossitza; Bibbo, Marluce

    2014-01-01

    Liquid-based cytology of nongynecological specimens is commonly used in cytology laboratories throughout the world and various processing methods, such as ThinPrep and SurePath, have been reported. The cytological features and performance of liquid-based cytology for various cytology specimens, including body cavity fluids, urine, brushing specimens and fine-needle aspiration of various lesions, were reviewed and compared with the experience of our laboratory and the literature published in PubMed. The parameters for the evaluation of liquid-based cytology and conventional smears were described in the various types of specimens. Criteria for the interpretation of nongynecological liquid-based cytology were highlighted to show differences in cell morphology, background and artifacts. The interpretation requires familiarity with the appearance of liquid-based cytology in the various types of preparations to avoid misdiagnosis. Cell blocks can be prepared with specimens preserved in a liquid-based cytology medium and immunocytochemical stains and molecular testing can be successfully performed. These are important adjuncts in order to reach a definitive diagnosis.

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

    Science.gov (United States)

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

    2012-09-01

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

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

    Science.gov (United States)

    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.

  10. In situ liquid-liquid extraction as a sample preparation method for matrix-assisted laser desorption/ionization MS analysis of polypeptide mixtures

    DEFF Research Database (Denmark)

    Kjellström, Sven; Jensen, Ole Nørregaard

    2003-01-01

    A novel liquid-liquid extraction (LLE) procedure was investigated for preparation of peptide and protein samples for matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). LLE using ethyl acetate as the water-immiscible organic solvent enabled segregation of hydrophobic...... matrix to the organic solvent enhanced the efficiency of the LLE-MALDI MS method for analysis of hydrophobic peptides and proteins. LLE-MALDI MS enabled the detection of the hydrophobic membrane protein bacteriorhodopsin as a component in a simple protein mixture. Peptide mixtures containing...... phosphorylated, glycosylated, or acylated peptides were successfully separated and analyzed by the in situ LLE-MALDI MS technique and demonstrate the potential of this method for enhanced separation and structural analysis of posttranslationally modified peptides in proteomics research....

  11. Determination of fungicide carbendazim in water and soil samples using dispersive liquid-liquid microextraction and microvolume UV-vis spectrophotometry.

    Science.gov (United States)

    Pourreza, Nahid; Rastegarzadeh, Saadat; Larki, Arash

    2015-03-01

    This article presents a new and sensitive method for the determination of trace amounts of fungicide carbendazim by dispersive liquid-liquid microextraction (DLLME) combined with UV-vis spectrophotometry. The method is based on the reduction of Fe(III) to Fe(II) by carbendazim, its reaction with potassium ferricynide to form a blue product and extraction into CCL4 by DLLME technique using methyltrioctylammonium chloride (Aliquat 336) as a disperser agent. Under the established optimum conditions, the calibration graph was linear in the range of 5-600 ng mL(-1) of carbendazim with a limit of detection of 2.1 ng mL(-1). The relative standard deviations for eight replicate determinations of 50 and 300 ng mL(-1) of carbendazim were 3.9% and 1.0%, respectively. The proposed method was successfully applied to determination of carbendazim in soil and water samples.

  12. Pico-litre Sample Introduction and Acoustic Levitation Systems for Time Resolved Protein Crystallography Experiments at XFELS

    Directory of Open Access Journals (Sweden)

    Peter Docker

    2017-07-01

    Full Text Available The system described in this work is a variant from traditional acoustic levitation first described by, Marzo et al. It uses multiple transducers eliminating the requirement for a mirror surface, allowing for an open geometry as the sound from multiple transducers combines to generate the acoustic trap which is configured to catch pico litres of crystal slurries. These acoustic traps also have the significant benefit of eliminating potential beam attenuation due to support structures or microfluidic devices. Additionally they meet the need to eliminate sample environments when experiments are carried out using an X-ray Free Electron Lasers (XFEL such as the Linac Coherent Light Source (LCLS as any sample environment would not survive the exposure to the X-Ray beam. XFELs generate Light a billion times brighter than the sun. The application for this system will be to examine turn over in Beta lactamase proteins which is responsible for bacteria developing antibiotic resistance and therefore of significant importance to future world health. The system will allow for diffraction data to be collected before and after turnover allowing for a better understanding of the underling processes. The authors first described this work at Nanotech 2017.

  13. Enhancement of Sensitivity for Determination of Phenols in Environmental Water Samples by Single-drop Liquid Phase Microextraction Using Ionic Liquid prior to HPLC

    Institute of Scientific and Technical Information of China (English)

    Qing Xiang ZHOU; Jun Ping XIAO; Cun Ling YE; Xin Ming WANG

    2006-01-01

    A single-drop liquid phase micro-extraction procedure using 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM][PF6]) was demonstrated for the sensitive determination of four phenols in water samples. Under the optimized conditions, the linear range of proposed phenol, 2-naphthol, 2-nitrophenol and 4-chlorophenol, respectively. The experimental results indicated that the effect of complex matrices natural water samples could be resolved with addition of sodium ethylene diamine tetracetate (EDTA) into the samples. Excellent spiked recoveries were achieved for these four phenols ranged from 86.2%-114.9 %. All these facts demonstrated that the proposed method with merits of low cost, simplicity and easy operating would be a competitive alternative procedure for the determination of such compounds at trace level.

  14. DEVELOPMENT OF METHODOLOGY AND FIELD DEPLOYABLE SAMPLING TOOLS FOR SPENT NUCLEAR FUEL INTERROGATION IN LIQUID STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Berry, T.; Milliken, C.; Martinez-Rodriguez, M.; Hathcock, D.; Heitkamp, M.

    2012-06-04

    This project developed methodology and field deployable tools (test kits) to analyze the chemical and microbiological condition of the fuel storage medium and determine the oxide thickness on the spent fuel basin materials. The overall objective of this project was to determine the amount of time fuel has spent in a storage basin to determine if the operation of the reactor and storage basin is consistent with safeguard declarations or expectations. This project developed and validated forensic tools that can be used to predict the age and condition of spent nuclear fuels stored in liquid basins based on key physical, chemical and microbiological basin characteristics. Key parameters were identified based on a literature review, the parameters were used to design test cells for corrosion analyses, tools were purchased to analyze the key parameters, and these were used to characterize an active spent fuel basin, the Savannah River Site (SRS) L-Area basin. The key parameters identified in the literature review included chloride concentration, conductivity, and total organic carbon level. Focus was also placed on aluminum based cladding because of their application to weapons production. The literature review was helpful in identifying important parameters, but relationships between these parameters and corrosion rates were not available. Bench scale test systems were designed, operated, harvested, and analyzed to determine corrosion relationships between water parameters and water conditions, chemistry and microbiological conditions. The data from the bench scale system indicated that corrosion rates were dependent on total organic carbon levels and chloride concentrations. The highest corrosion rates were observed in test cells amended with sediment, a large microbial inoculum and an organic carbon source. A complete characterization test kit was field tested to characterize the SRS L-Area spent fuel basin. The sampling kit consisted of a TOC analyzer, a YSI

  15. A Novel Sample Introduction Technique for the Simultaneous Determination of As, Se, Ge and Hg in Chinese Medicinal Material

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A novel technique of Moveable Reduction Bed Hydride Generator(MRBHG) was applied to the hydride generation or cold vapor generation of As, Se, Ge, and Hg existing in Traditional Chinese Medicinal Material(TCM). The simultaneous determination of the multi-elements was performed with ICP-MS. A solid reduction system involving the use of potassium tetraborohydride and tartaric acid was applied to generating metal hydride or cold vapor efficiently. The factors affecting the metal cold vapor generation were studied. The main advantage of the technique is that only a 4 μL volume of sample was required for the cold vapor generation. The absolute detection limits of all the elements studied are in 10-12 g level.

  16. Highly selective ionic liquid-based microextraction method for sensitive trace cobalt determination in environmental and biological samples

    Energy Technology Data Exchange (ETDEWEB)

    Berton, Paula [Analytical Chemistry Research and Development Group (QUIANID), (LISAMEN - CCT - CONICET - Mendoza), Av. Ruiz Leal S/N Parque General San Martin, M 5502 IRA Mendoza (Argentina); Wuilloud, Rodolfo G., E-mail: rwuilloud@mendoza-conicet.gov.ar [Analytical Chemistry Research and Development Group (QUIANID), (LISAMEN - CCT - CONICET - Mendoza), Av. Ruiz Leal S/N Parque General San Martin, M 5502 IRA Mendoza (Argentina); Instituto de Ciencias Basicas, Universidad Nacional de Cuyo, Mendoza (Argentina)

    2010-03-10

    A simple and rapid dispersive liquid-liquid microextraction procedure based on an ionic liquid (IL-DLLME) was developed for selective determination of cobalt (Co) with electrothermal atomic absorption spectrometry (ETAAS) detection. Cobalt was initially complexed with 1-nitroso-2-naphtol (1N2N) reagent at pH 4.0. The IL-DLLME procedure was then performed by using a few microliters of the room temperature ionic liquid (RTIL) 1-hexyl-3-methylimidazolium hexafluorophosphate [C{sub 6}mim][PF{sub 6}] as extractant while methanol was the dispersant solvent. After microextraction procedure, the Co-enriched RTIL phase was solubilized in methanol and directly injected into the graphite furnace. The effect of several variables on Co-1N2N complex formation, extraction with the dispersed RTIL phase, and analyte detection with ETAAS, was carefully studied in this work. An enrichment factor of 120 was obtained with only 6 mL of sample solution and under optimal experimental conditions. The resultant limit of detection (LOD) was 3.8 ng L{sup -1}, while the relative standard deviation (RSD) was 3.4% (at 1 {mu}g L{sup -1} Co level and n = 10), calculated from the peak height of absorbance signals. The accuracy of the proposed methodology was tested by analysis of a certified reference material. The method was successfully applied for the determination of Co in environmental and biological samples.

  17. Temperature-controlled ionic liquid dispersive liquid phase microextraction combined with ultra-high-pressure liquid chromatography for the rapid determination of triclosan,triclocarban and methyl-triclosan in aqueous samples

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    As extraction solvents,ionic liquids have green characteristics.In this study,an environmentally benign analytical method termed temperature-controlled ionic liquid dispersive liquid phase microextraction (TIL-DLME) combined with ultra-highpressure liquid chromatography (UHPLC)-tunable ultraviolet detection (TUV) was developed for the pre-concentration and determination of triclosan (TCS),triclocarban (TCC) and methyl-triclosan (M-TCS) in water samples.Significant parameters that may affect extraction efficiencies were examined and optimized,including the types and amount of ionic liquids,volume of the diluent,heating temperature,cooling time,salt effect and pH value.Under the optimum conditions,linearity of the method was observed in the ranges of 0.0100-100 μgL-1 for TCS and M-TCS,and 0.00500-50.0 μgL-1 for TCC with correlation coefficients (r2) > 0.9903.The limits of detection (LODs) ranged from 1.15 to 5.33 ngL-1.TCS in domestic water and TCC in reclaimed water were detected at the concentrations of 1.01 and 0.126 μgL-1,respectively.The spiked recoveries of the three target compounds in reclaimed water,irrigating water,waste water and domestic water samples were obtained in the ranges of 68.4%-71.9%,61.6%-87.8%,58.9%-74.9% and 64.9%-92.4%,respectively.Compared with the previous dispersive liquid-liquid microextraction method (DLLME) about the determination of TCS,TCC and M-TCS,this method is not only more environmentally friendly but also more sensitive.

  18. Vortex-assisted hollow fibre liquid-phase microextraction technique combined with high performance liquid chromatography-diode array detection for the determination of oestrogens in milk samples.

    Science.gov (United States)

    Wang, Peijin; Xiao, Yu; Liu, Wenjun; Wang, Juan; Yang, Yaling

    2015-04-01

    A rapid, simple, sensitive and environmentally friendly method has been developed for the determination of three oestrogens (17β-estradiol (17β-E2), estrone (E1), and diethylstilbestrol (DES)) in milk samples by using vortex-assisted hollow fibre liquid-phase microextraction (VA-HF-LPME) and high performance liquid chromatography. Method is based on the microextraction of oestrogens from sample solution into 15 μL of nonanoic acid as extracting agent, which is placed inside the hollow fibre followed by vortex-mixing. Vortex provided effective and mild mixing of sample solution and increased the contact between analytes and boundary layers of the hollow fibre, thereby enhancing mass transfer rate and leading to high recovery of target analytes. The extraction equilibrium is achieved within 2 min. Parameters influencing the recovery were investigated and optimized. The proposed technique provided good linearity (>0.9984), repeatability (RSD = 2.56-4.38), low limits of detection (0.06-0.17 ng mL(-1)), and high enrichment factor (330).

  19. Application of In-Syringe Dispersive Liquid-Liquid Microextraction Coupled to GC/FID for Determination of Trace Contamination of Phthalate Esters in Water Samples.

    Science.gov (United States)

    Sargazi, Shahnaz; Mirzaei, Ramazan; Rahmani, Mashaallah; Sheikh, Masoome

    2015-09-01

    In this work, a simple and easy to handle one-step in-syringe setup for the dispersive liquid-liquid microextraction method has been developed for preconcentration of trace quantities of four kinds of phthalate esters (PEs) in water samples as a prior step to its determination by gas chromatography/flame ionization detector. The environmental pollution at this method has been limited due to using a glass syringe as extraction unit and also a very small amount of n-hexane as a safe solvent. Some important parameters such as the type of extraction and disperser solvents, extraction and disperser solvents volume, sample volume and ionic strength were investigated and optimized. Validation experiments showed that the optimized method had precision (1.7-6.9%) and high recovery (94.32-104.7%), and the limits of detection were from 0.406 to 1.33 µg L(-1). At the end, the method was successfully applied for the determination of PEs in real water samples.

  20. Determination of Lead in Water Samples Using a New Vortex-Assisted, Surfactant-Enhanced Emulsification Liquid-Liquid Microextraction Combined with Graphite Furnace Atomic Absorption Spectrometry.

    Science.gov (United States)

    Peng, Guilong; He, Qiang; Lu, Ying; Mmereki, Daniel; Pan, Weiliang; Tang, Xiaohui; Zhou, Guangming; Mao, Yufeng; Su, Xaioxuan

    2016-04-01

    A low toxic solvent-based vortex-assisted surfactant-enhanced emulsification liquid-liquid microextraction (LT-VSLLME) combined with graphite furnace atomic absorption spectrometry was developed for the extraction and determination of lead (Pb) in water samples. In the LT-VSLLME method, the extraction solvent was dispersed into the aqueous samples by the assistance of vortex agitator. Meanwhile, the addition of a surfactant, which acted as an emulsifier, could enhance the speed of the mass-transfer from aqueous samples to the extraction solvent. The influences of analytical parameters, including extraction solvent type and its volume, surfactant type and its volume, pH, concentration of chelating agent, salt effect and extraction time were investigated. Under the optimized conditions, a good relative standard deviation of 3.69% at 10 ng L(-1) was obtained. The calibration graph showed a linear pattern in the ranges of 5-30 ngL(-1), with a limit of detection of 0.76 ng L(-1). The linearity was obtained by five points in the concentration range of 5-30 ngL(-1). The enrichment factor was 320. The procedure was applied to wastewater and river water, and the accuracy was assessed through the analysis of the recovery experiments.

  1. Determination of Trace Amounts of Palladium in Water Samples by Graphite Furnace Atomic Absorption Spectrometry after Dispersive Liquid-Liquid Microextraction

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Jamali

    2013-01-01

    Full Text Available A simple, rapid, and powerful microextraction technique was used for determination of palladium (II ion in water samples using dispersive liquid-liquid microextraction (DLLME followed by graphite furnace atomic absorption spectrometry (GF AAS. The different variables affecting the complexation and extraction conditions such as extraction and disperser solvent type, extraction time, pH, and concentration of chelating agent were optimized. Under the optimum conditions, the calibration graph was linear in the ranges of 0.05–1 μg L−1 with detection limit of 0.02 μg L−1. The precision (RSD % for ten replicate determination at 0.2 μg L−1 of palladium was better than 3.5% and the enrichment factor 166.5 was obtained from only 5.0 mL of sample. Under the presence of foreign ions, no significant interference was observed. Finally, accuracy and application of the method were estimated by using test samples of natural waters spiked with different amounts of palladium.

  2. Development of a new dispersive liquid-liquid microextraction method in a narrow-bore tube for preconcentration of triazole pesticides from aqueous samples.

    Science.gov (United States)

    Farajzadeh, Mir Ali; Djozan, Djavanshir; Khorram, Parisa

    2012-02-03

    In the present work a new, simple, rapid and environmentally friendly dispersive liquid-liquid microextraction (DLLME) method has been developed for extraction/preconcentration of some triazole pesticides in aqueous samples and in grape juice. The extract was analyzed with gas chromatography-flame ionization detection (GC-FID) or gas chromatography-mass spectrometry (GC-MS). The DLLME method was performed in a narrow-bore tube containing aqueous sample. Acetonitrile and a mixture of n-hexanol and n-hexane (75:25, v/v) were used as disperser and extraction solvents, respectively. The effect of several factors that influence performance of the method, including the chemical nature and volume of the disperser and extraction solvents, number of extraction, pH and salt addition, were investigated and optimized. Figures of merit such as linearity (r(2)>0.995), enrichment factors (EFs) (263-380), limits of detection (0.3-5 μg L(-1)) and quantification (0.9-16.7 μg L(-1)), and relative standard deviations (3.2-5%) of the proposed method were satisfactory for determination of the model analytes. The method was successfully applied for determination of target pesticides in grape juice and good recoveries (74-99%) were achieved for spiked samples. As compared with the conventional DLLME, the proposed DLLME method showed higher EFs and less environmental hazards with no need for centrifuging.

  3. A fully automated effervescence assisted dispersive liquid-liquid microextraction based on a stepwise injection system. Determination of antipyrine in saliva samples.

    Science.gov (United States)

    Medinskaia, Kseniia; Vakh, Christina; Aseeva, Darina; Andruch, Vasil; Moskvin, Leonid; Bulatov, Andrey

    2016-01-01

    A first attempt to automate the effervescence assisted dispersive liquid-liquid microextraction (EA-DLLME) has been reported. The method is based on the aspiration of a sample and all required aqueous reagents into the stepwise injection analysis (SWIA) manifold, followed by simultaneous counterflow injection of the extraction solvent (dichloromethane), the mixture of the effervescence agent (0.5 mol L(-1) Na2CO3) and the proton donor solution (1 mol L(-1) CH3COOH). Formation of carbon dioxide microbubbles generated in situ leads to the dispersion of the extraction solvent in the whole aqueous sample and extraction of the analyte into organic phase. Unlike the conventional DLLME, in the case of EA-DLLME, the addition of dispersive solvent, as well as, time consuming centrifugation step for disruption of the cloudy state is avoided. The phase separation was achieved by gentle bubbling of nitrogen stream (2 mL min(-1) during 2 min). The performance of the suggested approach is demonstrated by determination of antipyrine in saliva samples. The procedure is based on the derivatization of antipyrine by nitrite-ion followed by EA-DLLME of 4-nitrosoantipyrine and subsequent UV-Vis detection using SWIA manifold. The absorbance of the yellow-colored extract at the wavelength of 345 nm obeys Beer's law in the range of 1.5-100 µmol L(-1) of antipyrine in saliva. The LOD, calculated from a blank test based on 3σ, was 0.5 µmol L(-1).

  4. Liquid-liquid Microextraction Based on Solidification of Floating Organic Drops Coupled with Gas Chromatography for Analyzing Trace Benzene, Toluene and Xylene in Water Samples

    Institute of Scientific and Technical Information of China (English)

    ZHANG Mao-sheng; HUANG Jia-rong; ZHENG Xiang-hua; XIE Qiong-fang

    2011-01-01

    A new liquid-liquid microextraction method based on the solidification of floating organic drops coupled with gas chromatography was developed for the determination of trace benzene,toluene and xylene(BTX)in water samples.In the microextraction procedure,a microdrop of n-decanol was delivered to the surface of the analytes' solution,and stirred for a desired time.Following the absolute extraction,the sample vial was cooled in an ice bath for 10 min.The solidified n-decanol was then transferred into a plastic tube and melted naturally; and 1 μL of it was injected into gas chromatography for analysis.Factors relevant to the extraction efficiency were studied and optimized.The optimal experimental conditions were:15 μL of n-decanol as extractive solvent,30 mL of solution containing analytes,no salt,the stirring rate 400 r/min,the extraction temperature 30 ℃,and the extraction time 30 min.Under those optimized conditions,the detection limit(LOD)of analytes was in a range of 0.05-0.10 ng/mL by the developed method.A good linearity(r>0.99)in a calibration range of 0.01-100 μg/mL was obtained.The recoveries of the real samples at different spiked levels of BTX were in the range from 92.2% to 103.4%.

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

    Science.gov (United States)

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

    2009-12-04

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

  6. Enhanced spectrophotometric detection of Hg in water samples by surface plasmon resonance of Au nanoparticles after preconcentration with vortex-assisted liquid-liquid microextraction

    Science.gov (United States)

    Martinis, Estefanía M.; Wuilloud, Rodolfo G.

    2016-10-01

    This article presents an efficient, simple, and cost-effective method for the determination of trace amounts of Hg by vortex-assisted liquid-liquid microextraction (VALLME) coupled to microvolume UV-Vis spectrophotometry. This method correlates changes in the intensity of localized surface plasmon resonance (LSPR) of tetraoctylammonium bromide (TOABr) coated Au nanoparticles (NPs) after interaction with Hg2+ ion. Spectroscopic measurements of the TOABr-coated Au NPs phase with particular absorption properties (strong and well-defined absorption bands) after analyte extraction by VALLME, provide an accurate and sensitive determination of Hg in water samples, comparable with measurements obtained by atomic absorption spectrometry (AAS). Different variables including sample volume, extraction time, and TOABr-coated Au NPs dispersion volume were carefully studied; final experimental conditions were 5 mL, 120 μL and 5 min respectively. The limit of detection (LOD) was 0.8 ng mL- 1. The calibration curve was linear at concentrations between the limit of quantification (LOQ) (4.9 ng mL- 1) and up to at least 120 ng mL- 1 of Hg. The relative standard deviation for six replicate determinations of 20 ng mL- 1 of Hg was 4.7%. This method exhibited an excellent analytical performance in terms of selectivity and sensitivity and it was finally applied for Hg determination in spiked tap and mineral water samples.

  7. Analytical interferences of mercuric chloride preservative in environmental water samples: Determination of organic compounds isolated by continuous liquid-liquid extraction or closed-loop stripping

    Science.gov (United States)

    Foreman, W.T.; Zaugg, S.D.; Falres, L.M.; Werner, M.G.; Leiker, T.J.; Rogerson, P.F.

    1992-01-01

    Analytical interferences were observed during the determination of organic compounds in groundwater samples preserved with mercuric chloride. The nature of the interference was different depending on the analytical isolation technique employed. (1) Water samples extracted with dichloromethane by continuous liquid-liquid extraction (CLLE) and analyzed by gas chromatography/mass spectrometry revealed a broad HgCl2 'peak' eluting over a 3-5-min span which interfered with the determination of coeluting organic analytes. Substitution of CLLE for separatory funnel extraction in EPA method 508 also resulted in analytical interferences from the use of HgCl2 preservative. (2) Mercuric chloride was purged, along with organic contaminants, during closed-loop stripping (CLS) of groundwater samples and absorbed onto the activated charcoal trap. Competitive sorption of the HgCl2 by the trap appeared to contribute to the observed poor recoveries for spiked organic contaminants. The HgCl2 was not displaced from the charcoal with the dichloromethane elution solvent and required strong nitric acid to achieve rapid, complete displacement. Similar competitive sorption mechanisms might also occur in other purge and trap methods when this preservative is used.

  8. Standard Practice for Processing Aerospace Liquid Samples for Particulate Contamination Analysis Using Membrane Filters

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 This practice covers the processing of liquids in preparation for particulate contamination analysis using membrane filters and is limited only by the liquid-to-membrane filter compatibility. 1.2 The practice covers the procedure for filtering a measured volume of liquid through a membrane filter. When this practice is used, the particulate matter will be randomly distributed on the filter surface for subsequent contamination analysis methods. 1.3 The practice describes procedures to allow handling particles in the size range between 2 and 1000 μm with minimum losses during handling. 1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.

  9. Capabilities and limitations of dispersive liquid-liquid microextraction with solidification of floating organic drop for the extraction of organic pollutants from water samples.

    Science.gov (United States)

    Vera-Avila, Luz E; Rojo-Portillo, Tania; Covarrubias-Herrera, Rosario; Peña-Alvarez, Araceli

    2013-12-17

    Dispersive liquid-liquid microextraction with solidification of floating organic drop (DLLME-SFO) is one of the most interesting sample preparation techniques developed in recent years. Although several applications have been reported, the potentiality and limitations of this simple and rapid extraction technique have not been made sufficiently explicit. In this work, the extraction efficiency of DLLME-SFO for pollutants from different chemical families was determined. Studied compounds include: 10 polycyclic aromatic hydrocarbons, 5 pesticides (chlorophenoxy herbicides and DDT), 8 phenols and 6 sulfonamides, thus, covering a large range of polarity and hydrophobicity (LogKow 0-7, overall). After optimization of extraction conditions using 1-dodecanol as extractant, the procedure was applied for extraction of each family from 10-mL spiked water samples, only adjusting sample pH as required. Absolute recoveries for pollutants with LogKow 3-7 were >70% and recovery values within this group (18 compounds) were independent of structure or hydrophobicity; the precision of recovery was very acceptable (RSD0.995). Extraction recoveries for pollutants with LogKow 1.46-2.8 were in the range 13-62%, directly depending on individual LogKow values; however, good linearity (r(2)>0.993) and precision (RSD<6.5%) were also demonstrated for these polar solutes, despite recovery level. DLLME-SFO with 1-dodecanol completely failed for extraction of compounds with LogKow≤1 (sulfa drugs), other more polar extraction solvents (ionic liquids) should be explored for highly hydrophilic pollutants. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Application of activated zeolite to quantitative analysis of Pb liquid sample using commercial laser-induced breakdown spectroscopy (LIBS)

    Science.gov (United States)

    Suyanto, H.; Utomo, A. P.; Manurung, M.; Suharta, W. G.; Windaryoto

    2017-04-01

    The aim of this research is to figure out an activated zeolite ability to immobilize Pb element in liquid sample. The zeolite was made into powder with size of about 400 μm and was activated by NaOH with different concentrations of 0.5, 1, 1.5 and 2 M. Prior to being analyzed by commercial Laser-Induced Breakdown Spectroscopy (LIBS) technique, 0.05 gram activated zeolite of each concentration were soaked into 10 ml solution containing 100 ppm of Pb and then heated and stirred until become dry powder. The powder was then made into a pellet. After being analyzed by LIBS, activation by 1.0 M NaOH was the optimum condition for zeolite to immobilize Pb in solution. The minimum concentration of Pb in liquid sample which could be immobilized by this method was about 5.86 ppm.

  11. Development of a sample preparation procedure of sewage sludge samples for the determination of polycyclic aromatic hydrocarbons based on selective pressurized liquid extraction.

    Science.gov (United States)

    Pena, Maria Teresa; Casais, Maria Carmen; Mejuto, Maria Carmen; Cela, Rafael

    2010-01-22

    An automated, simple and sensitive method based on selective pressurized liquid extraction (SPLE) was developed for the analysis of polycyclic aromatic hydrocarbons in sewage sludge samples. The new sample preparation procedure consists of on-line clean-up by inclusion of sorbents in the extraction cell, and combines elevated temperatures and pressures with liquid solvents to achieve fast and efficient removal of target analytes from complex sewage sludge matrices. The effects of various operational parameters (e.g. sample pretreatment, extraction solvent, temperature, pressure, static time, etc.) on the performance of SPLE procedure were carefully investigated, obtaining the best results when SPLE conditions were fixed at 140 degrees C, 1500 psi, static time of 5 min and n-hexane as extraction solvent. A new programmed temperature vaporization-gas chromatography-tandem mass spectrometry method based on large volume injection (PTV-LVI-GC-MS/MS) was also developed and analytical determinations were performed by high performance liquid chromatography coupled with fluorescence detection and GC-MS/MS. The extraction yields for the different compounds obtained by SPLE ranged from 84.8% to 106.6%. Quantification limits obtained for all of these studied compounds (between 0.0001 and 0.005 microg g(-1), dry mass) were well below the regulatory limits for all compounds considered. To test the accuracy of the SPLE technique, the optimized methodology was applied to the analysis of a certified reference material (sewage sludge (BCR088)) and a reference material (sewage sludge (RTC-CNS312-04)), with excellent results.

  12. Comparison of three sampling instruments, Cytobrush, Curette and OralCDx, for liquid-based cytology of the oral mucosa.

    Science.gov (United States)

    Reboiras-López, M D; Pérez-Sayáns, M; Somoza-Martín, J M; Antúnez-López, J R; Gándara-Vila, P; Gayoso-Diz, P; Gándara-Rey, J M; García-García, A

    2012-01-01

    Exfoliative cytology of the oral cavity is a simple and noninvasive technique that permits the study of epithelial cells. Liquid-based cytology is an auxiliary diagnostic tool for improving the specificity and sensitivity of conventional cytology. The objective of our study was to compare the quality of normal oral mucosa cytology samples obtained using three different instruments, Cytobrush®, dermatological curette and Oral CDx® for liquid-based cytology. One hundred four cytological samples of oral cavity were analyzed. Samples were obtained from healthy volunteer subjects using all three instruments. The clinical and demographic variables were age, sex and smoking habits. We analyzed cellularity, quality of the preparation and types of cells in the samples. All preparations showed appropriate preparation quality. In all smears analyzed, cells were distributed uniformly and showed no mucus, bleeding, inflammatory exudate or artifacts. We found no correlation between the average number of cells and the type of instrument. The samples generally consisted of two types of cells: superficial and intermediate. No differences were found among the cytological preparations of these three instruments. We did not observe basal cells in any of the samples analyzed.

  13. Determination of Cu, Mn, Ni and Sn in gasoline by electrothermal vaporization inductively coupled plasma mass spectrometry, and emulsion sample introduction

    Science.gov (United States)

    Saint'Pierre, Tatiana D.; Dias, Lúcia Felicidade; Pozebon, Dirce; Aucélio, Ricardo Q.; Curtius, Adilson J.; Welz, Bernhard

    2002-12-01

    Trace metals in fuels, except in the case of additives, are usually undesirable and normally they occur in very low concentrations in gasoline, requiring sensitive techniques for their determination. Coupling of electrothermal vaporization with inductively coupled plasma mass spectrometry minimizes the problems related to the introduction of organic solvents into the plasma. Furthermore, sample preparation as oil-in-water emulsions reduces problems related to gasoline analysis. In this work, a method for determination of Cu, Mn, Ni and Sn in gasoline is proposed. Samples were prepared by forming a 10-fold diluted emulsion with a surfactant (Triton X-100), after treatment with concentrated HNO 3. The sample emulsion was pre-concentrated in the graphite tube by repeated pipetting and drying. External calibration was used with aqueous standards in a purified gasoline emulsion. Six samples from different gas stations were analyzed, and the analyte concentrations were found to be in the μg l -1 range or below. The limits of detection were 0.22, 0.02, 0.38 and 0.03 μg l -1 for Cu, Mn, Ni and Sn, respectively. The accuracy of the method was estimated using a recovery test.

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

    Science.gov (United States)

    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.

  15. Sensitive Determination of Terazosin in Pharmaceutical Formulations and Biological Samples by Ionic-Liquid Microextraction Prior to Spectrofluorimetry

    Directory of Open Access Journals (Sweden)

    Mohsen Zeeb

    2012-01-01

    Full Text Available An efficient and environmentally friendly sample preparation method based on the application of hydrophobic 1-Hexylpyridinium hexafluorophosphate [Hpy][PF6] ionic liquid (IL as a microextraction solvent was proposed to preconcentrate terazosin. The performance of the microextraction method was improved by introducing a common ion of pyridinium IL into the sample solution. Due to the presence of the common ion, the solubility of IL significantly decreased. As a result, the phase separation successfully occurred even at high ionic strength, and the volume of the settled IL-phase was not influenced by variations in the ionic strength (up to 30% w/v. After preconcentration step, the enriched phase was introduced to the spectrofluorimeter for the determination of terazosin. The obtained results revealed that this system did not suffer from the limitations of that in conventional ionic-liquid microextraction. Under optimum experimental conditions, the proposed method provided a limit of detection (LOD of 0.027 μg L−1 and a relative standard deviation (R.S.D. of 2.4%. The present method was successfully applied to terazosin determination in actual pharmaceutical formulations and biological samples. Considering the large variety of ionic liquids, the proposed microextraction method earns many merits, and will present a wide application in the future.

  16. Sensitive determination of terazosin in pharmaceutical formulations and biological samples by ionic-liquid microextraction prior to spectrofluorimetry.

    Science.gov (United States)

    Zeeb, Mohsen; Sadeghi, Mahdi

    2012-01-01

    An efficient and environmentally friendly sample preparation method based on the application of hydrophobic 1-Hexylpyridinium hexafluorophosphate [Hpy][PF(6)] ionic liquid (IL) as a microextraction solvent was proposed to preconcentrate terazosin. The performance of the microextraction method was improved by introducing a common ion of pyridinium IL into the sample solution. Due to the presence of the common ion, the solubility of IL significantly decreased. As a result, the phase separation successfully occurred even at high ionic strength, and the volume of the settled IL-phase was not influenced by variations in the ionic strength (up to 30% w/v). After preconcentration step, the enriched phase was introduced to the spectrofluorimeter for the determination of terazosin. The obtained results revealed that this system did not suffer from the limitations of that in conventional ionic-liquid microextraction. Under optimum experimental conditions, the proposed method provided a limit of detection (LOD) of 0.027 μg L(-1) and a relative standard deviation (R.S.D.) of 2.4%. The present method was successfully applied to terazosin determination in actual pharmaceutical formulations and biological samples. Considering the large variety of ionic liquids, the proposed microextraction method earns many merits, and will present a wide application in the future.

  17. Vortex-assisted liquid-liquid microextraction using a low-toxicity solvent for the determination of five organophosphorus pesticides in water samples by high-performance liquid chromatography.

    Science.gov (United States)

    Peng, Guilong; He, Qiang; Mmereki, Daniel; Zhou, Guangming; Pan, Weiliang; Gu, Li; Fan, Leilei; Tang, Xiaohui; Chen, Junhua; Mao, Yufeng

    2015-10-01

    Vortex-assisted liquid-liquid microextraction followed by high-performance liquid chromatography with UV detection was applied to determine Isocarbophos, Parathion-methyl, Triazophos, Phoxim and Chlorpyrifos-methyl in water samples. 1-Bromobutane was used as the extraction solvent, which has a higher density than water and low toxicity. Centrifugation and disperser solvent were not required in this microextraction procedure. The optimum extraction conditions for 15 mL water sample were: pH of the sample solution, 5; volume of the extraction solvent, 80 μL; vortex time, 2 min; salt addition, 0.5 g. Under the optimum conditions, enrichment factors ranging from 196 to 237 and limits of detection below 0.38 μg/L were obtained for the determination of target pesticides in water. Good linearities (r > 0.9992) were obtained within the range of 1-500 μg/L for all the compounds. The relative standard deviations were in the range of 1.62-2.86% and the recoveries of spiked samples ranged from 89.80 to 104.20%. The whole proposed methodology is simple, rapid, sensitive and environmentally friendly for determining traces of organophosphorus pesticides in the water samples.

  18. Rapid and sensitive analysis of polychlorinated biphenyls and acrylamide in food samples using ionic liquid-based in situ dispersive liquid-liquid microextraction coupled to headspace gas chromatography.

    Science.gov (United States)

    Zhang, Cheng; Cagliero, Cecilia; Pierson, Stephen A; Anderson, Jared L

    2017-01-20

    A simple and rapid ionic liquid (IL)-based in situ dispersive liquid-liquid microextraction (DLLME) method was developed and coupled to headspace gas chromatography (HS-GC) employing electron capture (ECD) and mass spectrometry (MS) detection for the analysis of polychlorinated biphenyls (PCBs) and acrylamide at trace levels from milk and coffee samples. The chemical structures of the halide-based ILs were tailored by introducing various functional groups to the cations to evaluate the effect of different structural features on the extraction efficiency of the target analytes. Extraction parameters including the molar ratio of IL to metathesis reagent and IL mass were optimized. The effects of HS oven temperature and the HS sample vial volume on the analyte response were also evaluated. The optimized in situ DLLME method exhibited good analytical precision, good linearity, and provided detection limits down to the low ppt level for PCBs and the low ppb level for acrylamide in aqueous samples. The matrix-compatibility of the developed method was also established by quantifying acrylamide in brewed coffee samples. This method is much simpler and faster compared to previously reported GC-MS methods using solid-phase microextraction (SPME) for the extraction/preconcentration of PCBs and acrylamide from complex food samples. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Comparison of hollow fiber liquid phase microextraction and dispersive liquid-liquid microextraction for the determination of organosulfur pesticides in environmental and beverage samples by gas chromatography with flame photometric detection.

    Science.gov (United States)

    Xiong, Jun; Hu, Bin

    2008-06-06

    Two methods based on hollow fiber liquid phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME), have been critically compared for the analysis of organosulfur pesticides (OSPs) in environmental and beverage samples by gas chromatography-flame photometric detection (GC-FPD). Experimental conditions including extraction solvent, solvent volume, extraction time, temperature and ionic strength have been investigated for both HF-LPME and DLLME. Under the optimal conditions, the limits of detection for the six target OSPs (malathion, chlorpyrifos, buprofezin, triazophos, carbosulfan and pyridaben) obtained by HF-LPME-GC-FPD and DLLME-GC-FPD were ranged from 1.16 microg/L to 48.48 microg/L and 0.21 microg/L to 3.05 microg/L, respectively. The relative standard deviations (RSDs, n=5) were in the range of 3.4-8.0% and 8.5-13.7%with the enrichment factors (EFs) of 27-530 and 176-946 folds for HF-LPME-GC-FPD and DLLME-GC-FPD, respectively. Both methods were found to be simple, fast, efficient, and inexpensive. Compared with HF-LPME, the advantages of DLLME technique were less extraction time, suitable for batches of samples pretreatment simultaneously, a higher extraction capacity when analyzing simple samples such as water samples. While for the analysis of complicated matrix samples such as soil and beverage samples, HF-LPME was demonstrated to be more robust and more suitable. Both methods were applied to the analysis of six OSPs in different waters, soil and beverage samples, and no target OSPs was found in these samples. For analysis of the spiked samples, the recovery of 81.7-114.4% with RSDs of 0.6-9.6% were obtained for HF-LPME, and the recovery of 78.5-117.2% with RSDs of 0.6-11.9% were obtained for DLLME.

  20. The capillary adhesion technique: a versatile method for determining the liquid adhesion force and sample stiffness

    Directory of Open Access Journals (Sweden)

    Daniel Gandyra

    2015-01-01

    Full Text Available We report a novel, practical technique for the concerted, simultaneous determination of both the adhesion force of a small structure or structural unit (e.g., an individual filament, hair, micromechanical component or microsensor to a liquid and its elastic properties. The method involves the creation and development of a liquid meniscus upon touching a liquid surface with the structure, and the subsequent disruption of this liquid meniscus upon removal. The evaluation of the meniscus shape immediately before snap-off of the meniscus allows the quantitative determination of the liquid adhesion force. Concurrently, by measuring and evaluating the deformation of the structure under investigation, its elastic properties can be determined. The sensitivity of the method is remarkably high, practically limited by the resolution of the camera capturing the process. Adhesion forces down to 10 µN and spring constants up to 2 N/m were measured. Three exemplary applications of this method are demonstrated: (1 determination of the water adhesion force and the elasticity of individual hairs (trichomes of the floating fern Salvinia molesta. (2 The investigation of human head hairs both with and without functional surface coatings (a topic of high relevance in the field of hair cosmetics was performed. The method also resulted in the measurement of an elastic modulus (Young’s modulus for individual hairs of 3.0 × 105 N/cm2, which is within the typical range known for human hair. (3 Finally, the accuracy and validity of the capillary adhesion technique was proven by examining calibrated atomic force microscopy cantilevers, reproducing the spring constants calibrated using other methods.

  1. Determination of oxytetracycline in milk samples by polymer inclusion membrane separation coupled to high performance liquid chromatography.

    Science.gov (United States)

    Pérez-Silva, Irma; Rodríguez, José A; Ramírez-Silva, Ma Teresa; Páez-Hernández, Ma Elena

    2012-03-09

    The determination of oxytetracycline in milk samples using a polymer inclusion membrane concept with high performance liquid chromatography (HPLC) was studied. The membranes developed are composed by cellulose acetate as polymer base, Cyanex 923 as carrier and o-nitrophenyl octyl ether as plasticizer. In the optimal conditions, the method exhibits good linearity in the range 0.03-0.20 mg L(-1) with a limit of detection and quantification of 8.2 and 27.3 μg L(-1) respectively. The method was successfully applied to the analysis of milk samples with high selectivity.

  2. Hydrophilic interaction chromatography combined with dispersive liquid-liquid microextraction as a preconcentration tool for the simultaneous determination of the panel of underivatized neurotransmitters in human urine samples.

    Science.gov (United States)

    Konieczna, Lucyna; Roszkowska, Anna; Niedźwiecki, Maciej; Bączek, Tomasz

    2016-01-29

    A simple and sensitive method using dispersive liquid-liquid microextraction (DLLME) followed by liquid chromatography coupled to mass spectrometry (LC-MS) with a hydrophilic interaction chromatography (HILIC) column was developed for the simultaneous determination of 13 compounds of different polarities, comprising monoamine neurotransmitters (dopamine, norepinephrine, epinephrine and serotonin) along with their respective precursors and metabolites, in human urine samples. The microextraction procedure was based on the fast injection of a mixture of ethanol (disperser solvent) and dichloromethane (extraction solvent) into a human urine sample, forming a cloudy solution in the Eppendorf tube. After centrifugation, the sedimented phase was collected and subsequently analyzed by LC-HILIC-MS in about 12min without a derivatization step. The separation was performed on an XBridge Amide™ BEH column 3.0×100mm, 3.5mm and the mobile phase consisted of phase A: 10mM ammonium formate buffer in water pH 3.0 and phase B: 10 mM ammonium formate buffer in acetonitrile, under gradient program elution. Tyrosine, tryptophan, 5-hydroxytryptophan, dopamine, epinephrine, norepinephrine, serotonin, 3-methoxytyramine, 5-hydroxyindole-3-acetic acid, 3,4-dihydroxy-l-phenylalanine and norvaline (internal standard) were detected in the positive ionization mode. While vanillylmandelic acid, homovanillic acid, 3,4-dihydroxyphenylacetic acid and 3,4-dihydroxybenzylamine (internal standard) were detected in the negative ionization mode. Parameters influencing DLLME and LC-HILIC-MS were investigated. Under the optimum conditions, the proposed method exhibited a low detection limit (5-10ngmL(-1)), and good linearity with R between 0.9991 and 0.9998. The recoveries in human urine samples were 99.0%±3.6%. for the 13 studied biogenic amines with intra- and inter-day RSDs of 0.24-9.55% and 0.31-10.0%, respectively. The developed DLLME-LC-MS method could be successfully applied for the

  3. Liquid Microjunction Surface Sampling Probe Electrospray Mass Spectrometry for Detection of Drugs and Metabolites in Thin Tissue Sections

    Energy Technology Data Exchange (ETDEWEB)

    Van Berkel, Gary J [ORNL; Kertesz, Vilmos [ORNL; Koeplinger, Kenneth A. [Merck Research Laboratories; Vavek, Marissa [Merck Research Laboratories; Kong, Ah-Ng Tony [Rutgers University

    2008-01-01

    A self-aspirating, liquid micro-junction surface sampling probe/electrospray emitter mass spectrometry system was demonstrated for use in the direct analysis of spotted and dosed drugs and their metabolites in thin tissue sections. Proof-of-principle sampling and analysis directly from tissue without the need for sample preparation was demonstrated first by raster scanning a region on a section of rat liver onto which reserpine was spotted. The mass spectral signal from selected reaction monitoring was used to develop a chemical image of the spotted drug on the tissue. The probe was also used to selectively spot sample areas of sagittal whole mouse body tissue sections that had been dosed orally (90 mg/kg) with R,S-sulforaphane 3 hrs prior to sacrifice. Sulforaphane and its glutathione and N-acetyl cysteine conjugates were monitored with selected reaction monitoring and detected in the stomach and various other tissues from the dosed mouse. No signal for these species was observed in the tissue from a control mouse. The same dosed tissue section was used to illustrate the possibility of obtaining a line scan across the whole body section. In total these results illustrate the potential for rapid screening of the distribution of drugs and metabolites in tissue sections with the micro-liquid junction surface sampling probe/electrospray mass spectrometry approach.

  4. Liquid-based thin-layer cytology can be routinely used in samples obtained via fiberoptic bronchoscope.

    Science.gov (United States)

    Kobayashi, Yukihiro; Uehara, Takeshi; Ota, Hiroyoshi

    2011-01-01

    The aim of this study was to evaluate liquid-based preparations (LBP) as a replacement for conventional smears (CS) of bronchial brushing (BB) and transbronchial fine-needle aspiration (TBNA) samples obtained via fiberoptic bronchoscope. Bronchial brushing and TBNA samples were obtained from 62 and 33 patients by fiberoptic bronchoscopy, respectively. Liquid-based preparations were prepared from needle rinse after initial CS preparation. We compared cellularity, cell morphology, and background between the LBP and CS slides. Correspondence rates between LBP and CS diagnoses in the above 3 categories were 90.3% in the BB and 97.0% in the TBNA samples. If suspicious cases were regarded as malignant, correspondence rates reached 98.4 and 100%, respectively. Histological diagnoses by LBP were mostly the same as those by CS and by biopsy or operation samples. Morphologically, cells and nuclei were shrunk in the LBP; however, the shrinking was not severe enough to influence cytological diagnoses. Blood background and air-drying, which were observed on many of the CS slides, were not detected on the LBP slides. It is possible to use LBP for routine laboratory processing of BB and TBNA samples as a replacement for CS. Copyright © 2010 S. Karger AG, Basel.

  5. Hollow fiber membrane-coated functionalized polymeric ionic liquid capsules for direct analysis of estrogens in milk samples.

    Science.gov (United States)

    Feng, Juanjuan; Sun, Min; Bu, Yanan; Luo, Chuannan

    2016-02-01

    Protein removal process is always time-consuming for the analysis of milk samples. In this work, hollow fiber membrane-coated functionalized polymeric ionic liquid (HF-PIL) capsules were synthesized and used as solid-phase microextraction (SPME) sorbent for direct analysis of estrogens in milk samples. The functionalized PIL monolith sorbent was obtained by copolymerization between 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate IL monomer and 1,6-di(3-vinylimidazolium) hexane bishexafluorophosphate IL-crosslinking agent. A group of four capsules were installed as SPME device, to determine four kinds of estrogens (estrone, diethylstilbestrol, hexestrol, and 17α-ethynylestradiol) in milk samples, coupled to high performance liquid chromatography. Extraction and desorption conditions were optimized to get satisfactory extraction efficiency. Good linearity was obtained in the range of 5-200 μg L(-1). The limits of detection were 1 μg L(-1) for diethylstilbestrol and 2 μg L(-1) for 17α-ethynylestradiol, estrone, and hexestrol. The present method was applied to analyze the model analytes in different milk samples. Relative recoveries were in the range of 85.5-112%. The HF-PIL SPME capsules showed satisfactory extraction efficiency and high resistance to sample matrix interference.

  6. Vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction for the determination of triazine herbicides in water samples by microemulsion electrokinetic chromatography.

    Science.gov (United States)

    Li, Ran-Hong; Liu, Dong-Hui; Yang, Zhong-Hua; Zhou, Zhi-Qiang; Wang, Peng

    2012-07-01

    A novel method based on the combination of microemulsion electrokinetic chromatography (MEEKC) and vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction (VSLLME) was developed for the determination of five triazine herbicides (simazine, atrazine, ametryn, prometryn, and terbutryn) in water samples. The five triazine herbicides were baseline separated by using the microemulsion buffer containing a 10 mmol/L borate buffer at pH 9.5, 2.5% (w/v) SDS as surfactant, 0.8% (w/v) ethyl acetate as oil phase, and 6.0% (w/v) 1-butanol as cosurfactant. The optimum extraction conditions of VSLLME were as follows: 100 μL chloroform was used as extraction solvent, 5.0 × 10⁻⁵ mol/L Tween-20 was chosen as the surfactant to enhance the emulsification, and the extraction process was carried out by vortex mixing for 3 min. Under these optimum experimental conditions, the calibration curve was linear in the range of 2.0-200.0 ng/mL, with the correlation coefficients (r²) varying from 0.9927 to 0.9958. The detection limits of the method varied from 0.41 to 0.62 ng/mL. The purposed method was applied to the determination of five triazine herbicides in real water samples, and the recoveries were between 80.6 and 107.3%.

  7. Dispersive Liquid-Liquid Microextraction Based on Solidification of Floating Organic Drop Followed by Gas Chromatography-Electron Capture Detector for Determination of Some Pesticides in Water Samples

    Directory of Open Access Journals (Sweden)

    Mostafa Bashiri Juybari

    2011-01-01

    Full Text Available In this study dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO followed by gas chromatography-electron capture detection (GC-ECD was developed for determination of some pesticides in the water samples. Some important parameters, such as type and volumes of extraction and disperser solvent and salt effect on the extraction recovery of analytes from aqueous solution were investigated. Under the optimum conditions (extraction solvent: 1-undecanol, 15.0 μL; disperser solvent: acetone, 1.0 mL, and without salt addition, the preconcentration factors were obtained ranged from 802 to 915 for analytes. The linear ranges were from 0.05 to 100 μg L−1, and detection limits ranged from 0.05 to 0.008 μg L−1. The relative standard deviations (RSDs%, =5 were between 3.2% and 6.7%. The proposed method was successfully applied to the determination of target analytes in the tap, sea, and river water samples, and satisfactory recoveries were obtained.

  8. Dispersive liquid-liquid microextraction method based on solidification of floating organic droplet for the determination of triazine herbicides in water and sugarcane samples.

    Science.gov (United States)

    Sanagi, Mohd Marsin; Abbas, Hana Hassan; Ibrahim, Wan Aini Wan; Aboul-Enien, Hassan Y

    2012-07-15

    Dispersive liquid-liquid microextraction method based on solidification of floating organic droplet (DLLME-SFO) was developed for the analysis of triazines. As model compounds four selected triazine herbicides namely, simazine, atrazine, secbumeton and cyanazine were employed to estimate the extraction efficiency. The experimental conditions were comprehensively studied for the DLLME-SFO method. Under the use of 10 μL of 1-undecanol as extraction solvent, 100 μL of acetonitrile as disperser solvent and 5% (w/v) NaCl for 3 min the results demonstrated that the repeatability (RSD%) of the optimised DLLME-SFO method ranged from 0.03% to 5.1% and the linearity in the range of 0.01-100 ppb. Low limits of detection (0.037-0.008 ppb), and good enrichment factors (195-322) were obtained. The DLLME-SFO method applied in water and sugarcane samples showed excellent relative recoveries (95.7-116.9%) with RSDs <8.6% (n=3) for all samples.

  9. Comparison of two novel in-syringe dispersive liquid-liquid microextraction techniques for the determination of iodide in water samples using spectrophotometry

    Science.gov (United States)

    Kaykhaii, Massoud; Sargazi, Mona

    2014-03-01

    Two new, rapid methodologies have been developed and applied successfully for the determination of trace levels of iodide in real water samples. Both techniques are based on a combination of in-syringe dispersive liquid-liquid microextraction (IS-DLLME) and micro-volume UV-Vis spectrophotometry. In the first technique, iodide is oxidized with nitrous acid to the colorless anion of ICl2- at high concentration of hydrochloric acid. Rhodamine B is added and by means of one step IS-DLLME, the ion-pair formed was extracted into toluene and measured spectrophotometrically. Acetone is used as dispersive solvent. The second method is based on the IS-DLLME microextraction of iodide as iodide/1, 10-phenanthroline-iron(II) chelate cation ion-pair (colored) into nitrobenzene. Methanol was selected as dispersive solvent. Optimal conditions for iodide extraction were determined for both approaches. Methods are compared in terms of analytical parameters such as precision, accuracy, speed and limit of detection. Both methods were successfully applied to determining iodide in tap and river water samples.

  10. Comparison of two novel in-syringe dispersive liquid-liquid microextraction techniques for the determination of iodide in water samples using spectrophotometry.

    Science.gov (United States)

    Kaykhaii, Massoud; Sargazi, Mona

    2014-01-01

    Two new, rapid methodologies have been developed and applied successfully for the determination of trace levels of iodide in real water samples. Both techniques are based on a combination of in-syringe dispersive liquid-liquid microextraction (IS-DLLME) and micro-volume UV-Vis spectrophotometry. In the first technique, iodide is oxidized with nitrous acid to the colorless anion of ICl2(-) at high concentration of hydrochloric acid. Rhodamine B is added and by means of one step IS-DLLME, the ion-pair formed was extracted into toluene and measured spectrophotometrically. Acetone is used as dispersive solvent. The second method is based on the IS-DLLME microextraction of iodide as iodide/1, 10-phenanthroline-iron((II)) chelate cation ion-pair (colored) into nitrobenzene. Methanol was selected as dispersive solvent. Optimal conditions for iodide extraction were determined for both approaches. Methods are compared in terms of analytical parameters such as precision, accuracy, speed and limit of detection. Both methods were successfully applied to determining iodide in tap and river water samples.

  11. Homogeneous Liquid-Liquid Microextraction for Determination of Organophosphorus Pesticides in Environmental Water Samples Prior to Gas Chromatography-Flame Photometric Detection.

    Science.gov (United States)

    Berijani, Sana; Sadigh, Mirhanif; Pournamdari, Elham

    2016-07-01

    In this study, homogeneous liquid-liquid microextraction (HLLME) was developed for preconcentration and extraction of 15 organophosphorus pesticides (OPPs) from water samples coupling with gas chromatography followed by a flame photometric detector (HLLME-GC-FPD). In this method, OPPs were extracted by the homogeneous phase in a ternary solvent system (water/acetic acid/chloroform). The homogeneous solution was excluded by the addition of sodium hydroxide as a phase separator reagent and a cloudy solution was formed. After centrifugation (3 min at 5,000 rpm), the fine particles of extraction solvent (chloroform) were sedimented at the bottom of the conical test tube (10.0 ± 0.5 µL). Furthermore, 0.5 µL of the sedimented phase was injected into the GC for separation and determination of OPPs. Optimal results were obtained under the following conditions: volume of the extracting solvent (chloroform), 53 µL; volume of the consolute solvent (acetic acid), 0.76 mL and concentration of sodium hydroxide, 40% (w/v). Under the optimum conditions, the enrichment factors of (260-665), the extraction percent of 75.8-104%, the dynamic linear range of 0.03-300 µg L(-1) and the limits of detection of 0.004-0.03 µg L(-1) were obtained for the OPPs. This method was successfully applied for the extraction and determination of the OPPs in environmental water samples.

  12. Liquid chromatography-mass spectrometric and liquid chromatography-tandem mass spectrometric determination of hallucinogenic indoles psilocin and psilocybin in "magic mushroom" samples.

    Science.gov (United States)

    Kamata, Tooru; Nishikawa, Mayumi; Katagi, Munehiro; Tsuchihashi, Hitoshi

    2005-03-01

    Accurate and sensitive analytical methods for psilocin (PC) and psilocybin (PB), tryptamine-type hallucinogens contained in "magic mushrooms," were investigated using liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS). The chromatographic separation on an ODS column and mass spectral information gave complete discrimination between PC and PB without derivatization. The mass spectrometric detection had a high sensitivity, and the tandem mass spectrometric detection provided more specificity and accuracy, as well as high sensitivity. The detection limits ranged from 1 to 25 pg by LC-MS in the selected ion monitoring mode, and the intra- and inter-day coefficients of variation were estimated to be 4.21-5.93% by LC-MS-MS in the selected reaction monitoring mode. By applying the present LC-MS-MS technique to four real samples, the contents of PC and PB were found to vary over a wide range (0.60-1.4 and 0.18-3.8 mg/g dry wt. for PC and PB, respectively) between samples.

  13. An introduction to the curation of Apollo lunar samples%美国阿波罗月球样品的处理与保存

    Institute of Scientific and Technical Information of China (English)

    孙灵芝; 凌宗成; 刘建忠

    2012-01-01

    中国嫦娥工程三期将进行月球样品的采集与返回,这是继美国Apollo和前苏联Luna之后,国际上最新的月球样品返回计划。月球样品的存储与管理方法将成为中国探月工程中亟待解决的重要问题之一。特别是如何最大程度地保持月球样品的科学研究价值,避免或减少可能的样品污染等问题,不仅为工程部门所关心,也是月球科学家所极为关注的问题。文中主要回顾和总结了美国Apollo月球样品的处理与保存方法,包括月球样品实验室简况、月球样品初步处理方法、月球样品初步测试分析及相关实验简介和月球样品的保存方法等内容,以期为中国月球样品的返回和地面存储提供有益的借鉴。%During the third phase of Chang'e Program,China will conduct the lunar sample return mission,which would collect the newest lunar samples after Apollo and Luna missions.Lunar sample curation will be of great concern for the Chinese lunar mission engineers as well as lunar scientists.The main goal of curating lunar samples is to preserve their scientific value and keep sample contamination and alteration to a minimum.Here we review the methods and experience of Apollo lunar sample curation in the following four sections: introduction of lunar sample laboratory,preliminary lunar sample processing,preliminary lunar sample examination,and lunar sample curating.

  14. Comparison of conventional Papanicolaou cytology samples with liquid-based cervical cytology samples from women in Pernambuco, Brazil

    Directory of Open Access Journals (Sweden)

    M.O.L.P. Costa

    2015-01-01

    Full Text Available In the present study, we compared the performance of a ThinPrep cytological method with the conventional Papanicolaou test for diagnosis of cytopathological changes, with regard to unsatisfactory results achieved at the Central Public Health Laboratory of the State of Pernambuco. A population-based, cross-sectional study was performed with women aged 18 to 65 years, who spontaneously sought gynecological services in Public Health Units in the State of Pernambuco, Northeast Brazil, between April and November 2011. All patients in the study were given a standardized questionnaire on sociodemographics, sexual characteristics, reproductive practices, and habits. A total of 525 patients were assessed by the two methods (11.05% were under the age of 25 years, 30.86% were single, 4.4% had had more than 5 sexual partners, 44% were not using contraception, 38.85% were users of alcohol, 24.38% were smokers, 3.24% had consumed drugs previously, 42.01% had gynecological complaints, and 12.19% had an early history of sexually transmitted diseases. The two methods showed poor correlation (k=0.19; 95%CI=0.11–0.26; P<0.001. The ThinPrep method reduced the rate of unsatisfactory results from 4.38% to 1.71% (χ2=5.28; P=0.02, and the number of cytopathological changes diagnosed increased from 2.47% to 3.04%. This study confirmed that adopting the ThinPrep method for diagnosis of cervical cytological samples was an improvement over the conventional method. Furthermore, this method may reduce possible losses from cytological resampling and reduce obstacles to patient follow-up, improving the quality of the public health system in the State of Pernambuco, Northeast Brazil.

  15. High transport efficiency of nanoparticles through a total-consumption sample introduction system and its beneficial application for particle size evaluation in single-particle ICP-MS.

    Science.gov (United States)

    Miyashita, Shin-Ichi; Mitsuhashi, Hiroaki; Fujii, Shin-Ichiro; Takatsu, Akiko; Inagaki, Kazumi; Fujimoto, Toshiyuki

    2017-02-01

    In order to facilitate reliable and efficient determination of both the particle number concentration (PNC) and the size of nanoparticles (NPs) by single-particle ICP-MS (spICP-MS) without the need to correct for the particle transport efficiency (TE, a possible source of bias in the results), a total-consumption sample introduction system consisting of a large-bore, high-performance concentric nebulizer and a small-volume on-axis cylinder chamber was utilized. Such a system potentially permits a particle TE of 100 %, meaning that there is no need to include a particle TE correction when calculating the PNC and the NP size. When the particle TE through the sample introduction system was evaluated by comparing the frequency of sharp transient signals from the NPs in a measured NP standard of precisely known PNC to the particle frequency for a measured NP suspension, the TE for platinum NPs with a nominal diameter of 70 nm was found to be very high (i.e., 93 %), and showed satisfactory repeatability (relative standard deviation of 1.0 % for four consecutive measurements). These results indicated that employing this total consumption system allows the particle TE correction to be ignored when calculating the PNC. When the particle size was determined using a solution-standard-based calibration approach without an NP standard, the particle diameters of platinum and silver NPs with nominal diameters of 30-100 nm were found to agree well with the particle diameters determined by transmission electron microscopy, regardless of whether a correction was performed for the particle TE. Thus, applying the proposed system enables NP size to be accurately evaluated using a solution-standard-based calibration approach without the need to correct for the particle TE.

  16. On-line sequential injection dispersive liquid-liquid microextraction system for flame atomic absorption spectrometric determination of copper and lead in water samples.

    Science.gov (United States)

    Anthemidis, Aristidis N; Ioannou, Kallirroy-Ioanna G

    2009-06-30

    A simple, sensitive and powerful on-line sequential injection (SI) dispersive liquid-liquid microextraction (DLLME) system was developed as an alternative approach for on-line metal preconcentration and separation, using extraction solvent at microlitre volume. The potentials of this novel schema, coupled to flame atomic absorption spectrometry (FAAS), were demonstrated for trace copper and lead determination in water samples. The stream of methanol (disperser solvent) containing 2.0% (v/v) xylene (extraction solvent) and 0.3% (m/v) ammonium diethyldithiophosphate (chelating agent) was merged on-line with the stream of sample (aqueous phase), resulting a cloudy mixture, which was consisted of fine droplets of the extraction solvent dispersed entirely into the aqueous phase. By this continuous process, metal chelating complexes were formed and extracted into the fine droplets of the extraction solvent. The hydrophobic droplets of organic phase were retained into a microcolumn packed with PTFE-turnings. A portion of 300 microL isobutylmethylketone was used for quantitative elution of the analytes, which transported directly to the nebulizer of FAAS. All the critical parameters of the system such as type of extraction solvent, flow-rate of disperser and sample, extraction time as well as the chemical parameters were studied. Under the optimum conditions the enhancement factor for copper and lead was 560 and 265, respectively. For copper, the detection limit and the precision (R.S.D.) were 0.04 microg L(-1) and 2.1% at 2.0 microg L(-1) Cu(II), respectively, while for lead were 0.54 microg L(-1) and 1.9% at 30.0 microg L(-1) Pb(II), respectively. The developed method was evaluated by analyzing certified reference material and applied successfully to the analysis of environmental water samples.

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

    Science.gov (United States)

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

    2016-10-01

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

  18. Determination of perfluorinated compounds (PFCs) in solid and liquid phase river water samples in Chao Phraya River, Thailand.

    Science.gov (United States)

    Kunacheva, Chinagarn; Tanaka, Shuhei; Fujii, Shigeo; Boontanon, Suwanna Kitpati; Musirat, Chanatip; Wongwattana, Thana

    2011-01-01

    Perfluorinated compounds (PFCs), especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are fully fluorinated organic compounds, which have been used in many industrial applications. These chemicals have contaminated surface water all over the world even in developing countries like Thailand. The previous study showed the contamination in Chao Phraya River in 2006 and 2007. The purposes of this field study were to determine the solid and liquid phase of PFCs contamination in Chao Phraya River and to compare the changes of PFC concentration in 2008. Surveys were conducted in the lower reach of Chao Phraya River in the industrialized area. A solid phase extraction (SPE) coupled with HPLC-ESI-MS/MS were used for the analysis for ten PFCs. Ten PFCs were analyzed to identify the contamination in both solid and liquid phases. PFCs were detected in both the solid and liquid phase in every sample. PFOA was the most dominant PFC while PFPA and PFOS were also highly detected in most samples. The average loadings of PFPA, PFOA and PFOS in Chao Phraya River were 94.3, 284.6 and 93.4 g/d, respectively. PFOS concentrations did not show differences between 2006 and 2008. However, PFOA concentrations were higher in 2008/5/26, while comparing other samplings. The ratio of solid:liquid PFPA (2.1:1.0) [(ng/g)/(ng/L)] was lower than PFOA (13.9:1.0) [(ng/g)/(ng/L)] and PFOS (17.6:1.0) [(ng/g)/(ng/L)]. The shorter chain (more hydrophilic) PFC was better to dissolve in water rather than adsorb onto suspended solids. PFOS also showed more potential to attach in the suspended solids than PFOA.

  19. Evaluation of Two Ionic Liquid-Based Epoxies from the MISSE-8 (Materials International Space Station Experiment-8) Sample Carrier

    Science.gov (United States)

    Rabenberg, Ellen; Kaukler, William; Grugel, Richard

    2015-01-01

    Two sets of epoxy mixtures, both containing the same ionic liquid (IL) based resin but utilizing two different curing agents, were evaluated after spending more than two years of continual space exposure outside of the International Space Station on the MISSE-8 sample rack. During this period the samples, positioned on nadir side, also experienced some 12,500 thermal cycles between approximately -40?C and +40 C. Initial examination showed some color change, a miniscule weight variance, and no cracks or de-bonding from the sample substrate. Microscopic examination of the surface reveled some slight deformities and pitting. These observations, and others, are discussed in view of the ground-based control samples. Finally, the impetus of this study in terms of space applications is presented.

  20. Development of optimal liquid based cytology sample processing methods for HPV testing: minimising the 'inadequate' test result.

    Science.gov (United States)

    Peevor, R; Jones, J; Fiander, A N; Hibbitts, S

    2011-05-01

    Incorporation of HPV testing into cervical screening is anticipated and robust methods for DNA extraction from liquid based cytology (LBC) samples are required. This study compared QIAamp extraction with Proteinase K digestion and developed methods to address DNA extraction failure (β-globin PCR negative) from clinical specimens. Proteinase K and QIAamp extraction methods in paired LBC samples were comparable with adequate DNA retrieved from 93.3% of clinical specimens. An HPV prevalence cohort (n=10,000) found 7% (n=676) LBC samples tested negative for β-globin, and were classified as inadequate. This 'failure' rate is unsuitable for population screening, particularly as the sampling method is intrusive. 379/676 samples were assessed to determine the cause of test failure. Re-testing confirmed adequate DNA in 21.6% of the original extracts; re-extraction from stored material identified 56.2% samples contained adequate material; dilution to overcome sample inhibition (1:10) resolved 51.7% cases in original extracts and 28% in new extracts. A standardised approach to HPV testing with an optimal DNA concentration input rather than standard volume input is recommended. Samples failing initial DNA extraction should be repeat extracted and assessed for sample inhibition to reduce the 7% of HPV tests being reported as inadequate and reduce the need for retesting of those women to <1%.

  1. 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.

    Science.gov (United States)

    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

  2. Serum Protein Profile Study of Clinical Samples Using High Performance Liquid Chromatography-Laser Induced Fluorescence

    DEFF Research Database (Denmark)

    Karemore, Gopal Raghunath; Ukendt, Sujatha; Rai, Lavanya

    2009-01-01

    The serum protein profiles of normal subjects, patients diagnosed with cervical cancer, and oral cancer were recorded using High Performance Liquid Chromatography combined with Laser Induced Fluorescence detection (HPLC-LIF). Serum protein profiles of the above three classes were tested for estab......The serum protein profiles of normal subjects, patients diagnosed with cervical cancer, and oral cancer were recorded using High Performance Liquid Chromatography combined with Laser Induced Fluorescence detection (HPLC-LIF). Serum protein profiles of the above three classes were tested...... for establishing the ability of HPLC-LIF protein profiling technique for discrimination, using hard clustering and Fuzzy clustering methods. The clustering algorithms have quite successfully classified the profiles as belonging to normal, cancer of cervix, and oral cancer conditions....

  3. 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.

    Science.gov (United States)

    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.

  4. Quantification of citalopram or escitalopram and their demethylated metabolites in neonatal hair samples by liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Frison, Giampietro; Favretto, Donata; Vogliardi, Susanna; Terranova, Claudio; Ferrara, Santo Davide

    2008-08-01

    Citalopram and escitalopram are highly selective serotonin reuptake inhibitors widely used in the treatment of depression. They exhibit adverse drug reactions and side effects, however, and the development of specific methods for their determination is of great interest in clinical and forensic toxicology. A liquid chromatography-tandem mass spectrometry method has been developed and validated for the assay of citalopram, escitalopram, and their demethylated metabolites in 10-mg hair samples. The analytes were extracted by incubation in methanol and liquid/liquid extraction with diethyl ether/dichloromethane. Gradient elution on a narrow bore C18 column was realized using clomipramine-d3 as an internal standard. Positive ion electrospray ionization and tandem mass spectrometry determination by collision-induced dissociation were performed in an ion trap mass spectrometer. The method exhibited a linear range of 25 to 2000 pg/mg, a quantification limit of 25 pg/mg for all analytes, relative standard deviations in the range of 12.10 to 9.80 (intraassay), and 13.80 to 11.78 (interassay), and accuracies (as percent recovery of the spiked standards) in the range of 90% to 110%; it was applied to the determination of citalopram and escitalopram and their metabolites in hair samples of two newborns to document their in utero exposure to the drugs. The method proved suitable for neonatal hair analysis of citalopram or escitalopram and was applied to two real cases of gestational exposure.

  5. Determination of Polycyclic Aromatic Hydrocarbons in Tea Infusions Samples by High Performance Liquid Chromatography with Fluorimetric Detection

    Directory of Open Access Journals (Sweden)

    Anna Maria Girelli

    2017-01-01

    Full Text Available This study focuses on the contamination of 15 polycyclic aromatic hydrocarbons (PAHs, recommended by the US Environmental Protection Agency, in 10 tea brands distributed in Italy. Analyses were carried out with a procedure based on saponification, liquid-liquid extraction, and PAHs determination by high performance liquid chromatography with fluorescence detector. A comparison with ultrasonic extraction in bath water was also reported. Contamination is expressed as the sum of analyzed PAHs and ranged between 347 and 4120 ng/L with a mean value of 1675 ng/L. PAHs with 3-4 rings were dominant with a contribution of 92%, while 7% and 1% were found for PAHs with 5 and 6 rings, respectively. Moreover, data revealed that three samples exceeded the EU 2008 criteria established for drinking water in which the sum of benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene is considered (<100 ng/L and two samples exceeded the 10 ng/L level allowed for benzo[a]pyrene.

  6. Direct Sampling and Analysis from Solid Phase Extraction Cards using an Automated Liquid Extraction Surface Analysis Nanoelectrospray Mass Spectrometry System

    Energy Technology Data Exchange (ETDEWEB)

    Walworth, Matthew J [ORNL; ElNaggar, Mariam S [ORNL; Stankovich, Joseph J [ORNL; WitkowskiII, Charles E. [Protein Discovery, Inc.; Norris, Jeremy L [ORNL; Van Berkel, Gary J [ORNL

    2011-01-01

    Direct liquid extraction based surface sampling, a technique previously demonstrated with continuous flow and autonomous pipette liquid microjunction surface sampling probes, has recently been implemented as the Liquid Extraction Surface Analysis (LESA) mode on the commercially available Advion NanoMate chip-based infusion nanoelectrospray ionization system. In the present paper, the LESA mode was applied to the analysis of 96-well format custom solid phase extraction (SPE) cards, with each well consisting of either a 1 or 2 mm diameter monolithic hydrophobic stationary phase. These substrate wells were conditioned, loaded with either single or multi-component aqueous mixtures, and read out using the LESA mode of a TriVersa NanoMate or a Nanomate 100 coupled to an ABI/Sciex 4000QTRAPTM hybrid triple quadrupole/linear ion trap mass spectrometer and a Thermo LTQ XL linear ion trap mass spectrometer. Extraction conditions, including extraction/nanoESI solvent composition, volume, and dwell times, were optimized in the analysis of targeted compounds. Limit of detection and quantitation as well as analysis reproducibility figures of merit were measured. Calibration data was obtained for propranolol using a deuterated internal standard which demonstrated linearity and reproducibility. A 10x increase in signal and cleanup of micromolar Angiotensin II from a concentrated salt solution was demonstrated. Additionally, a multicomponent herbicide mixture at ppb concentration levels was analyzed using MS3 spectra for compound identification in the presence of isobaric interferences.

  7. Dynamic liquid-liquid-solid microextraction based on molecularly imprinted polymer filaments on-line coupling to high performance liquid chromatography for direct analysis of estrogens in complex samples.

    Science.gov (United States)

    Zhong, Qisheng; Hu, Yufei; Hu, Yuling; Li, Gongke

    2012-06-08

    A novel sample preparation technique termed dynamic liquid-liquid-solid microextraction (DLLSME) was developed and on-line coupled to high performance liquid chromatography (HPLC) for direct extraction, desorption, and analysis of trace estrogens in complex samples. The DLLSME consists of the aqueous donor phase, the organic medium phase and the molecularly imprinted polymer filaments (MIPFs) as solid acceptor phase. The organic solvent with lesser density was directly added on top of the aqueous sample, and the dynamic extraction was performed by circulating the organic solvent through the MIPFs inserted into a PEEK tube which served as an extraction and desorption chamber. Afterwards, the extracted analytes on the MIPFs were on-line desorbed and then introduced into the HPLC for analysis. To evaluate the feasibility of the on-line system, a new DLLSME-HPLC method was developed for the analysis of five estrogens in aqueous samples by using 17β-estradiol MIPFs as the solid phase. Under the optimized conditions, the enrichment factors of 51-70, limits of detection of 0.08-0.25 μg/L and precision within 4.5-6.9% were achieved. Furthermore, the proposed method was applied to the analysis of real samples including urine, milk and skin toner, satisfactory recovery (81.9-99.8%) and reproducibility (4.1-7.9%) were obtained. Especially, 0.59 μg/L of 17β-estradiol was determined in female urine sample. The DLLSME offers an attractive alternative for direct analysis of trace analytes in aqueous samples and could potentially be extended to other adsorptive materials.

  8. Liquid Chromatography-Tandem Mass Spectrometry Analysis of Perfluorooctane Sulfonate and Perfluorooctanoic Acid in Fish Fillet Samples

    Directory of Open Access Journals (Sweden)

    Viviana Paiano

    2012-01-01

    Full Text Available Perfluorooctane sulfonate (PFOS and perfluorooctanoic (PFOA acid are persistent contaminants which can be found in environmental and biological samples. A new and fast analytical method is described here for the analysis of these compounds in the edible part of fish samples. The method uses a simple liquid extraction by sonication, followed by a direct determination using liquid chromatography-tandem mass spectrometry (LC-MS/MS. The linearity of the instrumental response was good, with average regression coefficients of 0.9971 and 0.9979 for PFOS and PFOA, respectively, and the coefficients of variation (CV of the method ranged from 8% to 20%. Limits of detection (LOD were 0.04 ng/g for both the analytes and recoveries were 90% for PFOS and 76% for PFOA. The method was applied to samples of homogenized fillets of wild and farmed fish from the Mediterranean Sea. Most of the samples showed little or no contamination by perfluorooctane sulfonate and perfluorooctanoic acid, and the highest concentrations detected among the fish species analyzed were, respectively, 5.96 ng/g and 1.89 ng/g. The developed analytical methodology can be used as a tool to monitor and to assess human exposure to perfluorinated compounds through sea food consumption.

  9. Cyclohexylamine as extraction solvent and chelating agent in extraction and preconcentration of some heavy metals in aqueous samples based on heat-induced homogeneous liquid-liquid extraction.

    Science.gov (United States)

    Sorouraddin, Saeed Mohammad; Farajzadeh, Mir Ali; Okhravi, Tohid

    2017-12-01

    A new sample preparation method has been developed for extraction and preconcentration of some heavy metal cations in aqueous samples using cyclohexylamine-based homogeneous liquid-liquid microextraction. In the proposed method, cyclohexylamine was used as both the complexing agent and the extraction solvent. For this purpose, cyclohexylamine at µL level was initially added into an aqueous solution containing Co(II), Ni(II), and Cu(II) ions which was placed in a glass test tube. The mixture was shaken for forming a homogeneous solution. Then sodium chloride was added to the solution. After shaking manually again, the test tube was placed in a water bath thermostated at 70°C. Due to lower solubility of cyclohexylamine at the elevated temperature, a cloudy solution was formed. The fine droplets of cyclohexylamine containing cation-cyclohexylamine complexes were collected on the top of the aqueous phase by centrifuging. The enriched analytes in the upper phase were determined by graphite furnace atomic absorption spectrometry. Several variables possibly affecting the extraction efficiency were investigated and optimized. Under the optimum conditions the calibration curves were linear in the ranges of 80-1000, 40-700, and 80-800ngL(-1) for Co(2+), Ni(2+), and Cu(2+), respectively. Repeatability of the proposed method, expressed as relative standard deviation, ranged from 3.3% to 5.2% (n = 6, C = 200ngL(-1)). Moreover, the obtained detection limits of the selected analytes were in the range of 15.3-37.7ngL(-1). The accuracy of the developed procedure was verified by analyzing a certified reference material, namely NRCC-SLRS4 Riverine water. Finally, the proposed method was successfully applied for the simultaneous analysis of the selected analytes in environmental water samples. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Isolation of iron and strontium from liquid samples and determination of {sup 55}Fe and {sup 89,90}Sr in liquid radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Grahek, Zeljko; Macefat, Martina Rozmaric

    2004-05-31

    This paper describes the method of isolating iron and strontium from liquid samples with a low concentration of ions that enables simple and rapid determination of {sup 55}Fe and {sup 89,90}Sr. The method consists of binding (concentrating) Fe and Sr at the cation exchanger Amberlite IR-120, their elution from cation exchanger with 4 M HCl or 8 M HNO{sub 3}, isolating Fe on the TRU extraction chromatographic column with 4 M HCl or 8 M HNO{sub 3}, and isolating Sr on the Sr.spec column with the mixture of 8 M HNO{sub 3}+2 M HCl or 5 M HNO{sub 3}. After the isolation, {sup 55}Fe is determined by liquid scintillation counting with scintillation solution, while activity of {sup 89,90}Sr is obtained by Cherenkov counting in 5 M HNO{sub 3}. It was shown that successive counting can be used for simultaneous determination of {sup 89,90}Sr activity. The activity ratio of {sup 89}Sr/{sup 90}Sr (up to 20:1) and vice versa does not impact the determination. {sup 55}Fe is also determined immediately after isolation. The measurements in {alpha},{beta} mode can be used to verify any presence of {alpha}-emitter (americium) in the fraction of iron and to correct the result. The method was tested by determining {sup 55}Fe and {sup 89,90}Sr in model samples and radioactive waste samples. The paper also shows that Fe and Zn can be bound to the TEVA and TRU resins from the solutions of HCl, HNO{sub 3}, and mixture of HCl+HNO{sub 3}. The binding strength depends on the type of resin and the concentration of the acid or the concentration of acids in the mixture. These resin and acids can be used for mutual separation of Fe and Zn and their separation from other elements.

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

    Science.gov (United States)

    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%.

  12. Identification of Unknown Contaminants in Water Samples from ISS Employing Liquid Chromatography/Mass Spectrometry/Mass Spectrometry

    Science.gov (United States)

    Rutz, Jeffrey A.; Schultz, John R.

    2008-01-01

    Mass Spectrometry/Mass Spectrometry (MS/MS) is a powerful technique for identifying unknown organic compounds. For non-volatile or thermally unstable unknowns dissolved in liquids, liquid chromatography/mass spectrometry/mass spectrometry (LC/MS/MS) is often the variety of MS/MS used for the identification. One type of LC/MS/MS that is rapidly becoming popular is time-of-flight (TOF) mass spectrometry. This technique is now in use at the Johnson Space Center for identification of unknown nonvolatile organics in water samples from the space program. An example of the successful identification of one unknown is reviewed in detail in this paper. The advantages of time-of-flight instrumentation are demonstrated through this example as well as the strategy employed in using time-of-flight data to identify unknowns.

  13. Microextraction Techniques Coupled to Liquid Chromatography with Mass Spectrometry for the Determination of Organic Micropollutants in Environmental Water Samples

    Directory of Open Access Journals (Sweden)

    Mª Esther Torres Padrón

    2014-07-01

    Full Text Available Until recently, sample preparation was carried out using traditional techniques, such as liquid–liquid extraction (LLE, that use large volumes of organic solvents. Solid-phase extraction (SPE uses much less solvent than LLE, although the volume can still be significant. These preparation methods are expensive, time-consuming and environmentally unfriendly. Recently, a great effort has been made to develop new analytical methodologies able to perform direct analyses using miniaturised equipment, thereby achieving high enrichment factors, minimising solvent consumption and reducing waste. These microextraction techniques improve the performance during sample preparation, particularly in complex water environmental samples, such as wastewaters, surface and ground waters, tap waters, sea and river waters. Liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS and time-of-flight mass spectrometric (TOF/MS techniques can be used when analysing a broad range of organic micropollutants. Before separating and detecting these compounds in environmental samples, the target analytes must be extracted and pre-concentrated to make them detectable. In this work, we review the most recent applications of microextraction preparation techniques in different water environmental matrices to determine organic micropollutants: solid-phase microextraction SPME, in-tube solid-phase microextraction (IT-SPME, stir bar sorptive extraction (SBSE and liquid-phase microextraction (LPME. Several groups of compounds are considered organic micropollutants because these are being released continuously into the environment. Many of these compounds are considered emerging contaminants. These analytes are generally compounds that are not covered by the existing regulations and are now detected more frequently in different environmental compartments. Pharmaceuticals, surfactants, personal care products and other chemicals are considered micropollutants. These

  14. The Iodine Status of Queensland Preschool Children After the Introduction of Mandatory Iodine Fortification in Bread: An Exploratory Study Using a Convenience Sample.

    Science.gov (United States)

    Samidurai, A J; Ware, R S; Davies, P S W

    2017-01-01

    Introduction Appropriate dietary iodine is essential for thyroid hormone synthesis, especially in young children. Following an iodine fortification in bread initiative, approximately 6 % of Australian preschool children were expected to have an excessive iodine status. The aim of this study was to document the current iodine status of preschool children using urinary iodine concentration (UIC) as a biomarker of iodine intake. Methods A convenience sample of fifty-one preschool children, aged 2-3 years, were recruited from south east Queensland. UIC was ascertained from spot morning and afternoon urine samples collected on two consecutive days and food frequency questionnaires were completed for each participant. Dietary iodine intake was extrapolated from UIC assuming 90 % of dietary iodine is excreted in urine and a urine volume of 0.5 L/day. Results A median UIC of 223.3 μg/L was found. The calculated median dietary iodine intake was 124.8 μg/day (SD 47.0) with 9.8 % of samples above the upper level of 200 μg for dietary iodine for children within this age group. No foods were associated with UIC. Discussion Limited by sample size and recruitment strategies, no association was found between usual food intake and UIC. Extrapolated dietary iodine intake indicated that children within this cohort consumed adequate amounts of dietary iodine, although the number of children consuming above the upper limit of 300 μg/day was almost double of expected. The development of a UIC criteria to assess appropriate parameters for varying degrees of iodine status is required for the monitoring of iodine nutrition in this vulnerable age group.

  15. Application and optimization of microwave-assisted extraction and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography for sensitive determination of polyamines in turkey breast meat samples.

    Science.gov (United States)

    Bashiry, Moein; Mohammadi, Abdorreza; Hosseini, Hedayat; Kamankesh, Marzieh; Aeenehvand, Saeed; Mohammadi, Zaniar

    2016-01-01

    A novel method based on microwave-assisted extraction and dispersive liquid-liquid microextraction (MAE-DLLME) followed by high-performance liquid chromatography (HPLC) was developed for the determination of three polyamines from turkey breast meat samples. Response surface methodology (RSM) based on central composite design (CCD) was used to optimize the effective factors in DLLME process. The optimum microextraction efficiency was obtained under optimized conditions. The calibration graphs of the proposed method were linear in the range of 20-200 ng g(-1), with the coefficient determination (R(2)) higher than 0.9914. The relative standard deviations were 6.72-7.30% (n = 7). The limits of detection were in the range of 0.8-1.4 ng g(-1). The recoveries of these compounds in spiked turkey breast meat samples were from 95% to 105%. The increased sensitivity in using the MAE-DLLME-HPLC-UV has been demonstrated. Compared with previous methods, the proposed method is an accurate, rapid and reliable sample-pretreatment method.

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

    Science.gov (United States)

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

    2017-08-15

    In this study, dispersive liquid-liquid microextraction coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry was developed for the analysis of five representative organophosphate esters (OPEs) in wine samples. Under optimized conditions, the proposed method resulted in good linearity (R(2)>0.9933) over the range of 0.1-100μgL(-1), with limits of detection (LODs, S/N =3) and quantification (LOQs, S/N =10) in the ranges of 0.48-18.8ngL(-1) and 1.58-62.5ngL(-1), respectively. Inter- and intra-assay precisions of RSD% ranged from 3.21% to 6.13% and from 1.69% to 7.63%, respectively. The spiked recoveries of target OPEs from white wine, red wine, and beer samples were in the ranges of 80-122%, 76-120%, and 76-110%, respectively, at two different concentration levels. The total concentrations of five OPEs found in white wine, red wine, and beer samples were in the ranges of 0.29-0.85μgL(-1), 1.00-3.05μgL(-1), and 0.86-1.47μgL(-1), respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Alternative solvent-based methyl benzoate vortex-assisted dispersive liquid-liquid microextraction for the high-performance liquid chromatographic determination of benzimidazole fungicides in environmental water samples.

    Science.gov (United States)

    Santaladchaiyakit, Yanawath; Srijaranai, Supalax

    2014-11-01

    Vortex-assisted dispersive liquid-liquid microextraction using methyl benzoate as an alternative extraction solvent for extracting and preconcentrating three benzimidazole fungicides (i.e., carbendazim, thiabendazole, and fluberidazole) in environmental water samples before high-performance liquid chromatographic analysis has been developed. The selected microextraction conditions were 250 μL of methyl benzoate containing 300 μL of ethanol, 1.0% w/v sodium acetate, and vortex agitation speed of 2100 rpm for 30 s. Under optimum conditions, preconcentration factors were 14.5-39.0 for the target fungicides. Limits of detection were obtained in the range of 0.01-0.05 μg/L. The proposed method was then applied to surface water samples and the recovery evaluations at three spiked concentration levels of 5, 30, and 50 μg/L were obtained in the range of 77.4-110.9% with the relative standard deviation water samples.

  18. Microbiological and biochemical characterization of fermented liquid feed samples from 40 Danish farms

    DEFF Research Database (Denmark)

    Canibe, Nuria; Pedersen, Anni Øyan; Jensen, Bent Borg;

    2010-01-01

    When feed and a liquid are mixed fermentation will spontaneously start. The microbial species dominating in the fermented mixture may vary depending on the environment and/or the ingredients being fermented. However, there is scarce knowledge on this subject. A study was carried out to investigate......' group. The biochemical characteristics and the microbiological composition to group level were determined. Furthermore, characterization of lactic acid bacteria and yeasts to species level was carried out. The biochemical characteristics and the composition of microbial groups of the two farm groups...

  19. Mobile membrane introduction tandem mass spectrometry for on-the-fly measurements and adaptive sampling of VOCs around oil and gas projects in Alberta, Canada

    Science.gov (United States)

    Krogh, E.; Gill, C.; Bell, R.; Davey, N.; Martinsen, M.; Thompson, A.; Simpson, I. J.; Blake, D. R.

    2012-12-01

    The release of hydrocarbons into the environment can have significant environmental and economic consequences. The evolution of smaller, more portable mass spectrometers to the field can provide spatially and temporally resolved information for rapid detection, adaptive sampling and decision support. We have deployed a mobile platform membrane introduction mass spectrometer (MIMS) for the in-field simultaneous measurement of volatile and semi-volatile organic compounds. In this work, we report instrument and data handling advances that produce geographically referenced data in real-time and preliminary data where these improvements have been combined with high precision ultra-trace VOCs analysis to adaptively sample air plumes near oil and gas operations in Alberta, Canada. We have modified a commercially available ion-trap mass spectrometer (Griffin ICX 400) with an in-house temperature controlled capillary hollow fibre polydimethylsiloxane (PDMS) polymer membrane interface and in-line permeation tube flow cell for a continuously infused internal standard. The system is powered by 24 VDC for remote operations in a moving vehicle. Software modifications include the ability to run continuous, interlaced tandem mass spectrometry (MS/MS) experiments for multiple contaminants/internal standards. All data are time and location stamped with on-board GPS and meteorological data to facilitate spatial and temporal data mapping. Tandem MS/MS scans were employed to simultaneously monitor ten volatile and semi-volatile analytes, including benzene, toluene, ethylbenzene and xylene (BTEX), reduced sulfur compounds, halogenated organics and naphthalene. Quantification was achieved by calibrating against a continuously infused deuterated internal standard (toluene-d8). Time referenced MS/MS data were correlated with positional data and processed using Labview and Matlab to produce calibrated, geographical Google Earth data-visualizations that enable adaptive sampling protocols

  20. Liquid-based cytology versus conventional cytology for evaluation of cervical Pap smears: Experience from the first 1000 split samples

    Directory of Open Access Journals (Sweden)

    Vikrant Bhar Singh

    2015-01-01

    Full Text Available Context and Aim: Screening programs using conventional cytology conventional Pap smear (CPS have successfully reduced cervical cancer, but newer tests like liquid-based cytology (LBC and human papillomavirus testing might enhance screening. The main aim of the present study was to assess the diagnostic accuracy of LBC versus CPS using "split samples." Materials and Methods: This was a prospective study comprising of 1000 consecutive cervical "split samples" over a period of 1 year. Split sample was obtained using cervex-brush. CPS was prepared from the brush and the brush head was suspended in the LBC vial and processed by SurePath™ LBC. Results: There were 4.3% unsatisfactory (U/S cases in CPS and 1.7% in LBC; the main cause is insufficient cells, and excess of blood in CPS. About 25/100 (2.5% split samples had epithelial abnormalities both in CPS and LBC (1.2%-atypical squamous cells of undetermined significance; 0.4%-low grade squamous intraepithelial lesion; 0.2%-high grade squamous intraepithelial lesion; 0.5%-squamous cell carcinoma; 0.1%-atypical glandular cells favouring neoplasia; 0.2%-adenocarcinoma. Inflammatory organisms were almost equally identified in both techniques but were better seen in LBC samples. Conclusions: LBC technique leads to significant reduction of U/S rate. LBC samples offered better clarity, uniform spread of smears, less time for screening and better handling of hemorrhagic and inflammatory samples. LBC had equivalent sensitivity and specificity to CPS.

  1. Simultaneous determination of seven bisphenols in environmental water and solid samples by liquid chromatography-electrospray tandem mass spectrometry.

    Science.gov (United States)

    Yang, Yunjia; Lu, Libin; Zhang, Jing; Yang, Yi; Wu, Yongning; Shao, Bing

    2014-02-01

    This article presents a simple and universal analytical method for the simultaneous analysis of bisphenol S (BPS), bisphenol F (BPF), bisphenol A (BPA), bisphenol B (BPB), bisphenol AF (BPAF), tetrachlorobisphenol A (TCBPA), and tetrabromobisphenol A (TBBPA) in environmental water (river water, sewage) and solid samples (sediment, sludge) based on liquid chromatography-electrospray tandem mass spectrometry (LC-MS/MS). Analytes were extracted from water samples using hydrophilic lipophilic balanced (HLB) solid-phase extraction (SPE) cartridges, and the extracts were further purified using MAX SPE cartridges. For the solid samples, a combination of ultrasonic extraction with the same SPE clean-up procedures used for the water samples was employed. The absolute recoveries for all analytes in the water and solid samples ranged from 57.1 to 114.3%. Good method reproducibility was achieved in terms of intra- and inter-day precision, yielding relative standard deviations (RSDs) less than 16.9 and 18.1%, respectively. The method limits of quantitation (MLOQ) for the seven compounds in environmental water and solid samples ranged from 0.05 to 4.35ng/L and from 0.06 to 2.83ng/g (dry weight, d.w.), respectively. Finally, this method was successfully applied to real environmental sample analysis, which revealed that all of the tested BPs were present, with the exception of BPB.

  2. Ion pair-dispersive liquid-liquid microextraction coupled to microsample injection system-flame atomic absorption spectrometry for determination of gold at trace level in real samples.

    Science.gov (United States)

    Hol, Aysen; Kartal, Aslıhan Arslan; Akdogan, Abdullah; Elçi, Aydan; Arslan, Tuba; Elçi, Lati

    2015-01-01

    A novel ion pair-dispersive liquid-liquid microextraction (IP-DLLME) of gold followed by its determination with microsample injection system-flame atomic absorption spectrometry (MIS-FAAS) detection was developed. The extraction method was based on the reaction of anionic tetrachloro gold(III) complex with the cationic form of Rhodamine B to give a violet ion pair complex, which is extracted from 1.0 mol L(-1) HCl solution of 8.0 mL to fine droplets of chloroform of 500 µL. A Plackett-Burman experimental design of MINITAB statistical program was employed to optimize the influence of main parameters to be controlled in DLLME. After optimizing the extraction conditions, gold was quantitatively recovered by preconcentration factor of 40, limit of detection (LOD) of 1.8 μg L(-1) and relative standard deviation of less than 6.8%. The proposed method was successfully applied to the preconcentration and determination of gold in some samples such as tap water, waste water, copper electrolysis solution and copper wire coated nickel.

  3. Graphene oxide reinforced polymeric ionic liquid monolith solid-phase microextraction sorbent for high-performance liquid chromatography analysis of phenolic compounds in aqueous environmental samples.

    Science.gov (United States)

    Sun, Min; Bu, Yanan; Feng, Juanjuan; Luo, Chuannan

    2016-01-01

    A graphene oxide reinforced polymeric ionic liquids monolith was obtained by copolymerization of graphene oxide doped 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate monomer and 1,6-di-(3-vinylimidazolium) hexane bihexafluorophosphate cross-linking agent. Coupled to high-performance liquid chromatography, the monolith was used as a solid-phase microextraction sorbent to analyze several phenolic compounds in aqueous samples. Under the optimized extraction and desorption conditions, linear ranges were 5-400 μg/L for 3-nitrophenol, 2-nitrophenol, and 2,5-dichlorophenol and 2-400 μg/L for 4-chlorophenol, 2-methylphenol, and 2,4,6-trichlorophenol (R(2) = 0.9973-0.9988). The limits of detection were 0.5 μg/L for 3-nitrophenol and 2-nitrophenol and 0.2 μg/L for the rest of the analytes. The proposed method was used to determine target analytes in groundwater from an industrial park and river water. None of the analytes was detected. Relative recoveries were in the range of 75.5-113%.

  4. 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.

    Science.gov (United States)

    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.

  5. APTIMA assay on SurePath liquid-based cervical samples compared to endocervical swab samples facilitated by a real time database

    Directory of Open Access Journals (Sweden)

    Khader Samer

    2010-01-01

    Full Text Available Background: Liquid-based cytology (LBC cervical samples are increasingly being used to test for pathogens, including: HPV, Chlamydia trachomatis (CT and Neisseria gonorrhoeae (GC using nucleic acid amplification tests. Several reports have shown the accuracy of such testing on ThinPrep (TP LBC samples. Fewer studies have evaluated SurePath (SP LBC samples, which utilize a different specimen preservative. This study was undertaken to assess the performance of the Aptima Combo 2 Assay (AC2 for CT and GC on SP versus endocervical swab samples in our laboratory. Materials and Methods: The live pathology database of Montefiore Medical Center was searched for patients with AC2 endocervical swab specimens and SP Paps taken the same day. SP samples from CT- and/or GC-positive endocervical swab patients and randomly selected negative patients were studied. In each case, 1.5 ml of the residual SP vial sample, which was in SP preservative and stored at room temperature, was transferred within seven days of collection to APTIMA specimen transfer tubes without any sample or patient identifiers. Blind testing with the AC2 assay was performed on the Tigris DTS System (Gen-probe, San Diego, CA. Finalized SP results were compared with the previously reported endocervical swab results for the entire group and separately for patients 25 years and younger and patients over 25 years. Results: SP specimens from 300 patients were tested. This included 181 swab CT-positive, 12 swab GC-positive, 7 CT and GC positive and 100 randomly selected swab CT and GC negative patients. Using the endocervical swab results as the patient′s infection status, AC2 assay of the SP samples showed: CT sensitivity 89.3%, CT specificity 100.0%; GC sensitivity and specificity 100.0%. CT sensitivity for patients 25 years or younger was 93.1%, versus 80.7% for patients over 25 years, a statistically significant difference (P = 0.02. Conclusions: Our results show that AC2 assay of 1.5 ml SP

  6. Radiocarbon dating of archaeological samples (sambaqui) using CO(2) absorption and liquid scintillation spectrometry of low background radiation.

    Science.gov (United States)

    Mendonça, Maria Lúcia T G; Godoy, José M; da Cruz, Rosana P; Perez, Rhoneds A R

    2006-01-01

    Sambaqui means, in the Tupi language, a hill of shells. The sambaquis are archaeological sites with remains of pre-historical Brazilian occupation. Since the sambaqui sites in the Rio de Janeiro state region are older than 10,000 years, the applicability of CO(2) absorption on Carbo-sorb and (14)C determination by counting on a low background liquid scintillation counter was tested. In the present work, sambaqui shells were treated with H(3)PO(4) in a closed vessel in order to generate CO(2). The produced CO(2) was absorbed on Carbo-sorb. On saturation about 0.6g of carbon, as CO(2), was mixed with commercial liquid scintillation cocktail (Permafluor), and the (14)C activity determined by counting on a low background counter, Packard Tricarb 3170 TR/SL, for a period of 1000 mins to enable detection of a radiocarbon age of 22,400 BP. But only samples with ages up to 3500 BP were submitted to the method because the samples had been collected in the municipality of Guapimirim, in archaeological sambaqui-type sites belonging to this age range. The same samples were sent to the (14)C Laboratory of the Centro de Energia Nuclear na Agricultura (CENA/USP) where similar results were obtained.

  7. Hollow-fiber liquid phase microextraction for lignin pyrolysis acids in aerosol samples and gas chromatography-mass spectrometry analysis.

    Science.gov (United States)

    Hyder, Murtaza; Jönsson, Jan Åke

    2012-08-03

    A method based on three-phase hollow fiber liquid phase microextraction was developed and successfully applied to aerosols for the analysis of lignin pyrolysis acids such as syringic acid, vanillic acid and p-salicylic acid. Important parameters related to extraction process like organic solvent for membrane phase, tri-n-octylphosphine (TOPO) oxide contents in organic solvent, stirring speed, extraction time etc. were optimized. 6-Undecanone with 15% TOPO contents (w/v) was found a suitable solvent for organic liquid membrane, 900 rpm was the optimum stirring speed and time of 4h was found optimum extraction time. Donor phase pH was 1.3 while acceptor phase pH was adjusted to 9.5. The optimized extraction method was used for the extraction of real aerosol samples. Analytes were derivatized using BSTFA containing 1% trimethylsilyl chloride and gas chromatography mass spectrometry was used for analysis. Very low limits of detection in the range 0.2-1.0 ng L(-1) were found, corresponding to 10-50 pg m(-3) of analytes in aerosols. Extraction efficiency obtained ranged 60.3-71.7% and enrichment factors ranged 3015-3585 times. The optimized method was successfully applied to aerosol samples and all of the selected analytes were detected in the analyzed samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. An environmentally-friendly, highly efficient, gas pressure-assisted sample introduction system for ICP-MS and its application to detection of cadmium and lead in human plasma.

    Science.gov (United States)

    Cao, Yupin; Deng, Biyang; Yan, Lizhen; Huang, Hongli

    2017-05-15

    An environmentally friendly and highly efficient gas pressure-assisted sample introduction system (GPASIS) was developed for inductively-coupled plasma mass spectrometry. A GPASIS consisting of a gas-pressure control device, a customized nebulizer, and a custom-made spray chamber was fabricated. The advantages of this GPASIS derive from its high nebulization efficiencies, small sample volume requirements, low memory effects, good precision, and zero waste emission. A GPASIS can continuously, and stably, nebulize 10% NaCl solution for more than an hour without clogging. Sensitivity, detection limits, precision, long-term stability, double charge and oxide ion levels, nebulization efficiencies, and matrix effects of the sample introduction system were evaluated. Experimental results indicated that the performance of this GPASIS, was equivalent to, or better than, those obtained by conventional sample introduction systems. This GPASIS was successfully used to determine Cd and Pb by ICP-MS in human plasma. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Application of dispersive liquid–liquid microextraction and reversed phase-high performance liquid chromatography for the determination of two fungicides in environmental water samples

    Science.gov (United States)

    Cheng, Jing; Zhou, Yiwen; Zuo, Mei; Dai, Liping; Guo, Xiaojie

    2010-01-01

    Dispersive liquid–liquid microextraction (DLLME) has been developed for the extraction and preconcentration of diethofencarb (DF) and pyrimethanil (PM) in environmental water. In the method, a suitable mixture of extraction solvent (50 μL carbon tetrachloride) and dispersive solvent (0.75 mL acetonitrile) are injected into the aqueous samples (5.00 mL) and the cloudy solution is observed. After centrifugation, the enriched analytes in the sediment phase were determined by HPLC-VWD. Different influencing factors, such as the kind and volume of extraction and dispersive solvent, extraction time and salt effect were investigated. Under the optimum conditions, the enrichment factors for DF and PM were both 108 and the limit of detection were 0.021 ng mL−1 and 0.015 ng mL−1, respectively. The linear ranges were 0.08–400 ng mL−1 for DF and 0.04–200 ng mL−1 for PM. The relative standard deviation (RSDs) were both almost at 6.0% (n = 6). The relative recoveries from samples of environmental water were from the range of 87.0 to 107.2%. Compared with other methods, DLLME is a very simple, rapid, sensitive (low limit of detection) and economical (only 5 mL volume of sample) method. PMID:20862191

  10. Speciation and determination of ultra trace amounts of inorganic tellurium in environmental water samples by dispersive liquid-liquid microextraction and electrothermal atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Najafi, Nahid Mashkouri, E-mail: n-najafi@sbu.ac.ir [Department of Chemistry, Faculty of Science, Shahid Beheshti Uinversity, Evin, Tehran (Iran, Islamic Republic of); Tavakoli, Hamed; Alizadeh, Reza; Seidi, Shahram [Department of Chemistry, Faculty of Science, Shahid Beheshti Uinversity, Evin, Tehran (Iran, Islamic Republic of)

    2010-06-18

    A simple and powerful method has been developed for the rapid and selective determination of Te(IV) and Te(VI), employing dispersive liquid-liquid microextraction combined with electrothermal atomic absorption spectrometry using palladium as permanent modifier. Under acidic conditions pH 1, only Te(IV) can form a complex with ammonium pyrrolidine dithiocarbamate (APDC) and therefore be extracted into fine droplets of carbon tetrachloride (extraction solvent) which are dispersed with ethanol into the water sample solution. After centrifugation, Te(IV) was determined in the sedimented organic phase while Te(VI) remained in the aqueous phase. Total inorganic tellurium was determined after the reduction of the Te(VI) to Te(IV). Te(VI) was calculated as the difference between the measured total inorganic tellurium and Te(IV) content. The effective parameters for improving the efficiency of microextraction process were investigated by using experimental and central composite designs. Under optimal conditions the enrichment factor was 125 and the calibration graph was linear in the range of 0.015-1 ng mL{sup -1} with detection limit and characteristic mass of 0.004 ng mL{sup -1} and 0.033 pg, respectively. The relative standard deviation for 0.5 ng mL{sup -1} of tellurium measurement was 3.6% (n = 6) at ash and atomization temperature, 900 and 2600 deg. C, respectively. The recoveries of spiked Te(IV) and Te(VI) to the environmental water samples were 89.6-101.3% and 96.6-99.1%, respectively. The accuracy is also evaluated by applying the proposed method to certified reference material (NIST SRM 1643e), for which the result was in a good agreement with the certified values reported for this CRM (95% confidence level).

  11. Sampling

    CERN Document Server

    Thompson, Steven K

    2012-01-01

    Praise for the Second Edition "This book has never had a competitor. It is the only book that takes a broad approach to sampling . . . any good personal statistics library should include a copy of this book." —Technometrics "Well-written . . . an excellent book on an important subject. Highly recommended." —Choice "An ideal reference for scientific researchers and other professionals who use sampling." —Zentralblatt Math Features new developments in the field combined with all aspects of obtaining, interpreting, and using sample data Sampling provides an up-to-date treat

  12. 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.

    Science.gov (United States)

    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.

  13. Highly specific quantification of ergotamine in urine, blood, and hair samples by liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Favretto, Donata; Frison, Giampietro; Vogliardi, Susanna; Ferrara, Santo Davide

    2007-06-01

    Ergotamine has been used for therapeutic purposes since the 1950s, usually to treat vascular headache. It is highly toxic and in large, repeated doses can produce all the symptoms of ergot poisoning. A selective and sensitive method, based on liquid chromatography-tandem mass spectrometry (LC-MS2), has been developed for quantifying ergotamine in biological fluids with use of a quick and easy sample preparation. Ergotamine and the internal standard, trideuterated lysergic acid diethylamide, were extracted from human urine, blood, and hair by means of liquid-liquid extraction at alkaline pH. Gradient elution on a cyanopropyl column was used for chromatographic separation. Positive ion electrospray ionization and tandem mass spectrometry determination by collision-induced dissociation were performed in an ion trap mass spectrometer. The method was validated and successfully applied to a case of iatrogenic ergotism resulting from the intake of ergotamine tartrate for treating headache. For the first time, ergotamine was identified and quantified in hair. The ergotamine concentrations measured were 320 pg/mL in blood, 100 pg/mL in urine, 24 pg/mg in proximal hair, and 15 pg/mg in distal hair.

  14. True non-contact atomic force microscopy imaging of heterogeneous biological samples in liquids: topography and material contrast.

    Science.gov (United States)

    Almonte, Lisa; Colchero, Jaime

    2017-02-23

    The present work analyses how the tip-sample interaction signals critically determine the operation of an Atomic Force Microscope (AFM) set-up immersed in liquid. On heterogeneous samples, the conservative tip-sample interaction may vary significantly from point to point - in particular from attractive to repulsive - rendering correct feedback very challenging. Lipid membranes prepared on a mica substrate are analyzed as reference samples which are locally heterogeneous (material contrast). The AFM set-up is operated dynamically at low oscillation amplitude and all available experimental data signals - the normal force, as well as the amplitude and frequency - are recorded simultaneously. From the analysis of how the dissipation (oscillation amplitude) and the conservative interaction (normal force and resonance frequency) vary with the tip-sample distance we conclude that dissipation is the only appropriate feedback source for stable and correct topographic imaging. The normal force and phase then carry information about the sample composition ("chemical contrast"). Dynamic AFM allows imaging in a non-contact regime where essentially no forces are applied, rendering dynamic AFM a truly non-invasive technique.

  15. Preparation and examination of monolithic in-needle extraction (MINE) device for the direct analysis of liquid samples

    Energy Technology Data Exchange (ETDEWEB)

    Pietrzyńska, Monika, E-mail: monikapietrzynska@gmail.com; Voelkel, Adam; Bielicka-Daszkiewicz, Katarzyna

    2013-05-07

    Graphical abstract: -- Highlights: •MINE device for isolation of analytes from water samples. •Nine polymer poly(styrene-divinylbenzene) monoliths prepared in stainless steel needles. •High efficiency of in-needle extraction systems based on monolithic materials. •New possibilities in sample preparation area. -- Abstract: Combination of extraction and chromatographic techniques opens NEW possibilities in sample preparation area. Macroporous poly(styrene-divinylbenzene) (PS-DVB) monoliths were prepared by in situ polymerization in stainless steel needles. The surface of stainless steel needle was modified earlier by the silane coupling agent. Monolithic materials located inside needles were used as the in-needle extraction device. Scanning electron microscope (SEM) images were obtained for nine monoliths. Spectra of prepared materials were also performed with the use of two techniques: Attenuated Total Reflectance (ATR) and Fourier Transform Infrared Spectroscopy (FTIR). The new monolithic in-needle extraction (MINE) devices were used in the preparation of a series of test water samples for chromatographic analysis. The extraction of phenolic compounds from water samples was carried out by pumping liquid samples through the MINE device. Obtained results indicate a high efficiency of in-needle extraction systems based on monolithic materials. Breakthrough volume and the sorption efficiency of prepared monolithic in-needle extraction devices were determined experimentally. The achieved recovery was close to 90%, and determined LOQ values varied between 0.4 and 6 μg.

  16. Solid-phase extraction and liquid chromatographic quantitation of quinfamide in biological samples.

    Science.gov (United States)

    Morales, J M; Jung, C H; Alarcón, A; Barreda, A

    2000-09-15

    This paper describes a high-performance liquid chromatographic method for the assay of quinfamide and its main metabolite, 1-(dichloroacetyl)-1,2,3,4,-tetrahydro-6-quinolinol, in plasma, urine and feces. It requires 1 ml of biological fluid, an extraction using Sep-Pack cartridges and acetonitrile for drug elution. Analysis was performed on a CN column (5 microm) using water-acetonitrile-methanol (40:50:10) as a mobile phase at 269 nm. Results showed that the assay was linear in the range between 0.08 and 2.0 microg/ml. The limit of quantitation was 0.08 microg/ml. Maximum assay coefficient of variation was 14%. Recovery obtained in plasma, urine and feces ranged from 82% to 98%.

  17. Efficacy of liquid-based cytology versus conventional smears in FNA samples

    Directory of Open Access Journals (Sweden)

    Kalpalata Tripathy

    2015-01-01

    Conclusion: LBC performed on FNA samples can be a simple and valuable technique. Only in few selected cases, where background factor is an essential diagnostic clue, a combination of both CP and TP is necessary.

  18. Determination of Cu, Zn, and Se in microvolumes of liquid biological samples

    Science.gov (United States)

    Shaban, H. A.; Shaltout, A. A.; Abdou, M.; Al Ashker, E. A.; Elgohary, M.

    2011-01-01

    Cu, Zn, and Se were successfully determined in a few microliters (<100 μl) of biological samples using discrete injection atomic absorption spectrometry. Different factors were investigated in order to obtain a biological sample volume which is valid for analysis. Among them are the effect of microsampling volume variations (starting from 40 to 200 μl), nebulization efficiency, detection limits, precision, and finally the calibration and sensitivity of the proposed method. It was found that 60 μl of the biological sample was adequate for the quantitative analysis with reasonable precision. The advantages of the proposed method are not only rapidity, simplicity, sensitivity, and good precision, but also, contrary to conventional flame atomic absorption spectrometry, the capability of analyzing microvolumes of samples.

  19. Dispersive liquid-liquid microextraction coupled with dispersive micro-solid-phase extraction for the fast determination of polycyclic aromatic hydrocarbons in environmental water samples.

    Science.gov (United States)

    Shi, Zhi-Guo; Lee, Hian Kee

    2010-02-15

    A new two-step microextraction technique, combining dispersive liquid-liquid microextraction (DLLME) and dispersive microsolid-phase extraction (D-micro-SPE), was developed for the fast gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons (PAHs) in environmental samples. A feature of the new procedure lies in that any organic solvent immiscible with water can be used as extractant in DLLME. A special apparatus, such as conical-bottom test tubes, and tedious procedures of centrifugation, refrigeration of the solvent, and then thawing it, associated with classical DLLME or similar techniques are not necessary in the new procedure, which potentially lends itself to possible automation. In the present D-micro-SPE approach, hydrophobic magnetic nanoparticles were used to retrieve the extractant of 1-octanol in the DLLME step. It is noteworthy that the target of D-micro-SPE was the 1-octanol rather than the PAHs. Because of the rapid mass transfer associated with the DLLME and the D-micro-SPE steps, fast extraction could be achieved. Parameters affecting the extraction efficiency were investigated in detail. The optimal conditions were as follows: vortex at 3200 rpm in the DLLME step for 2 min and in D-micro-SPE for 1 min and then desorption by sonication for 4 min with acetonitrile as the solvent. The results demonstrated that enrichment factors ranging from 110- to 186-fold were obtained for the analytes. The limits of detection and the limits of quantification were in the range of 11.7-61.4 pg/mL and 0.04-0.21 ng/mL, respectively. The linearities were 0.5-50, 1-50, or 2-50 ng/mL for different PAHs. Finally, the two-step extraction method was successfully used for the fast determination of PAHs in river water samples. This two-step method, combining two different and efficient miniaturized techniques, provides a fast means of sample pretreatment for environmental water samples.

  20. A micro-fluidic sub-microliter sample introduction system for direct analysis of Chinese rice wine by inductively coupled plasma mass spectrometry using external aqueous calibration

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Heyong [Institute of Microanalytical Systems, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (China); College of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036 (China); Liu, Jinhua [College of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036 (China); Xu, Zigang [Institute of Analytical and Applied Chemistry, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (China); Yin, Xuefeng, E-mail: yinxf@zju.edu.cn [Institute of Microanalytical Systems, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (China); College of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036 (China)

    2012-07-15

    . The recoveries of three Chinese rice wine samples ranged between 95.5 and 102.8%. Furthermore, the determined contents of Cd and Pb in a certified reference material of red wine (GBW 10031) and a quality control test material of wine (FAPAS T07163QC) by the proposed method were in fairly good accordance with the certified/assigned values. All results verified the accuracy of our method. - Highlights: Black-Right-Pointing-Pointer A microfluidic sub-microliter sample introduction system was developed for ICP-MS. Black-Right-Pointing-Pointer Direct analysis of Chinese rice wine by ICP-MS was achieved. Black-Right-Pointing-Pointer No carbon deposit or matrix effect from Chinese rice wine was observed.

  1. CTEPP STANDARD OPERATING PROCEDURE FOR EXTRACTING AND PREPARING LIQUID FOOD SAMPLES FOR ANALYSIS OF PERSISTENT ORGANIC POLLUTANTS (SOP-5.19)

    Science.gov (United States)

    This SOP describes the procedures for homogenizing, extracting, and concentrating liquid food samples for neutral persistent organic pollutants such as organochlorine compounds, organophosphate compounds, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and phenols.

  2. CTEPP STANDARD OPERATING PROCEDURE FOR EXTRACTING AND PREPARING LIQUID FOOD SAMPLES FOR ANALYSIS OF PERSISTENT ORGANIC POLLUTANTS (SOP-5.19)

    Science.gov (United States)

    This SOP describes the procedures for homogenizing, extracting, and concentrating liquid food samples for neutral persistent organic pollutants such as organochlorine compounds, organophosphate compounds, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and phenols.

  3. Tandem Extraction/Liquid Chromatography-Mass Spectrometry Protocol for the Analysis of Acrylamide and Surfactant-related Compounds in Complex Aqueous Environmental Samples

    Science.gov (United States)

    The development of a liquid chromatography‐mass spectrometry (LC‐MS)‐based strategy for the detection and quantitation of acrylamide and surfactant‐related compounds in aqueous complex environmental samples.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hsieh, Kai-Ta; Liu, Pei-Han [Department of Applied Chemistry, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China); Urban, Pawel L. [Department of Applied Chemistry, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China); Institute of Molecular Science, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China)

    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{sup −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. - Highlights: • Mass spectrometric analysis normally requires sample preparation. • Liquid–liquid extraction can isolate analytes from complex matrices. • The proposed system automates

  5. A high performance liquid chromatographic method of analysis of 4'-O-tetrahydropyranyladriamycin and their metabolites in biological samples.

    Science.gov (United States)

    Matsushita, Y; Iguchi, H; Kiyosaki, T; Tone, H; Ishikura, T; Takeuchi, T; Umezawa, H

    1983-07-01

    A method for measuring 4'-O-tetrahydropyranyladriamycin (THP) and its metabolites in biological samples are described. By reversed-phase high performance liquid chromatography using fluorescence detection, THP and its metabolites were all separated on a single chromatogram within 18 minutes. A linear calibration curve was obtained up to 2,000 ng/ml of THP in plasma. The recovery of THP in the analysis was more than 95% above 5 ng/ml and 87.1% even at 1.25 ng/ml. Thus the lower limit was 1.25 ng/ml in biological samples. Blood levels and urinary excretion in mice and dogs were satisfactory measured by this analytical method.

  6. Determination of levamisole and tetramisole in seized cocaine samples by enantioselective high-performance liquid chromatography and circular dichroism detection.

    Science.gov (United States)

    Bertucci, Carlo; Tedesco, Daniele; Fabini, Edoardo; Di Pietra, Anna Maria; Rossi, Francesca; Garagnani, Marco; Del Borrello, Elia; Andrisano, Vincenza

    2014-10-10

    Levamisole, an anthelmintic drug, has been increasingly employed as an adulterant of illicit street cocaine over the last decade; recently, the use of tetramisole, the racemic mixture of levamisole and its enantiomer dexamisole, was also occasionally observed. A new enantioselective high-performance liquid chromatography (HPLC) method, performed on cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phases in normal-phase mode, was validated to determine the enantiomeric composition of tetramisole enantiomers in seized cocaine samples. Furthermore, the hyphenation of the validated HPLC method with a circular dichroism (CD) detection system allowed the direct determination of elution order and a selective monitoring of levamisole and dexamisole in the presence of possible interferences. The method was applied to the identification and quantitation of the two enantiomers of tetramisole in seized street cocaine samples.

  7. Optimized nested Markov chain Monte Carlo sampling: application to the liquid nitrogen Hugoniot using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Shaw, Milton Sam [Los Alamos National Laboratory; Coe, Joshua D [Los Alamos National Laboratory; Sewell, Thomas D [UNIV OF MISSOURI-COLUMBIA

    2009-01-01

    An optimized version of the Nested Markov Chain Monte Carlo sampling method is applied to the calculation of the Hugoniot for liquid nitrogen. The 'full' system of interest is calculated using density functional theory (DFT) with a 6-31 G* basis set for the configurational energies. The 'reference' system is given by a model potential fit to the anisotropic pair interaction of two nitrogen molecules from DFT calculations. The EOS is sampled in the isobaric-isothermal (NPT) ensemble with a trial move constructed from many Monte Carlo steps in the reference system. The trial move is then accepted with a probability chosen to give the full system distribution. The P's and T's of the reference and full systems are chosen separately to optimize the computational time required to produce the full system EOS. The method is numerically very efficient and predicts a Hugoniot in excellent agreement with experimental data.

  8. Determination of insoluble soap in agricultural soil and sewage sludge samples by liquid chromatography with ultraviolet detection.

    Science.gov (United States)

    Cantarero, Samuel; Zafra-Gómez, Alberto; Ballesteros, Oscar; Navalón, Alberto; Vílchez, José L; Crovetto, Guillermo; Verge, Coral; de Ferrer, Juan A

    2010-11-01

    We have developed a new analytical procedure for determining insoluble Ca and Mg fatty acid salts (soaps) in agricultural soil and sewage sludge samples. The number of analytical methodologies that focus in the determination of insoluble soap salts in different environmental compartments is very limited. In this work, we propose a methodology that involves a sample clean-up step with petroleum ether to remove soluble salts and a conversion of Ca and Mg insoluble salts into soluble potassium salts using tripotassium ethylenediaminetetraacetate salt and potassium carbonate, followed by the extraction of analytes from the samples using microwave-assisted extraction with methanol. An improved esterification procedure using 2,4-dibromoacetophenone before the liquid chromatography with ultraviolet detection analysis also has been developed. The absence of matrix effect was demonstrated with two fatty acid Ca salts that are not commercial and are never detected in natural samples (C₁₃:₀ and C₁₇:₀). Therefore, it was possible to evaluate the matrix effect because both standards have similar environmental behavior (adsorption and precipitation) to commercial soaps (C₁₀:₀) to C₁₈:₀). We also studied the effect of the different variables on the clean-up, the conversion of Ca soap, and the extraction and derivatization procedures. The quantification limits found ranged from 0.4 to 0.8 mg/kg. The proposed method was satisfactorily applied for the development of a study on soap behavior in agricultural soil and sewage sludge samples.

  9. A new liquid chromatography-tandem mass spectrometry method for determination of parabens in human placental tissue samples.

    Science.gov (United States)

    Jiménez-Díaz, I; Vela-Soria, F; Zafra-Gómez, A; Navalón, A; Ballesteros, O; Navea, N; Fernández, M F; Olea, N; Vílchez, J L

    2011-05-15

    Endocrine disruptors are a group of organic compounds widely used, which are ubiquitous in the environment and in biological samples. The main effect of these compounds is associated with their ability to mimic or block the action of natural hormones in living organisms, including humans. Parabens (esters of p-hydroxybenzoic acid) belong to this group of compounds. In this work, we propose a new liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to asses the presence of parabens most commonly used in industrial applications (methyl-, ethyl-, propyl- and butyl-paraben) in samples of human placental tissue. The method involves the extraction of the analytes from the samples using ethyl acetate, followed by a clean-up step using centrifugation prior to their quantification by LC-MS/MS using an atmospheric pressure chemical ionization (APCI) interface in the negative mode. Deuterated bisphenol A (BPA-d(16)) was used as surrogate. Found detection limits (LOD) ranged from 0.03 to 0.06 ng g(-1) and quantification limits (LOQ) from 0.1 to 0.2 ng g(-1), while inter- and intra-day variability was under 13.8%. The method was validated using standard addition calibration and a spike recovery assay. Recovery rates for spiked samples ranged from 82% to 108%. This method was satisfactorily applied for the determination of parabens in 50 placental tissue samples collected from women who live in the province of Granada (Spain).

  10. Testing automated liquid-based cytology samples with a manual liquid-based cytology method using residual cell suspensions from 500 ThinPrep cases.

    Science.gov (United States)

    Maksem, John A; Dhanwada, Vijaya; Trueblood, Joy E; Weidmann, James; Kane, Bruce; Bolick, David R; Bedrossian, Carlos W M; Kurtycz, Daniel F I; Stewart, Jim

    2006-06-01

    We report a technical improvement upon a previously disclosed manual liquid-based cytology (MLBC) method; and, we use the improved method to prepare slides from residual ThinPrep specimens in order to see how often ThinPrep diagnoses correspond to diagnoses derived from exhaustive examination of their parent sample suspensions. Residual cell suspensions from 500 ThinPrep cases comprising (1) 20 low-grade squamous intraepithelial lesions (LSILs); (2) 200 high risk (HR) negatives and 20 ASC-US; and (3) 260 screening cytology specimens were studied. Institutional review committee guidelines allowed us to know diagnoses by groups of specimens, but did not allow us to know individual patient diagnoses, so we could not perform case-by-case matched outcome-comparisons. Cells were concentrated by conventional centrifugation and sedimented into a polymer gel that was then vortex-mixed and converted into a viscous cell-rich suspension. The cell suspension was smeared between two clean glass slides, which were air-dried and stained with the Papanicolaou stain. Two study-sets were created, comprising one slide from each case. Each of the two study sets was examined by two cytopathologists, and discordant diagnoses were adjudicated. Because of the ambiguity involved in the "atypical" (ASC-US, ASC-H, AGC) diagnosis categories, only outcomes at the level of LSIL or greater were recorded. All MLBC SILs were digitally imaged and abnormal slides plus digital images were sent to the laboratory that provided the residual automated liquid-based cytology (ALBC) suspensions. The final diagnoses were confirmed by the laboratory that provided the residual ALBC specimens. MLBC slides of the 20 LSIL cases afforded 2 high-grade squamous intraepithelial lesions (HSILs) and 18 LSILs. Those of the 200 HR-Negatives showed 3 HSILs and 30 LSILs; and those of the 20 HR-ASC-US showed 3 HSILs and 9 LSILs. MLBC slides of the 260 screening cytology specimens showed 1 Carcinoma, 3 HSILs and 20 LSILs

  11. Evaluation of Mercury in Environmental Samples by a Supramolecular SolventBased Dispersive LiquidLiquid Microextraction Method Before Analysis by a Cold Vapor Generation Technique.

    Science.gov (United States)

    Ali, Jamshed; Tuzen, Mustafa; Kazi, Tasneem G

    2017-02-01

    Supramolecular solvent–based dispersive liquid–liquid microextraction was used as a preconcentration method for the determination of trace levels of Hg. This simple method accurately measured oxidized HgII content in claystone and sandstone samples obtained from the Thar Coalfield in Pakistan. Cold vapor atomic absorption spectrometry was used as the detection technique because it is reliable and accurate. The HgII in acidic media forms a complex with dithizone (DTz) in the presence of supramolecular solvent (tetrahydrofuran and 1-undecanol), forming reverse micelles. Formation of the Hg-DTz complex was achieved to increase the interactions with the supramolecular solvent phase at pH 2.5 under the optimized experimental conditions. After addition of the supramolecular solvent to the aqueous solution, the micelles were uniformly mixed using a vortex mixer. The cloudy solution was centrifuged, and the Hg-DTz complex was extracted into the supramolecular solvent phase. Under optimized experimental conditions, the LOD and enrichment factor were found to be 5.61 ng/L and 77.8, respectively. Accuracy of the developed method was checked with Certified Reference Materials. The developed method was successfully applied for the determination of HgII in claystone and sandstone samples from the Block VII and Block VIII areas of the Thar Coalfield on the basis of depth.

  12. Liquid chromatographic determination of quinolones in water and human urine samples after microextraction by packed sorbent.

    Science.gov (United States)

    Rani, Susheela; Kumar, Ashwini; Malik, Ashok Kumar; Singh, Baldev

    2012-01-01

    A method for the simultaneous determination of quinolones in water and urine samples by microextraction in a sorbent-packed syringe (MEPS) with LC is described. MEPS is a new miniaturized SPE technique that can be used with chromatographic instruments without any modifications. In MEPS, approximately 1 mg of the solid packing material is inserted into a syringe (100-250 microL) as a plug. Sample preparation takes place on the packed bed. The new method is promising, easy to use, economical, and rapid. The determination of quinolones in groundwater and urine was performed using MEPS as a sample preparation method with LC-UV determination. Four quinolone antibiotics--enrofloxacin, enoxacin, danofloxacin, and nalidixic acid--in groundwater and urine samples were used as analytes. The extraction recovery was found to be between 64.9 and 98.9%. The results showed high correlation coefficients (R2 > 0.992) for all of the analytes within the calibration range. The LOQ was between 0.091 and 0.315 ng/mL.

  13. Hollow porous ionic liquids composite polymers based solid phase extraction coupled online with high performance liquid chromatography for selective analysis of hydrophilic hydroxybenzoic acids from complex samples.

    Science.gov (United States)

    Dai, Xingping; Wang, Dongsheng; Li, Hui; Chen, Yanyi; Gong, Zhicheng; Xiang, Haiyan; Shi, Shuyun; Chen, Xiaoqing

    2017-02-10

    Polar and hydrophilic properties of hydroxybenzoic acids usually made them coelute with interferences in high performance liquid chromatography (HPLC) analysis. Then selective analysis of them was necessary. Herein, hollow porous ionic liquids composite polymers (PILs) based solid phase extraction (SPE) was firstly fabricated and coupled online with HPLC for selective analysis of hydroxybenzoic acids from complex matrices. Hollow porous PILs were firstly synthesized using Mobil Composition of Matter No. 48 (MCM-48) spheres as sacrificial support, 1-vinyl-3-methylimidazolium chloride (VMIM(+)Cl(-)) as monomer, and ethylene glycol dimethacrylate (EGDMA) as cross-linker. Various parameters affecting synthesis, adsorption and desorption behaviors were investigated and optimized. Steady-state adsorption studies showed the resulting hollow porous PILs exhibited high adsorption capacity, fast adsorption kinetics, and excellent specific adsorption. Subsequently, the application of online SPE system was studied by selective analysis of protocatechuic acid (PCA), 4-hydroxybenzoic acid (4-HBA), and vanillic acid (VA) from Pollen Typha angustifolia. The obtained limit of detection (LOD) varied from 0.002 to 0.01μg/mL, the linear range (0.05-5.0μg/mL) was wide with correlation coefficient (R) from 0.9982 to 0.9994, and the average recoveries at three spiking levels ranged from 82.7 to 102.4%, with column-to-column relative standard deviation (RSD) below 8.1%. The proposed online method showed good accuracy, precision, specificity and convenience, which opened up a universal and efficient route for selective analysis of hydroxybenzoic acids from complex samples.

  14. Planar graphene oxide-based magnetic ionic liquid nanomaterial for extraction of chlorophenols from environmental water samples coupled with liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Cai, Mei-Qiang; Su, Jie; Hu, Jian-Qiang; Wang, Qian; Dong, Chun-Ying; Pan, Sheng-Dong; Jin, Mi-Cong

    2016-08-12

    A planar graphene oxide-based magnetic ionic liquid nanomaterial (PGO-MILN) was synthesized. The prepared PGO-MILN was characterized by transmission electronmicroscopy (TEM) and Fourier-transform infrared spectrometry (FTIR). The results of adsorption experiments showed that the PGO-MILN had great adsorption capacity for 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) and pentachlorophenol (PCP). Based on the adsorption experimental data, a sensitive magnetic method for determination of the five CPs in environmental water samples was developed by an effective magnetic solid-phase extraction (MSPE) procedure coupled with high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). The effects of main MSPE parameters including the solution pH, extraction time, desorption time, and volume of desorption solution on the extraction efficiencies had been investigated in detail. The recoveries ranged from 85.3 to 99.3% with correlation coefficients (r) higher than 0.9994 and the linear ranges were between 10 and 500ngL(-1). The limits of detection (LODs) and limits of quantification (LOQs) of the five CPs ranged from 0.2 to 2.6ngL(-1) and 0.6 to 8.7ngL(-1), respectively. The intra- and inter- day relative standard deviations (RSDs) were in the range from 0.6% to 7.4% and from 0.7% to 8.4%, respectively. It was confirmed that the PGO-MILN was a kind of highly effective MSPE materials used for enrichment of trace CPs in the environmental water. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. A simple and selective method for determination of phthalate biomarkers in vegetable samples by high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry.

    Science.gov (United States)

    Zhou, Xi; Cui, Kunyan; Zeng, Feng; Li, Shoucong; Zeng, Zunxiang

    2016-06-01

    In the present study, solid-phase extraction cartridges including silica reversed-phase Isolute C18, polymeric reversed-phase Oasis HLB and mixed-mode anion-exchange Oasis MAX, and liquid-liquid extractions with ethyl acetate, n-hexane, dichloromethane and its mixtures were compared for clean-up of phthalate monoesters from vegetable samples. Best recoveries and minimised matrix effects were achieved using ethyl acetate/n-hexane liquid-liquid extraction for these target compounds. A simple and selective method, based on sample preparation by ultrasonic extraction and liquid-liquid extraction clean-up, for the determination of phthalate monoesters in vegetable samples by liquid chromatography/electrospray ionisation-tandem mass spectrometry was developed. The method detection limits for phthalate monoesters ranged from 0.013 to 0.120 ng g(-1). Good linearity (r(2)>0.991) between MQLs and 1000× MQLs was achieved. The intra- and inter-day relative standard deviation values were less than 11.8%. The method was successfully used to determine phthalate monoester metabolites in the vegetable samples.

  16. Determination of extremely low {sup 236}U/{sup 238}U isotope ratios in environmental samples by sector-field inductively coupled plasma mass spectrometry using high-efficiency sample introduction

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, Sergei F. [Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University Mainz, Duesbergweg 10-14, 55099 Mainz (Germany)]. E-mail: sergei.boulyga@univie.ac.at; Heumann, Klaus G. [Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University Mainz, Duesbergweg 10-14, 55099 Mainz (Germany)

    2006-07-01

    A method by inductively coupled plasma mass spectrometry (Icp-Ms) was developed which allows the measurement of {sup 236}U at concentration ranges down to 3 x 10{sup -14} g g{sup -1} and extremely low {sup 236}U/{sup 238}U isotope ratios in soil samples of 10{sup -7}. By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5000 counts fg{sup -1} uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH{sup +}/U{sup +} down to a level of 10{sup -6}. An abundance sensitivity of 3 x 10{sup -7} was observed for {sup 236}U/{sup 238}U isotope ratio measurements at mass resolution 4000. The detection limit for {sup 236}U and the lowest detectable {sup 236}U/{sup 238}U isotope ratio were improved by more than two orders of magnitude compared with corresponding values by alpha spectrometry. Determination of uranium in soil samples collected in the vicinity of Chernobyl nuclear power plant (NPP) resulted in that the {sup 236}U/{sup 238}U isotope ratio is a much more sensitive and accurate marker for environmental contamination by spent uranium in comparison to the {sup 235}U/{sup 238}U isotope ratio. The ICP-MS technique allowed for the first time detection of irradiated uranium in soil samples even at distances more than 200 km to the north of Chernobyl NPP (Mogilev region). The concentration of {sup 236}U in the upper 0-10 cm soil layers varied from 2 x 10{sup -9} g g{sup -1} within radioactive spots close to the Chernobyl NPP to 3 x 10{sup -13} g g{sup -1} on a sampling site located by >200 km from Chernobyl.

  17. Triple-Quadrupole Inductively Coupled Plasma-Mass Spectrometry with a High-Efficiency Sample Introduction System for Ultratrace Determination of (135)Cs and (137)Cs in Environmental Samples at Femtogram Levels.

    Science.gov (United States)

    Zheng, Jian; Cao, Liguo; Tagami, Keiko; Uchida, Shigeo

    2016-09-06

    High yield fission products, (135)Cs and (137)Cs, have entered the environment as a result of anthropogenic nuclear activities. Analytical methods for ultratrace measurement of (135)Cs and (137)Cs are required for environmental geochemical and nuclear forensics studies. Here we report a highly sensitive method combining a desolvation sample introduction system (APEX-Q) with triple-quadrupole inductively coupled plasma mass spectrometry (AEPX-ICPMS/MS) for the determination of (135)Cs and (135)Cs/(137)Cs isotope ratio at femtogram levels. Using this system, we introduced only selected ions into the collision/reaction cell to react with N2O, significantly reducing the isobaric interferences ((135)Ba(+) and (137)Ba(+)) and polyatomic interferences ((95,97)Mo(40)Ar(+), (119)Sn(16)O(+), and (121)Sb(16)O(+)). Compared to the instrument setup of ICPMS/MS, the APEX-ICPMS/MS enables a 10-fold sensitivity increase. In addition, an effective chemical separation scheme consisting of ammonium molybdophosphate (AMP) Cs-selective adsorption and two-stage ion-exchange chromatographic separation was developed to remove major matrix and interfering elements from environmental samples (10-40 g). This separation method showed high decontamination factors (10(4)-10(7)) for major matrix elements (Al, Ca, K, Mg, Na, and Si) and interfering elements (Ba, Mo, Sb, and Sn). The high sensitivity of APEX-ICPMS/MS and the effective removal sample matrix allowed reliable analysis of (135)Cs and (137)Cs with extremely low detection limits (0.002 pg mL(-1), corresponding to 0.006 Bq mL(-1) (137)Cs). The accuracy and applicability of the APEX-ICPMS/MS method was validated by analysis of seven standard reference materials (soils, sediment, and plants). For the first time, ultratrace determination of (135)Cs and (135)Cs/(137)Cs isotope ratio at global fallout source environmental samples was achieved with the ICPMS technique.

  18. Simultaneous determination of bisphenol A and estrogens in hair samples by liquid chromatography-electrospray tandem mass spectrometry.

    Science.gov (United States)

    Lee, Chaelin; Kim, Chong Hyeak; Kim, Sunghwan; Cho, Sung-Hee

    2017-07-15

    Bisphenol A (BPA), an endocrine disrupter, is widely used to make chemicals for polycarbonate, plastics, beverage containers, epoxy resins, and cash register receipts. BPA is one of the known xenoestrogens, which have weak estrogenic activity and cause obesity, diabetes, breast cancer, and reproductive disorders. Even though the concentration level of metabolomes in hair is usually lower than that in urine and blood, there are several reasons why we chose to use hair samples. First, the sampling procedure of hairs is simple. Second, it is also easy to preserve the sample for long term and track the drug-exposure record of a given sample. Third, deformation and contamination of samples rarely occur. In this study, an improved analytical method to determine the levels of BPA and estrogens in hair samples was developed by liquid chromatography-electrospray tandem mass spectrometry (LC-ESI/MS/MS). Hair samples were extracted by an Oasis HLB extraction cartridge after incubation with 1N HCl and derivatized with dansyl chloride to increase sensitivity. BPA and estrogens (estrone, 17β-estradiol, and estriol) were separated using Shiseido CAPCELL PAK C18 column (2.0×100mm, 3μm) and a mobile phase consisting of 10mM ammonium acetate in water and acetonitrile with a gradient program at a flow rate of 0.3mL/min and were monitored with electrospray tandem mass spectrometry (ESI-MS/MS). The linearity of this method was over 0.995. The limits of detection (LOD) at a signal-to-noise (S/N) ratio of 3 were 0.25-6.0ng/g. The alteration of estrogens levels induced by BPA may play important role to understanding probable endocrine disruptive exposure, and the described methods could be used to evaluate and monitor exposure of endocrine disruptor. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Low-density solvent-based dispersive liquid-liquid microextraction combined with single-drop microextraction for the fast determination of chlorophenols in environmental water samples by high performance liquid chromatography-ultraviolet detection.

    Science.gov (United States)

    Li, Xiaoyi; Xue, Aifang; Chen, Hao; Li, Shengqing

    2013-03-08

    A new format of fast three-phase microextraction by combining low-density solvent-based dispersive liquid-liquid microextraction (DLLME) and single-drop microextraction (SDME) was for the first time developed for the determination of chlorophenols in environmental water samples. The extraction procedure includes a 2 min DLLME pre-extraction and a 10 min SDME back-extraction. A portion of low-density solvent (toluene) was used as organic phase and injected into the aqueous sample (donor phase) with methanol as disperser. The analytes were pre-extracted into the organic phase within 2 min. A thin layer of the organic phase formed on the top of the aqueous phase by a 2 min centrifugation. Then a drop of acceptor solution was introduced into the upper layer and SDME was carried out for the back-extraction. The stirring step typically involved in SDME and LLLME is avoided with the benefit of the high speed and efficiency of DLLME pre-extraction. After extraction, the acceptor drop was withdrawn and directly injected into a high performance liquid chromatography instrument with ultraviolet detection for analysis. Five chlorophenols, 4-chlorophenol, 2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol, were selected as model compounds for developing and evaluating the method. Factors affecting extraction efficiency were studied, including the organic solvent, the disperser solvent, the composition of donor phase and acceptor phase, the volume of acceptor microdrop, and the extraction time. At optimal conditions, the method showed low detection limit (0.016-0.084 μg/L) for the five chlorophenols, good linearity (from 0.2-250 to 1.0-250 μg/L, depending on the analytes) and repeatability (RSD below 8.2, n=5). The simple, fast, and efficient feature of the proposed method was demonstrated by the analysis of chlorophenols in environmental water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Utility of manual liquid-based cytology and conventional smears in the evaluation of various fine-needle aspiration samples

    Directory of Open Access Journals (Sweden)

    P Arul

    2016-01-01

    Full Text Available Background: Liquid-based cytology (LBC preparation is a way to improve and refine the fine-needle aspiration (FNA samples. There are a few studies comparing LBC with conventional smear (CS. Aim: The present study was undertaken to evaluate the utility of manual LBC (MLBC and CS preparations in various FNA samples. Materials and Methods: In this cross-sectional study, a total of 100 FNA samples from various anatomical sites were evaluated using MLBC and CS preparations. Cellularity, blood, informative background, monolayers, cell architecture, cytoplasmic, and nuclear preservation were compared with MLBC and CS preparations by Wilcoxon signed rank test. P < 0.05 is considered statistically significant. Results: MLBC preparations were superior to CS preparations in view of absence of blood and debris (P = 0.001, presence of monolayers (P < 0.001, and preservation of cytoplasmic (P = 0.001 and nuclear details (P = 0.001. However, no statistically significant differences were found between MLBC and CS preparations with regard to cellularity (P = 0.157, informative background (P = 0.083, and architecture (P = 0.739. Conclusion: MLBC preparations in FNAC are a safe, easy, and less time-consuming procedure, and it may have promising diagnostic value in the evaluation of FNA samples from various anatomical sites. However, the use of both MLBC and CS preparations is recommended to achieve optimal diagnostic yield.

  1. Utility of manual liquid-based cytology and conventional smears in the evaluation of various fine-needle aspiration samples.

    Science.gov (United States)

    Arul, P

    2016-01-01

    Liquid-based cytology (LBC) preparation is a way to improve and refine the fine-needle aspiration (FNA) samples. There are a few studies comparing LBC with conventional smear (CS). The present study was undertaken to evaluate the utility of manual LBC (MLBC) and CS preparations in various FNA samples. In this cross-sectional study, a total of 100 FNA samples from various anatomical sites were evaluated using MLBC and CS preparations. Cellularity, blood, informative background, monolayers, cell architecture, cytoplasmic, and nuclear preservation were compared with MLBC and CS preparations by Wilcoxon signed rank test. P < 0.05 is considered statistically significant. MLBC preparations were superior to CS preparations in view of absence of blood and debris (P = 0.001), presence of monolayers (P < 0.001), and preservation of cytoplasmic (P = 0.001) and nuclear details (P = 0.001). However, no statistically significant differences were found between MLBC and CS preparations with regard to cellularity (P = 0.157), informative background (P = 0.083), and architecture (P = 0.739). MLBC preparations in FNAC are a safe, easy, and less time-consuming procedure, and it may have promising diagnostic value in the evaluation of FNA samples from various anatomical sites. However, the use of both MLBC and CS preparations is recommended to achieve optimal diagnostic yield.

  2. Determination of parabens in environmental solid samples by ultrasonic-assisted extraction and liquid chromatography with triple quadrupole mass spectrometry.

    Science.gov (United States)

    Núñez, L; Tadeo, J L; García-Valcárcel, A I; Turiel, E

    2008-12-19

    Analysis of various p-hydroxybenzoic esters (methyl, ethyl, isopropyl, propyl, benzyl, and butylparaben) in environmental solid samples was carried out by sonication-assisted extraction in small columns (SAESC) followed by liquid chromatography with triple quadrupole mass spectrometry (MS/MS). Solid samples were placed in small glass columns and extraction performed assisted by sonication in two consecutive steps of 15 min using acetonitrile as extraction solvent. Sample extracts were evaporated under nitrogen stream to 1 ml and analysed by LC-MS/MS. Satisfactory recoveries were obtained ranging from 83% to 110% depending on the analyte. Good limits of quantification (LOQs), between 0.11 and 0.49 ng g(-1) were obtained for LC-MS/MS, making this technique suitable for the determination of parabens in environmental solid samples, particularly at trace level. The developed method was applied to the determination of target analytes in different types of soil and sediments, finding levels between LOD and 6.35 ng g(-1).

  3. Supercritical Fluid Extraction and Ultra Performance Liquid Chromatography of Respiratory Quinones for Microbial Community Analysis in Environmental and Biological Samples

    Directory of Open Access Journals (Sweden)

    Koichi Fujie

    2012-03-01

    Full Text Available Microbial community structure plays a significant role in environmental assessment and animal health management. The development of a superior analytical strategy for the characterization of microbial community structure is an ongoing challenge. In this study, we developed an effective supercritical fluid extraction (SFE and ultra performance liquid chromatography (UPLC method for the analysis of bacterial respiratory quinones (RQ in environmental and biological samples. RQ profile analysis is one of the most widely used culture-independent tools for characterizing microbial community structure. A UPLC equipped with a photo diode array (PDA detector was successfully applied to the simultaneous determination of ubiquinones (UQ and menaquinones (MK without tedious pretreatment. Supercritical carbon dioxide (scCO2 extraction with the solid-phase cartridge trap proved to be a more effective and rapid method for extracting respiratory quinones, compared to a conventional organic solvent extraction method. This methodology leads to a successful analytical procedure that involves a significant reduction in the complexity and sample preparation time. Application of the optimized methodology to characterize microbial communities based on the RQ profile was demonstrated for a variety of environmental samples (activated sludge, digested sludge, and compost and biological samples (swine and Japanese quail feces.

  4. Determination of neonicotinoid insecticides and strobilurin fungicides in particle phase atmospheric samples by liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Raina-Fulton, Renata

    2015-06-01

    A liquid chromatography-tandem mass spectrometry method has been developed for the determination of neonicotinoids and strobilurin fungicides in the particle phase fraction of atmosphere samples. Filter samples were extracted with pressurized solvent extraction, followed by a cleanup step with solid phase extraction. Method detection limits for the seven neonicotinoid insecticides and six strobilurin fungicides were in the range of 1.0-4.0 pg/m(3). Samples were collected from June to September 2013 at two locations (Osoyoos and Oliver) in the southern Okanagan Valley Agricultural Region of British Columbia, where these insecticides and fungicides are recommended for use on tree fruit crops (apples, pears, cherries, peaches, apricots) and vineyards. This work represents the first detection of acetamiprid, imidacloprid, clothianidin, kresoxim-methyl, pyraclostrobin, and trifloxystrobin in particle phase atmospheric samples collected in the Okanagan Valley in Canada. The highest particle phase atmospheric concentrations were observed for imidacloprid, pyraclostrobin, and trifloxystrobin at 360.0, 655.6, and 1908.2 pg/m(3), respectively.

  5. Supercritical fluid extraction and ultra performance liquid chromatography of respiratory quinones for microbial community analysis in environmental and biological samples.

    Science.gov (United States)

    Hanif, Muhammad; Atsuta, Yoichi; Fujie, Koichi; Daimon, Hiroyuki

    2012-03-05

    Microbial community structure plays a significant role in environmental assessment and animal health management. The development of a superior analytical strategy for the characterization of microbial community structure is an ongoing challenge. In this study, we developed an effective supercritical fluid extraction (SFE) and ultra performance liquid chromatography (UPLC) method for the analysis of bacterial respiratory quinones (RQ) in environmental and biological samples. RQ profile analysis is one of the most widely used culture-independent tools for characterizing microbial community structure. A UPLC equipped with a photo diode array (PDA) detector was successfully applied to the simultaneous determination of ubiquinones (UQ) and menaquinones (MK) without tedious pretreatment. Supercritical carbon dioxide (scCO(2)) extraction with the solid-phase cartridge trap proved to be a more effective and rapid method for extracting respiratory quinones, compared to a conventional organic solvent extraction method. This methodology leads to a successful analytical procedure that involves a significant reduction in the complexity and sample preparation time. Application of the optimized methodology to characterize microbial communities based on the RQ profile was demonstrated for a variety of environmental samples (activated sludge, digested sludge, and compost) and biological samples (swine and Japanese quail feces).

  6. Multivariate optimization and simultaneous determination of hydride and non-hydride-forming elements in samples of a wide pH range using dual-mode sample introduction with plasma techniques: application on leachates from cement mortar material.

    Science.gov (United States)

    Mulugeta, Mesay; Wibetoe, Grethe; Engelsen, Christian J; Asfaw, Alemayehu

    2009-02-01

    Analytical methods have been developed for the simultaneous determination of hydride-forming (As, Sb) and non-hydride-forming (Cr, Mo, V) elements in aqueous samples of a wide pH range (pH 3-13). The methods used dual-mode (DM) sample introduction with ICP-AES and ICP-MS instruments. The effect of selected experimental variables, i.e., sample pH and concentrations of HNO(3), thiourea, and NaBH(4), were studied in a multivariate way using face-centered central composite design (FC-CCD). Compromised optimum values of the experimental parameters were identified using a response optimizer. The statistically found optimum values were verified experimentally. The methods provided improved sensitivities for the hydride-forming elements compared with the respective conventional nebulization (Neb) systems by factors of 67 (As) and 64 (Sb) for ICP-AES and 36 (As) and 54 (Sb) for ICP-MS. Slight sensitivity improvements were also observed for the non-hydride-forming elements. The limits of detection (LOD) of As and Sb were lowered, respectively, to 0.8 and 0.9 microg L(-1) with the DM-ICP-AES system and to 0.01 and 0.02 microg L(-1) with the DM-ICP-MS system. The short-term stabilities of both methods were between 2.1 and 5.4%. The methods were applied for the analysis of leachates of a cement mortar material prepared in the pH range 3-13. The elemental concentration of the leachates determined by the two DM methods were statistically compared with the values obtained from Neb-ICP-MS analysis; the values showed good agreement at the 95% confidence level. Quantitative spike recoveries were obtained for the analytes from most of the leachates using both DM methods.

  7. Validation of a liquid chromatography ultraviolet method for determination of herbicide diuron and its metabolites in soil samples

    Directory of Open Access Journals (Sweden)

    ANA LUCIA S.M. FELICIO

    2016-01-01

    Full Text Available ABSTRACT Diuron is one of the most widely herbicide used worldwide, which can undergo degradation producing three primary metabolites: 3,4-dichlorophenylurea, 3-(3,4-dichlorophenyl-1-methylurea, and 3,4-dichloroaniline. Since the persistence of diuron and its by-products in ecosystems involves risk of toxicity to environment and human health, a reliable quantitative method for simultaneous monitoring of these compounds is required. Hence, a simple method without preconcentration step was validated for quantitation of diuron and its main metabolites by high performance liquid chromatography with ultraviolet detection. Separation was achieved in less than 11 minutes using a C18 column, mobile phase composed of acetonitrile and water (45:55 v/v at 0.86 mL min-1 and detection at 254 nm. The validated method using solid-liquid extraction followed by an isocratic chromatographic elution proved to be specific, precise and linear (R2 ˃ 0.99, presenting more than 90% of recovery. The method was successfully applied to quantify diuron and their by-products in soil samples collected in a sugarcane cultivation area, focusing on the environmental control.

  8. Capillary gas-liquid chromatography separation of phenethylamines in amphetamine-positive urine samples.

    Science.gov (United States)

    DePace, A; Verebey, K; elSohly, M

    1990-11-01

    Good gas chromatography (GC) separation of molecules is essential for clean gas chromatography/mass spectrometry (GC/MS) confirmation of compounds. The trifluoro derivatives of ephedrine (E) and methamphetamine (MA) coelute on dimethyl silicone capillary columns, such as DB-1, which are most commonly used by chromatographers. Methods are described to separate E and MA to aid GC/MS confirmations of methamphetamine, ephedrine, or both E and MA together, whichever may be present in Enzyme Immunoassay (EIA)-analyzed amphetamine-positive urine samples. The use of the heptafluoro derivatives of E and MA on a DB-1 column, or the trifluoro derivatives of E and MA on a DB-17 column, is suggested for good gas chromatographic separation.

  9. Electrokinetic extraction on artificial liquid membranes of amphetamine-type stimulants from urine samples followed by high performance liquid chromatography analysis.

    Science.gov (United States)

    Seidi, Shahram; Yamini, Yadollah; Baheri, Tahmineh; Feizbakhsh, Rouhollah

    2011-07-01

    Electromembrane extraction (EME) coupled with high performance liquid chromatography and ultraviolet detection was developed for determination of amphetamine-type stimulants in human urine samples. Amphetamines migrated from 3 mL of different human urine matrices, through a thin layer of 2-nitrophenyl octyl ether (NPOE) containing 15% tris-(2-ethylhexyl) phosphate (TEHP) immobilized in the pores of a porous hollow fiber, and into a 15 μL acidic aqueous acceptor solution present inside the lumen of the fiber. Equilibrium extraction conditions were obtained after 7 min of operation. Experimental design and response surface methodology (RSM) were used for optimization of EME parameters. Under optimal conditions, amphetamines were effectively extracted with recoveries in the range of 54-70%, which corresponded to preconcentration factors in the range of 108-140. The calibration curves were investigated in the range of 0-7 μg mL(-1) and good linearity was achieved with a coefficient of estimation better than 0.991. Detection limits and inter-day precision (n=3) were less than 0.01 μg mL(-1) and 11.2%, respectively.

  10. Detection of an intermediate biaxial phase in the phase diagram of biaxial liquid crystals: Entropic sampling study

    Science.gov (United States)

    Kamala Latha, B.; Jose, Regina; Murthy, K. P. N.; Sastry, V. S. S.

    2014-05-01

    We investigate the phase sequence of biaxial liquid crystals, based on a general quadratic model Hamiltonian over the relevant parameter space, with a Monte Carlo simulation which constructs equilibrium ensembles of microstates, overcoming possible (free) energy barriers (combining entropic and frontier sampling techniques). The resulting phase diagram qualitatively differs from the universal phase diagram predicted earlier from mean-field theory (MFT), as well as the Monte Carlo simulations with the Metropolis algorithm. The direct isotropic-to-biaxial transition predicted by the MFT is replaced in certain regions of the space by the onset of an additional intermediate biaxial phase of very low order, leading to the sequence NB-NB1-I. This is due to inherent barriers to fluctuations of the components comprising the total energy, and may explain the difficulties in the experimental realization of these phases.

  11. Comprehensive ultra-performance liquid chromatographic separation and mass spectrometric analysis of eicosanoid metabolites in human samples.

    Science.gov (United States)

    Wang, Yan; Armando, Aaron M; Quehenberger, Oswald; Yan, Chao; Dennis, Edward A

    2014-09-12

    Over the past decade, the number of known eicosanoids has expanded immensely and we have now developed an ultra-performance liquid chromatography-electrospray ionization triple quadrupole mass spectrometric (UPLC-QTRAP/MS/MS) method to monitor and quantify numerous eicosanoids. The UPLC-QTRAP/MS/MS approach utilizes scheduled multiple reaction monitoring (MRM) to optimize sensitivity, number of metabolites that can be analyzed and the time requirement of the analysis. A total of 184 eicosanoids including 26 deuterated internal standards can be separated and monitored in a single 5min UPLC run. To demonstrate a practical application, human plasma samples were analyzed following solid-phase extraction (SPE) and the recovery rate and matrix effects were determined for the 26 deuterated internal standards added to the plasma. The method was validated and shown to be sensitive with the limit of quantitation at pg levels for most compounds, accurate with recovery rates of 70-120%, and precise with a CVeicosanoids.

  12. Sampling and sample preparation development for analytical and on-line measurement techniques of process liquids; Naeytteenoton ja kaesittelyn kehittaeminen prosessinesteiden analytiikan ja on-line mittaustekniikan tarpeisiin - MPKT 11

    Energy Technology Data Exchange (ETDEWEB)

    Karttunen, K. [Oulu Univ. (Finland)

    1998-12-31

    Main goal of the research project is to develop sampling and sample handling methods and techniques for pulp and paper industry to be used for analysis and on-line purposes. The research focus specially on the research and development of the classification and separation methods and techniques needed for liquid and colloidal substances as well as in ion analysis. (orig.)

  13. Rapid Isolation and Determination of Flavones in Biological Samples Using Zinc Complexation Coupled with High-Performance Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    Chenghe Sun

    2016-08-01

    Full Text Available Chlorophyll-type contaminants are commonly encountered in the isolation and determination of flavones of plant aerial plant parts. Heme is also a difficult background substance in whole blood analysis. Both chlorophyll and heme are porphyrin type compounds. In this study, a rapid method for isolating flavones with 5-hydroxyl or ortho-hydroxyl groups from biological samples was developed based on the different solubilities of porphyrin-metal and flavone-metal complexes. It is important that other background substances, e.g., proteins and lipids, are also removed from flavones without an additional processing. The recoveries of scutellarin, baicalin, baicalein, wogonoside and wogonin, which are the primary constituents of Scutellaria baicalensis (skullcaps were 99.65% ± 1.02%, 98.98% ± 0.73%, 99.65% ± 0.03%, 97.59% ± 0.09% and 95.19% ± 0.47%, respectively. As a sample pretreatment procedure, this method was coupled to high-performance liquid chromatography (HPLC with good separation, sensitivity and linearity and was applied to determine the flavone content in different aerial parts of S. baicalensis and in dried blood spot samples.

  14. Pressurized liquid extraction followed by gas chromatography with atomic emission detection for the determination of fenbutatin oxide in soil samples.

    Science.gov (United States)

    Canosa, P; Montes, R; Lamas, J P; García-López, M; Orriols, I; Rodríguez, I

    2009-08-15

    A novel method for the determination of the miticide bis[tris(2-methyl-2-phenylpropyl)tin] oxide, also known as fenbutatin oxide (FBTO), in agricultural soils is presented. Pressurized liquid extraction (PLE) followed by analyte derivatization and extraction into isooctane was the used sample preparation approach. Selective determination was achieved by gas chromatography with atomic emission detection (GC-AED). Influence of different parameters on the performance of the extraction process is thoroughly discussed; moreover, some relevant aspects related to derivatization, determination and quantification steps are also presented. As regards PLE, the type of solvent and the temperature were the most relevant variables. Under optimized conditions, acetone, without any acidic modifier, was employed as extractant at 80 degrees C. Cells were pressurized at 1500 psi, and 2 static cycles of 1 min each were applied. Acetone extracts (ca. 25 mL) were concentrated to 1 mL, derivatized with sodium tetraethyl borate (NaBEt(4)) and the FBTO derivative, resulting from cleavage of the Sn-O-Sn bond followed by ethylation of the hydroxyl fragments, extracted into isooctane and determined by GC-AED. Under final working conditions, the proposed method provided recoveries from 76 to 99% for spiked soil samples, a limit of quantification of 2 ng g(-1) and an acceptable precision. Analysis of samples from vineyards sprayed with FBTO, confirmed the persistence of the miticide in soil for more than 1 year after being applied.

  15. Analysis of thyreostatic drugs in thyroid samples by ultra-performance liquid chromatography tandem mass spectrometry detection.

    Science.gov (United States)

    Abuín, S; Centrich, F; Rúbies, A; Companyó, R; Prat, M D

    2008-06-09

    A method based on ultra-performance liquid chromatography-electrospray ionisation-tandem mass spectrometry for the determination of six thyreostatic drugs in thyroid tissue has been optimised and validated in accordance with the Decision 2002/657/EC. Samples are extracted with methanol and the extracts cleaned-up on silica cartridges. The recoveries range from 40% for 6-phenyl-2-thiouracil to 79% for 2-thiouracil. Quantification is carried out with blank tissue samples spiked with the analytes in the range 25-500 microg kg(-1). 5,6-Dimethyl-2-thiouracil is used as internal standard. CCalpha and CCbeta are in the ranges 4.3-16.1 microg kg(-1) and 8.7-20.7 microg kg(-1), respectively. Accuracy, expressed as percentage of error, is lower than 6% and relative standard deviation in reproducibility conditions falls between 5.6 and 10.3%. Nowadays, the proposed method is routinely implemented in the laboratory of the Agència de Salut Pública de Barcelona and allows processing of up to 20 samples per day.

  16. Quinolones control in milk and eggs samples by liquid chromatography using a surfactant-mediated mobile phase.

    Science.gov (United States)

    Rambla-Alegre, M; Collado-Sánchez, M A; Esteve-Romero, J; Carda-Broch, S

    2011-05-01

    Four quinolones (danofloxacin, difloxacin, flumequine and marbofloxacin) were determined in milk and egg samples by a simplified high-performance liquid chromatographic procedure using a micellar mobile phase. No extraction was needed to precipitate the proteins from the matrices since they were solubilised in micelles. The only pretreatment steps required were homogenisation, dilution and filtration before injecting the sample into the chromatographic system. An adequate resolution of the quinolones was achieved by a chemometrics approach where retention was modelled as a first step using the retention factors in only five mobile phases. Afterwards, an optimisation criterion was applied to consider the position and shape of the chromatographic peaks. Analytical separation involved a C18 reversed-phase column, a hybrid micellar mobile phase of 0.05 M sodium dodecyl sulphate, 10% (v/v) butanol and 0.5% (v/v) triethylamine buffered at pH 3 and fluorimetric detection. Quinolones were eluted in less than 15 min without the protein band or other endogenous compounds from the food matrices interfering. The calculated relevant validation parameters, e.g., decision limit (CC(α)), detection capability (CC(β)), repeatability, within-laboratory reproducibility, recoveries and robustness, were acceptable and complied with European Commission Decision 2002/657/EC. Finally, the proposed method was successfully employed in quantifying the four quinolones in spiked egg and milk samples.

  17. Sensitive determination of cadmium in water samples by room temperature ionic liquid-based preconcentration and electrothermal atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Martinis, Estefania M. [Laboratory of Environmental Research and Services of Mendoza (LISAMEN), (CCT - CONICET - Mendoza), Av. Ruiz Leal S/N Parque General San Martin, C.C. 131, M 5502 IRA Mendoza (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Olsina, Roberto A. [Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Departamento de Quimica Analitica, Facultad de Quimica, Bioquimica y Farmacia, Universidad Nacional de San Luis (Argentina); Altamirano, Jorgelina C. [Laboratory of Environmental Research and Services of Mendoza (LISAMEN), (CCT - CONICET - Mendoza), Av. Ruiz Leal S/N Parque General San Martin, C.C. 131, M 5502 IRA Mendoza (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Instituto de Ciencias Basicas, Universidad Nacional de Cuyo, Mendoza (Argentina); Wuilloud, Rodolfo G. [Laboratory of Environmental Research and Services of Mendoza (LISAMEN), (CCT - CONICET - Mendoza), Av. Ruiz Leal S/N Parque General San Martin, C.C. 131, M 5502 IRA Mendoza (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET) (Argentina); Instituto de Ciencias Basicas, Universidad Nacional de Cuyo, Mendoza (Argentina)], E-mail: rwuilloud@mendoza-conicet.gov.ar

    2008-10-17

    A sensitive preconcentration methodology for Cd determination at trace levels in water samples was developed in this work. 1-Butyl-3-methylimidazolium hexafluorophosphate ([C{sub 4}MIM][PF{sub 6}]) room temperature ionic liquid (RTIL) was successfully used for Cd preconcentration, as cadmium-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex [Cd-5-Br-PADAP]. Subsequently, Cd was back-extracted from the RTIL phase with 500 {mu}L of 0.5 mol L{sup -1} nitric acid and determined by electrothermal atomic absorption spectrometry (ETAAS). A preconcentration factor of 40 was achieved with 20 mL of sample. The limit of detection (LOD) obtained under optimum conditions was 3 ng L{sup -1} and the relative standard deviation (R.S.D.) for 10 replicates at 1 {mu}g L{sup -1} Cd{sup 2+} concentration level was 3.5%, calculated at peak heights. The calibration graph was linear from concentration levels near the detection limits up to at least 5 {mu}g L{sup -1}. A correlation coefficient of 0.9997 was achieved. Validation of the methodology was performed by standard addition method and analysis of certified reference material (CRM). The method was successfully applied to the determination of Cd in river and tap water samples.

  18. New sample treatment for determination of linear alkylbenzene sulfonate (LAS) in agricultural soils by liquid chromatography with fluorescence detection.

    Science.gov (United States)

    Nimer, M; Ballesteros, O; Navalón, A; Crovetto, G; Verge, C; López, I; Berna, J L; Vílchez, J L

    2007-03-01

    A new sample-treatment procedure has been developed for determination of total linear alkylbenzene sulfonate (LAS), i.e. homologues and isomers, in agricultural soil. The procedure involves two steps, ultrasound-assisted extraction of LAS from the samples with methanol then clean-up of the methanolic extracts and preconcentration of the LAS by solid-phase extraction on two adsorbent cartridges (SAX and C18). The ultrasound-assisted procedure reduces extraction time (10 min in contrast with 6-12 h for conventional Soxhlet extraction) and requires only small volumes of organic solvent. The effect of different variables interacting in the ultrasound-assisted extraction process was studied. Finally, separation and quantification of the homologues and isomers of LAS was performed by liquid chromatography with fluorescence detection (LC-FD). 2-Octylbenzenesulfonic acid sodium salt (Na-2ØC8-LAS) was used as internal standard. The proposed method was satisfactorily used for determination of LAS in agricultural soil samples from the fertile plain of Granada (Spain).

  19. Statistics a biomedical introduction

    CERN Document Server

    Brown, Byron Wm

    2009-01-01

    CHAPTER 1: Introduction 1 CHAPTER 2: Elementary Rules of Probability 13 CHAPTER 3: Populations, Samples, and the Distribution of the Sample Mean 37 1. Populations and Distributions 38 2. Sampling from Finite Populations 64 3. The Distribution of the Sample Mean 72 CHAPTER 4: Analysis of Matched Pairs Using Sample Means 85 1. A Confidence Interval for the Treatment Effect 86 2. A Hypothesis Test for the Treatment Effect 96 3. Determining the Sample Size 102 CHAPTER 5: Analysis of the Two-Sample Location Problem Using Sample Means 109 1. A Confidence Interval for the Diffe

  20. Determination of serotonin and its precursors in chocolate samples by capillary liquid chromatography with mass spectrometry detection.

    Science.gov (United States)

    Guillén-Casla, V; Rosales-Conrado, N; León-González, M E; Pérez-Arribas, L V; Polo-Díez, L M

    2012-04-06

    A method for the analysis of serotonin (5-HT) and its precursors, 5-hydroxytryptophan (5-HTP) and l-tryptophan (TP) in chocolate samples by capillary liquid chromatography-mass spectrometry (cLC-MS) has been developed. Optimum chromatographic conditions were established by using a personalized multifactorial experimental design. Finally the cLC separation was achieved through a mixture of acetonitrile and 5mM ammonium formate at pH 4 (3:97, v/v) as mobile phase in gradient elution, setting the injection volume at 10 μL and using pure water as injection solvent for focusing purposes on the head of the capillary column. For extraction of targets in chocolate samples a new, fast and simple procedure based on the use of acidic extraction medium and sonication was developed. Working in selected ion mode (m/z 177 for 5-HT, m/z 205 for l-tryptophan and m/z 221 for 5-HTP) detection limits were between 0.01 and 0.11 μg g(-1) and linearity was in the concentration range of 0.5-25 μg g(-1). Recoveries higher than 76% with RSDs lower than 8% were obtained from spiked samples for all analytes, showing the effectiveness of the proposed method. Serotonin and its precursors were determined in 5 kinds of commonly consumed chocolates with different cocoa contents (70-100%). The highest serotonin content was found in chocolate with a cocoa content of 85% (2.93 μg g(-1)). Regarding l-tryptophan, the highest content of this amino acid (13.27-13.34 μg g(-1)) was found in chocolate samples with the lowest cocoa content (70-85%). 5-Hydroxytryptophan was not detected in any chocolate samples. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. Optimization of dynamic headspace extraction system for measurement of halogenated volatile organic compounds in liquid or viscous samples

    Science.gov (United States)

    Taniai, G.; Oda, H.; Kurihara, M.; Hashimoto, S.

    2010-12-01

    Halogenated volatile organic compounds (HVOCs) produced in the marine environment are thought to play a key role in atmospheric reactions, particularly those involved in the global radiation budget and the depression of tropospheric and stratospheric ozone. To evaluate HVOCs concentrations in the various natural samples, we developed an automated dynamic headspace extraction method for the determination of 15 HVOCs, such as chloromethane, bromomethane, bromoethane, iodomethane, iodoethane, bromochloromethane, 1-iodopropane, 2-iodopropane, dibromomethane, bromodichloromethane, chloroiodomethane, chlorodibromomethane, bromoiodomethane, tribromomethane, and diiodomethane. Dynamic headspace system (GERSTEL DHS) was used to purge the gas phase above samples and to trap HVOCs on the adsorbent column from the purge gas. We measured the HVOCs concentrations in the adsorbent column with gas chromatograph (Agilent 6890N)- mass spectrometer (Agilent 5975C). In dynamic headspace system, an glass tube containing Tenax TA or Tenax GR was used as adsorbent column for the collection of 15 HVOCs. The parameters for purge and trap extraction, such as purge flow rate (ml/min), purge volume (ml), incubation time (min), and agitator speed (rpm), were optimized. The detection limits of HVOCs in water samples were 1270 pM (chloromethane), 103 pM (bromomethane), 42.1 pM (iodomethane), and 1.4 to 10.2 pM (other HVOCs). The repeatability (relative standard deviation) for 15 HVOCs were < 9 % except chloromethane (16.2 %) and bromomethane (11.0 %). On the basis of the measurements for various samples, we concluded that this analytical method is useful for the determination of wide range of HVOCs with boiling points between - 24°C (chloromethane) and 181°C (diiodomethane) for the liquid or viscous samples.

  2. The measurement of tritium in water samples with electrolytic enrichment using liquid scintillation counter

    Directory of Open Access Journals (Sweden)

    Janković Marija M.

    2012-01-01

    Full Text Available Tritium (3H present in the environment decreased in the last decades and nowadays it has low activity concentrations. Measurement of low-level tritium activities in natural waters, e. g. in precipitation, groundwater, and river water requires special techniques for water pretreatment and detection of low-level radioactivity. In order to increase the tritium concentration to an easily measurable level, electrolytic enrichment must be applied. This paper presents the enrichment method performed by electrolysis in a battery of 18 cells, giving an enrichment factor of 5.84 (calculated from 59 electrolyses. The calculated mean values of the separation factor and enrichment parameter were 4.10 and 0.84, respectively. Results for tritium activity in precipitation and surface water collected in Belgrade during 2008 and 2009 are presented. The Radiation and Environmental Protection Department of the Vinča Institute of Nuclear Sciences, participated in the IAEA TRIC2008 international intercomparison exercise. The participation in the intercomparisons for any laboratory doing low-level 3H measurements in the waters is very important and useful. It is considered the best way to check the entire procedure and methods of the measurements and the reliability of the standard used. The analysis of the reported 3H activity results showed that all results for five intercomparison samples, for which electrolytic enrichment were applied prior to the 3H measurement, are acceptable.

  3. FIELD-DEPLOYABLE SAMPLING TOOLS FOR SPENT NUCLEAR FUEL INTERROGATION IN LIQUID STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Berry, T.; Milliken, C.; Martinez-Rodriguez, M.; Hathcock, D.; Heitkamp, M.

    2012-09-12

    Methodology and field deployable tools (test kits) to analyze the chemical and microbiological condition of aqueous spent fuel storage basins and determine the oxide thickness on the spent fuel basin materials were developed to assess the corrosion potential of a basin. this assessment can then be used to determine the amount of time fuel has spent in a storage basin to ascertain if the operation of the reactor and storage basin is consistent with safeguard declarations or expectations and assist in evaluating general storage basin operations. The test kit was developed based on the identification of key physical, chemical and microbiological parameters identified using a review of the scientific and basin operations literature. The parameters were used to design bench scale test cells for additional corrosion analyses, and then tools were purchased to analyze the key parameters. The tools were used to characterize an active spent fuel basin, the Savannah River Site (SRS) L-Area basin. The sampling kit consisted of a total organic carbon analyzer, an YSI multiprobe, and a thickness probe. The tools were field tested to determine their ease of use, reliability, and determine the quality of data that each tool could provide. Characterization confirmed that the L Area basin is a well operated facility with low corrosion potential.

  4. As, Cd, Cr, Ni and Pb pressurized liquid extraction with acetic acid from marine sediment and soil samples

    Energy Technology Data Exchange (ETDEWEB)

    Moreda-Pineiro, Jorge [Department of Analytical Chemistry, Faculty of Sciences, University of A Coruna. Campus da Zapateira s/n. E-15071. A Coruna (Spain)]. E-mail: jmoreda@udc.es; Alonso-Rodriguez, Elia [Department of Analytical Chemistry, Faculty of Sciences, University of A Coruna. Campus da Zapateira s/n. E-15071. A Coruna (Spain); Lopez-Mahia, Purificacion [Department of Analytical Chemistry, Faculty of Sciences, University of A Coruna. Campus da Zapateira s/n. E-15071. A Coruna (Spain); University Institute of Environment, University of A Coruna, Pazo de Longora, Lians, E-15179. Oleiros (Spain); Muniategui-Lorenzo, Soledad [Department of Analytical Chemistry, Faculty of Sciences, University of A Coruna. Campus da Zapateira s/n. E-15071. A Coruna (Spain); Prada-Rodriguez, Dario [Department of Analytical Chemistry, Faculty of Sciences, University of A Coruna. Campus da Zapateira s/n. E-15071. A Coruna (Spain); University Institute of Environment, University of A Coruna, Pazo de Longora, Lians, E-15179. Oleiros (Spain); Moreda-Pineiro, Antonio [Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, University of Santiago de Compostela, Avenida das Ciencias, s/n. E-15782, Santiago de Compostela (Spain); Bermejo-Barrera, Adela [Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, University of Santiago de Compostela, Avenida das Ciencias, s/n. E-15782, Santiago de Compostela (Spain); Bermejo-Barrera, Pilar [Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, University of Santiago de Compostela, Avenida das Ciencias, s/n. E-15782, Santiago de Compostela (Spain)

    2006-12-15

    Rapid leaching procedures by Pressurized Liquid Extraction (PLE) have been developed for As, Cd, Cr, Ni and Pb leaching from environmental matrices (marine sediment and soil samples). The Pressurized Liquid Extraction is completed after 16 min. The released elements by acetic acid Pressurized Liquid Extraction have been evaluated by inductively coupled plasma-optical emission spectrometry. The optimum multi-element leaching conditions when using 5.0 ml stainless steel extraction cells, were: acetic acid concentration 8.0 M, extraction temperature 100 deg. C, pressure 1500 psi, static time 5 min, flush solvent 60%, two extraction steps and 0.50 g of diatomaceous earth as dispersing agent (diatomaceous earth mass/sample mass ratio of 2). Results have showed that high acetic acid concentrations and high extraction temperatures increase the metal leaching efficiency. Limits of detection (between 0.12 and 0.5 {mu}g g{sup -1}) and repeatability of the over-all procedure (around 6.0%) were assessed. Finally, accuracy was studied by analyzing PACS-2 (marine sediment), GBW-07409 (soil), IRANT-12-1-07 (cambisol soil) and IRANT-12-1-08 (luvisol soil) certified reference materials (CRMs). These certified reference materials offer certified concentrations ranges between 2.9 and 26.2 {mu}g g{sup -1} for As, from 0.068 to 2.85 {mu}g g{sup -1} for Cd, between 26.4 and 90.7 {mu}g g{sup -1} for Cr, from 9.3 to 40.0 {mu}g g{sup -1} for Ni and between 16.3 and 183.0 {mu}g g{sup -1} for Pb. Recoveries after analysis were between 95.7 and 105.1% for As, 96.2% for Cd, 95.2 and 100.6% for Cr, 95.7 and 103% for Ni and 94.2 and 105.5% for Pb.

  5. Determination of Pesticide Residues in Honeybees using Modified QUEChERS Sample Work-Up and Liquid Chromatography-Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Żaneta Bargańska

    2014-03-01

    Full Text Available Increasing emissions of chemical compounds to the environment, especially of pesticides, is one of factors that may explain present honeybee colony losses. In this work, an analytical method employing liquid chromatography-tandem mass spectrometry (LC-MS/MS was optimized for the simultaneous screening of 19 pesticides which have not been yet determined in honeybee samples from northern Poland (Pomerania. The sample preparation, based on the QuEChERS method combining salting-out liquid-liquid extraction to acetonitrile and a dispersive-SPE clean-up, was adjusted to honeybee samples by adding a small amount of hexane to eliminate beeswax. The recovery of analytes ranged from 70% to 120% with relative standard deviation ≤20%. The limits of detection were in the range of 0.91–25 ng/g. A total of 19 samples of honeybees from suspected pesticide poisoning incidents were analyzed, in which 19 different pesticides were determined.

  6. CTEPP STANDARD OPERATING PROCEDURE FOR EXTRACTING AND PREPARING LIQUID FOOD SAMPLES FOR ANALYSIS OF POLAR ORGANIC POLLUTANTS (SOP-5.29)

    Science.gov (United States)

    This SOP describes the extraction and preparation of a liquid food sample for analysis of acidic persistent organic pollutants such as acid herbicides, pentachlorphenol, and 3,5,6-trichloro-2-phenol. It covers the extraction, concentration and derivatization of samples that are t...

  7. CTEPP STANDARD OPERATING PROCEDURE FOR EXTRACTING AND PREPARING LIQUID FOOD SAMPLES FOR ANALYSIS OF POLAR ORGANIC POLLUTANTS (SOP-5.29)

    Science.gov (United States)

    This SOP describes the extraction and preparation of a liquid food sample for analysis of acidic persistent organic pollutants such as acid herbicides, pentachlorphenol, and 3,5,6-trichloro-2-phenol. It covers the extraction, concentration and derivatization of samples that are t...

  8. A novel fatty-acid-based in-tube dispersive liquid-liquid microextraction technique for the rapid determination of nonylphenol and 4-tert-octylphenol in aqueous samples using high-performance liquid chromatography-ultraviolet detection.

    Science.gov (United States)

    Shih, Hou-Kuang; Shu, Ting-Yun; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

    2015-01-07

    In this study, a novel fatty-acid-based in-tube dispersive liquid-liquid microextraction (FA-IT-DLLME) technique is proposed for the first time and is developed as a simple, rapid and eco-friendly sample extraction method for the determination of alkylphenols in aqueous samples using high-performance liquid chromatography-ultraviolet detection (HPLC-UV). In this extraction method, medium-chain saturated fatty acids were investigated as a pH-dependent phase because they acted as either anionic surfactants or neutral extraction solvents based on the acid-base reaction caused solely by the adjustment of the pH of the solution. A specially designed home-made glass extraction tube with a built-in scaled capillary tube was utilized as the phase-separation device for the FA-IT-DLLME to collect and measure the separated extractant phase for analysis. Nonylphenol (NP) and 4-tert-octylphenol (4-tOP) were chosen as model analytes. The parameters influencing the FA-IT-DLLME were thoroughly investigated and optimized. Under the optimal conditions, the detector responses of NP and 4-tOP were linear in the concentration ranges of 5-4000 μg L(-1), with correlation coefficients of 0.9990 and 0.9996 for NP and 4-tOP, respectively. The limits of detection based on a signal-to-noise ratio of 3 were 0.7 and 0.5 μg L(-1), and the enrichment factors were 195 and 143 for NP and 4-tOP, respectively. The applicability of the developed method was demonstrated for the analysis of alkylphenols in environmental wastewater samples, and the recoveries ranged from 92.9 to 107.1%. The extraction process required less than 4 min and utilized only acids, alkalis, and fatty acids to achieve the extraction. The results demonstrated that the presented FA-IT-DLLME approach is highly cost-effective, simple, rapid and environmentally friendly in its sample preparation.

  9. Separation and pre-concentration of glucocorticoids in water samples by ionic liquid supported vortex-assisted synergic microextraction and HPLC determination.

    Science.gov (United States)

    Qin, Hui; Li, Bi; Liu, Mou Sheng; Yang, Ya Ling

    2013-04-01

    We have developed a synergic microextraction procedure based on ionic liquid for the pre-concentration and determination of glucocorticoids in water samples. Using nonionic surfactant Triton X-100 (TX-100) as synergic reagent, 1-butyl-3-methylimidazolium hexa-fluorophosphate accomplished extraction rapidly without heating in water bath. One key property of ionic liquids that highlights their potential is their wide liquid temperature range. The improved extraction was named as ionic liquid supported vortex-assisted synergic microextraction. Compared with the traditional liquid-liquid extraction and cloud point extraction, ionic liquid supported vortex-assisted synergic microextraction was accomplished in 8 min with considerably high recovery. The proposed method greatly improved the sensitivity of HPLC for the determination of glucocorticoids. The results obtained indicated a good linearity with the correlation coefficient of 0.997 over the range of 0.6-300 ng/mL and high sensitivity with LODs of 4.11, 9.19, and 7.50 ng/mL for hydrocortisone butyrate, beclomethasone dipropionate, and nandrolone phenylpropionate, respectively. The RSD of the method was 1.57-1.81% (n = 6) with enrichment factor of 99.85, and good recovery (≥97.24%). The method was successfully applied to the determination of glucocorticoids in mineral water, water of Dianchi lake, and tap water samples.

  10. Improved detection of multiple environmental antibiotics through an optimized sample extraction strategy in liquid chromatography-mass spectrometry analysis.

    Science.gov (United States)

    Yi, Xinzhu; Bayen, Stéphane; Kelly, Barry C; Li, Xu; Zhou, Zhi

    2015-12-01

    A solid-phase extraction/liquid chromatography/electrospray ionization/multi-stage mass spectrometry (SPE-LC-ESI-MS/MS) method was optimized in this study for sensitive and simultaneous detection of multiple antibiotics in urban surface waters and soils. Among the seven classes of tested antibiotics, extraction efficiencies of macrolides, lincosamide, chloramphenicol, and polyether antibiotics were significantly improved under optimized sample extraction pH. Instead of only using acidic extraction in many existing studies, the results indicated that antibiotics with low pK a values (antibiotics with high pK a values (>7) were extracted more efficiently under neutral conditions. The effects of pH were more obvious on polar compounds than those on non-polar compounds. Optimization of extraction pH resulted in significantly improved sample recovery and better detection limits. Compared with reported values in the literature, the average reduction of minimal detection limits obtained in this study was 87.6% in surface waters (0.06-2.28 ng/L) and 67.1% in soils (0.01-18.16 ng/g dry wt). This method was subsequently applied to detect antibiotics in environmental samples in a heavily populated urban city, and macrolides, sulfonamides, and lincomycin were frequently detected. Antibiotics with highest detected concentrations were sulfamethazine (82.5 ng/L) in surface waters and erythromycin (6.6 ng/g dry wt) in soils. The optimized sample extraction strategy can be used to improve the detection of a variety of antibiotics in environmental surface waters and soils.

  11. Molecularly imprinted SPE coupled with HPLC for the selective separation and enrichment of alkyl imidazolium ionic liquids in environmental water samples.

    Science.gov (United States)

    Xia, Gao; Jing, Fan; Guifen, Zhu; Xiaolong, Wang; Jianji, Wang

    2013-10-01

    A novel 1-butyl-3-methylimidazolium chloride ionic liquid surface imprinted solid-phase sorbent was synthesized. The as-prepared material was characterized by SEM, Brunauer-Emmett-Teller surface area analysis and Fourier Transform IR measurements. Then its adsorption properties for alkyl imidazolium ionic liquids, including adsorption capacities, adsorption kinetics, and properties of selective separation and enrichment were studied in detail. It was shown that the ionic liquid surface imprinted polymer exhibited high selective recognition characteristics for the imidazolium chloride ionic liquids with short alkyl chains (C(n)mimCl, n = 2, 4, 6, 8) and the adsorption equilibrium was achieved within 25 min. Various parameters were optimized for the 1-butyl-3-methylimidazolium chloride ionic liquid surface imprinted polymer SPE column, such as flow rate, eluent solvent, selectivity, and reusability of the column. Then, the SPE column coupled with HPLC was used for the determination of alkyl imidazolium ionic liquids. Experimental results showed that the existence of their structural analogs and common concomitants in environmental matrices did not affect the enrichment of 1-butyl-3-methyl imidazolium chloride ionic liquid. The average recoveries of 1-butyl-3-methylimidazolium chloride ionic liquid in spiked water samples were in the range of 92.0-102.0% with the RSD lower than 5.8%.

  12. Rapid screening and analysis of alpha- and gamma-emitting radionuclides in liquids using a single sample preparation procedure.

    Science.gov (United States)

    Parsa, Bahman; Henitz, James B; Carter, Jennifer A

    2011-02-01

    A multifaceted radiochemical testing procedure has been developed to analyze a large number of liquid samples and measure a wide range of radionuclides in a short period of time. This method involves a single, unique and fast sample preparation procedure and allows sequential/concurrent determination of analytes with accuracy and precision. The same prepared sample can be selectively analyzed by gross alpha counting, gamma-ray spectroscopy, and alpha spectroscopy. This method is especially attractive in radiological emergency events where analytical data will be needed urgently as a basis for protective action. Given the simplicity and rapidity of the method, it may be suitable for field portable laboratories, which could save time and the cost associated with the transit of samples to a fixed laboratory. A 100 mL aliquot of sample was spiked with ¹³³Ba and ⁵⁹Fe tracers and subjected to a chemical separation procedure using a combined BaSO4 and Fe(OH)3 co-precipitation scheme. Then, the gross alpha-particle activity of the prepared sample was measured with a low-background gas-proportional counter, followed by the analysis of its photon-emitters using a gamma-ray spectroscopy system with high-purity intrinsic Ge detectors. Gamma-ray determination of ¹³³Ba and ⁵⁹Fe tracers was used to assess the chemical recoveries of BaSO4 and Fe(OH)3 fractions, respectively. Selectivity of the radionuclides for co-precipitation with either BaSO4 or Fe(OH)3 components was also investigated. Alpha mass-efficiency curves were derived using ²³⁰Th and ²⁴¹Am standards as alpha-calibration sources. Various mixtures of radionuclides, including ⁵⁴Mn, ⁵⁷Co, ⁶⁰Co, ⁸⁵Sr, ⁸⁸Y, ¹⁰⁹Cd, ¹¹³Sn, ¹³⁷Cs, ¹³⁹Ce, ²⁰³Hg, ²⁰⁹Po, ²²⁶Ra, ²²⁸Ra, ²³⁰Th, ²⁴¹Am, and natural uranium were used in this study. Most were quantitatively assayed with high chemical recoveries. Alpha-isotope identification and assessment of the prepared

  13. On-line parallel reversed phase two-dimensional liquid chromatography for high-throughput analysis of complex proteomic samples

    Institute of Scientific and Technical Information of China (English)

    WANG Zhicong; ZHANG Qinghe; LI Tong; ZHAO Zhongyi; ZHANG Weibing

    2006-01-01

    A comprehensive two-dimensional liquid chromatographic system (2D SCX/RP) is constructed with a 10-port-2-way valve using strong cation exchange chromatography (Hypersil SCX, 100 mm×4.6 mm I.D.) followed by reversed phase chromatography (Hypersil BDS C18, 15 mm×4.6 mm I.D.) to separate the complex peptides from globin peptic hydrolysate. After the sample was loaded on the SCX column, the phosphate buffer (pH 4.0) was used to elute the peptides. Then, elutes flowed through the interface and the peptides focused on the head of the trapping columns (Hypersil BDS C18, 15 mm×4.6 mm I.D.) but salt passed into the waste. After the valve was switched, the samples were flushed with a backward flow into the RP analytical column. The peptides on the SCX were eluted with 12 discontinuous steps linearly increasing salt concentrations. The peptides enriched on the trapping column were desalted and separated by the RP columns. The resolution and the resolved peaks of the 2D SCX/RP system were greatly increased and the total peak capacity reached as high as 2280.

  14. Detection of Yersinia pestis in environmental and food samples by intact cell immunocapture and liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Chenau, Jérôme; Fenaille, François; Simon, Stéphanie; Filali, Sofia; Volland, Hervé; Junot, Christophe; Carniel, Elisabeth; Becher, François

    2014-06-17

    Yersinia pestis is the causative agent of bubonic and pneumonic plague, an acute and often fatal disease in humans. In addition to the risk of natural exposure to plague, there is also the threat of a bioterrorist act, leading to the deliberate spread of the bacteria in the environment or food. We report here an immuno-liquid chromatography-tandem mass spectrometry (immuno-LC-MS/MS) method for the direct (i.e., without prior culture), sensitive, and specific detection of Y. pestis in such complex samples. In the first step, a bottom-up proteomics approach highlighted three relevant protein markers encoded by the Y. pestis-specific plasmids pFra (murine toxin) and pPla (plasminogen activator and pesticin). Suitable proteotypic peptides were thoroughly selected to monitor the three protein markers by targeted MS using the selected reaction monitoring (SRM) mode. Immunocapture conditions were optimized for the isolation and concentration of intact bacterial cells from complex samples. The immuno-LC-SRM assay has a limit of detection of 2 × 10(4) CFU/mL in milk or tap water, which compares well with those of state-of-the-art immunoassays. Moreover, we report the first direct detection of Y. pestis in soil, which could be extremely useful in confirming Y. pestis persistence in the ground.

  15. Determination of tamoxifen and its main metabolites in plasma samples from breast cancer patients by micellar liquid chromatography.

    Science.gov (United States)

    Peris-Vicente, Juan; Ochoa-Aranda, Enrique; Bose, Devasish; Esteve-Romero, Josep

    2015-01-01

    A method was developed for the analysis of tamoxifen and its main derivatives (4-hydroxytamoxifen, N-desmethyl-tamoxifen, tamoxifen-N-oxide and endoxifen) in human plasma, using micellar liquid chromatography coupled with fluorescence detection. Analytes were off-line derivatized by sample UV-irradiation for 20 min to form the photocycled fluorescent derivatives. Then samples were diluted, filtered and directly injected, thus avoiding extraction steps. The analytes were resolved using a mobile phase containing 0.08 M SDS-4.5% butanol at pH 3 running at 1.5 mL/min through a C18 column at 40°C, without interferences from endogenous compounds in plasma. Excitation and emission wavelengths were 260 and 380 nm, respectively. The chromatographic analysis time was less than 40 min. The analytical methodology was validated following the International Conference on Harmonization of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH) guidelines in terms of: selectivity, linear range (0.3-15 μg/mL), linearity (r(2)>0.999), sensitivity (LOD, 65-80 ng/mL; LOQ, 165-200 ng/mL), intra- and interday accuracy (-12.2-11.5%) and precision (<9.2%) and robustness (<6.3%). The method was used to quantify the tamoxifen and tamoxifen derivatives in several breast cancer patients from a local hospital, in order to study the correlation between the genotype of the patient and the ability to metabolize tamoxifen.

  16. Sampling and identification of natural dyes in historical maps and drawings by liquid chromatography with diode-array detection.

    Science.gov (United States)

    Blanc, Rosario; Espejo, Teresa; López-Montes, Ana; Torres, David; Crovetto, Guillermo; Navalón, Alberto; Vílchez, José Luis

    2006-07-28

    A simple and rapid liquid chromatographic with diode-array UV-vis spectrophotometric detection (HPLC-DAD) method for identification of natural dyes has been developed. Chromatographic retention of carminic acid, indigotin, crocetin, gambogic acid, alizarin and purpurin has been studied. The mobile phase consisted of 40 mM SDS-10 mM phosphate buffer solution (pH 2.3)-0.1% TFA (eluent A) and acetonitrile (eluent B) using a programmed gradient (5% B to 95% B). Analyses were carried out on a Phenomenex, Luna 5u NH2 100(a) column (250 mm x 4.60 mm i.d., 5 microm particle) and the operating conditions were: 0.6 ml min(-1) flow rate, 20 microl volume injection and 35 degrees C column temperature. Extracts of samples of natural dyes taken from historical maps belonging to The Royal Chancellery Archives in Granada were successfully analyzed using the proposed method including a new technique for sampling.

  17. Comprehensive quantitative and qualitative liquid chromatography-radioisotope-mass spectrometry analysis for safety testing of tolbutamide metabolites without standard samples.

    Science.gov (United States)

    Tozuka, Zenzaburo; Aoyama, Shinsuke; Nozawa, Kohei; Akita, Shoji; Oh-Hara, Toshinari; Adachi, Yasuhisa; Ninomiya, Shin-ichi

    2011-09-01

    Liquid chromatography-radioisotope-mass spectrometry (LC-RI-MS) analysis was used to determine the structures of 12 (four previously unknown) (14) C-tolbutamide (TB) metabolites in rat biological samples (plasma, urine, bile, feces, and microsomes). The four novel metabolites are ω-carboxy TB, hydroxyl TB (HTB)-O-glucuronide, TB-ortho or meta-glutathion, and tolylsulphoaminocarbo-glutathion. In rat plasma, after oral administration of (14) C-TB at therapeutic dose (1 mg/kg) and microdose (1.67 µg/kg), the total RI and six metabolites [HTB, carboxy TB (CTB), M1: desbutyl TB, M2: ω-hydroxyl TB, M3: α-hydroxyl TB, and M4: ω-1-hydroxyl TB] were quantified by LC-RI-MS. The plasma concentrations were calculated using their response factors (MS-RI intensity ratio) without standard samples, and the area under the curve (AUC) of plasma concentration per time for evaluation of Safety Testing of Drug Metabolites (MIST) was calculated using the ratio of TB metabolites AUC/total RI AUC. The ratios were as follows: TB 94.5% and HTB 2.5% for the microdose (1.67 µg/kg) and TB 95.6%, HTB 0.96%, CTB 0.065%, M1 0.62%, M2 0.0035%, M3 0.077%, and M4 0.015% for the therapeutic dose (1 mg/kg). These values were less than 10% of the MIST criteria.

  18. Extraction of aflatoxins from liquid foodstuff samples with polydopamine-coated superparamagnetic nanoparticles for HPLC-MS/MS analysis.

    Science.gov (United States)

    McCullum, Cassandra; Tchounwou, Paul; Ding, Li-Sheng; Liao, Xun; Liu, Yi-Ming

    2014-05-14

    A facile magnetic solid phase extraction (MSPE) of aflatoxins (AFs) from liquid samples was developed using polydopamine-coated magnetic nanoparticles (PD-MNPs) as the adsorbent. PD-MNPs were prepared from amine-terminated MNPs and dopamine via an in situ oxidative self-polymerization approach. Under the selected MSPE conditions, extraction yields ranging from 59.3% for AF G2 to 89.0% for AF B1 were obtained with good repeatability. Coupled with HPLC-MS/MS quantification, the MSPE procedure serves not only for sample cleanup but also for AFs enrichment that is highly desired for trace analysis. The proposed MSPE-HPLC-MS/MS method had a linear calibration curve in the concentration range from 0.00600 to 3.00 ng/mL aflatoxin and limits of detection of 0.0012 ng/mL for AF B1, AF B2, and AF G1, and 0.0031 ng/mL for AF G2.

  19. Quantitative determination of acetylcholine in microdialysis samples using liquid chromatography/atmospheric pressure spray ionization mass spectrometry.

    Science.gov (United States)

    Keski-Rahkonen, Pekka; Lehtonen, Marko; Ihalainen, Jouni; Sarajärvi, Timo; Auriola, Seppo

    2007-01-01

    A fast, simple and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed for the determination of acetylcholine in rat brain microdialysis samples. The chromatographic separation was achieved in 3 min on a reversed-phase column with isocratic conditions using a mobile phase containing 2% (v/v) of acetonitrile and 0.05% (v/v) of trifluoroacetic acid (TFA). A stable isotope-labeled internal standard was included in the analysis and detection was carried out with a linear ion trap mass spectrometer using selected reaction monitoring (SRM). Analyte ionization was performed with an atmospheric pressure chemical ionization (APCI) source without applying discharge current (atmospheric pressure spray ionization). This special ionization technique offered significant advantages over electrospray ionization for the analysis of acetylcholine with reversed-phase ion-pairing chromatography. The lower limit of quantification was 0.15 nM (1.5 fmol on-column) and linearity was maintained over the range of 0.15-73 nM, providing a concentration range that is significantly wider than that of the existing LC/MS methods. Good accuracy and precision were obtained for concentrations within the standard curve range. The method was validated and has been used extensively for the determination of acetylcholine in rat brain microdialysis samples.

  20. Optimization of pressurized liquid extraction (PLE) of dioxin-furans and dioxin-like PCBs from environmental samples.

    Science.gov (United States)

    Antunes, Pedro; Viana, Paula; Vinhas, Tereza; Capelo, J L; Rivera, J; Gaspar, Elvira M S M

    2008-05-30

    Pressurized liquid extraction (PLE) applying three extraction cycles, temperature and pressure, improved the efficiency of solvent extraction when compared with the classical Soxhlet extraction. Polychlorinated-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like PCBs (coplanar polychlorinated biphenyls (Co-PCBs)) in two Certified Reference Materials [DX-1 (sediment) and BCR 529 (soil)] and in two contaminated environmental samples (sediment and soil) were extracted by ASE and Soxhlet methods. Unlike data previously reported by other authors, results demonstrated that ASE using n-hexane as solvent and three extraction cycles, 12.4 MPa (1800 psi) and 150 degrees C achieves similar recovery results than the classical Soxhlet extraction for PCDFs and Co-PCBs, and better recovery results for PCDDs. ASE extraction, performed in less time and with less solvent proved to be, under optimized conditions, an excellent extraction technique for the simultaneous analysis of PCDD/PCDFs and Co-PCBs from environmental samples. Such fast analytical methodology, having the best cost-efficiency ratio, will improve the control and will provide more information about the occurrence of dioxins and the levels of toxicity and thereby will contribute to increase human health.

  1. Supercritical fluid carbon dioxide extraction and liquid chromatographic separation with electrochemical detection of methylmercury from biological samples

    Science.gov (United States)

    Simon, N.S.

    1997-01-01

    Using the coupled methods presented in this paper, methylmercury can be accurately and rapidly extracted from biological samples by modified supercritical fluid carbon dioxide and quantitated using liquid chromatography with reductive electrochemical detection. Supercritical fluid carbon dioxide modified with methanol effectively extracts underivatized methylmercury from certified reference materials Dorm-1 (dogfish muscle) and Dolt-2 (dogfish liver). Calcium chloride and water, with a ratio of 5:2 (by weight), provide the acid environment required for extracting methylmercury from sample matrices. Methylmercury chloride is separated from other organomercury chloride compounds using HPLC. The acidic eluent, containing 0.06 mol L-1 NaCl, insures the presence of methylmercury chloride and facilitates the reduction of mercury on a glassy carbon electrode. If dual glassy carbon electrodes are used, a positive peak is observed at -0.65 to -0.70 V and a negative peak is observed at -0.90V with the organomercury compounds that were tested. The practical detection limit for methylmercury is 5 X 10-8 mol L-1 (1 X 10-12 tool injected) when a 20 ??L injection loop is used.

  2. Extraction of Aflatoxins from Liquid Foodstuff Samples with Polydopamine-Coated Superparamagnetic Nanoparticles for HPLC-MS/MS Analysis

    Science.gov (United States)

    2015-01-01

    A facile magnetic solid phase extraction (MSPE) of aflatoxins (AFs) from liquid samples was developed using polydopamine-coated magnetic nanoparticles (PD-MNPs) as the adsorbent. PD-MNPs were prepared from amine-terminated MNPs and dopamine via an in situ oxidative self-polymerization approach. Under the selected MSPE conditions, extraction yields ranging from 59.3% for AF G2 to 89.0% for AF B1 were obtained with good repeatability. Coupled with HPLC-MS/MS quantification, the MSPE procedure serves not only for sample cleanup but also for AFs enrichment that is highly desired for trace analysis. The proposed MSPE-HPLC-MS/MS method had a linear calibration curve in the concentration range from 0.00600 to 3.00 ng/mL aflatoxin and limits of detection of 0.0012 ng/mL for AF B1, AF B2, and AF G1, and 0.0031 ng/mL for AF G2. PMID:24766417

  3. Chiral liquid chromatography-mass spectrometry (LC-MS/MS) method development for the detection of salbutamol in urine samples.

    Science.gov (United States)

    Chan, Sue Hay; Lee, Warren; Asmawi, Mohd Zaini; Tan, Soo Choon

    2016-07-01

    A sequential solid-phase extraction (SPE) method was developed and validated using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) for the detection and quantification of salbutamol enantiomers in porcine urine. Porcine urine samples were hydrolysed with β-glucuronidase/arylsulfatase from Helix pomatia and then subjected to a double solid-phase extraction (SPE) first using the Abs-Elut Nexus SPE and then followed by the Bond Elut Phenylboronic Acid (PBA) SPE. The salbutamol enantiomers were separated using the Astec CHIROBIOTIC™ T HPLC column (3.0mm×100mm; 5μm) maintained at 15°C with a 15min isocratic run at a flow rate of 0.4mL/min. The mobile phase constituted of 5mM ammonium formate in methanol. Salbutamol and salbutamol-tert-butyl-d9 (internal standard, IS) was monitored and quantified with the multiple reaction monitoring (MRM) mode. The method showed good linearity for the range of 0.1-10ng/mL with limit of quantification at 0.3ng/mL. Analysis of the QC samples showed intra- and inter-assay precisions to be less than 5.04%, and recovery ranging from 83.82 to 102.33%.

  4. Determination of Antioxidant Flavonoids in Sudanese Honey Samples by Solid Phase Extraction and High Performance Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    Suzan Zein Alabdeen Makawi

    2009-01-01

    Full Text Available Flavonoids were extracted by solid phase extraction (SPE from seven floral honey samples of different botanical origin from different regions of Sudan. The flavonoids were determined by high performance liquid chromatography (HPLC technique using photo diode array detector (PDA. An isocratic and gradient systems for the resolution, identification and quantification of five flavonoids, namely; quercetin, kaempferol, apigenin, hesperetin and isorhamnetin, were developed. Although the isocratic system resolved the five compounds, however it suffered from interference by the complex mixture of honey samples. The gradient system resolved three of five flavonoids, namely, quercetin, kaempferol, and isorhamnetin, without interference by the complex honey matrix. Two flavonoids, apigenin and hesperetin, were observed to elute at close retention times, which lead to their interference with each other when injected in a mixture; however, absorption wavelength selection was found indicative of the presence or absence of either compound. The quantification of these flavonoids was done through the calibration curves of their standards. The obtained results were compared with reported results.

  5. Two-phase and three-phase liquid-phase microextraction of hydrochlorothiazide and triamterene in urine samples.

    Science.gov (United States)

    Ahmad Panahi, Homayon; Ejlali, Maryam; Chabouk, Monireh

    2016-07-01

    This paper reports the applicability of two-phase and three-phase hollow fiber based liquid-phase microextraction (HF-LPME) for the extraction of hydrochlorothiazide (HYD) and triamterene (TRM) from human urine. The HYD in two-phase HF-LPME is extracted from 24 mL of the aqueous sample into an organic phase with microliter volume located inside the pores and lumen of a polypropylene hollow fiber as acceptor phase, but the TRM in three-phase HF-LPME is extracted from aqueous donor phase to organic phase and then back-extracted to the aqueous acceptor phase, which can be directly injected into HPLC for analysis. Under optimized conditions preconcentration factors of HYD and TRM were obtained as 128 and 239, respectively. The calibration curves were linear (R(2)  ≥ 0.995) in the concentration range of 1.0-100 µg/L for HYD and 2.0-100 µg/L for TRM. The limits of detection for HYD and TRM were 0.5 µg/L. The intra-day and inter-day RSD based on four replicates were obtained as ≤5.8 and ≤9.3%, respectively. The methods were successfully applied for determining the concentration of the drugs in urine samples. Copyright © 2015 John Wiley & Sons, Ltd.

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

    Science.gov (United States)

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

    2016-11-01

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

  7. Dispersive liquid-liquid microextraction and its application in analysis of biological samples%分散液相微萃取技术及其在生物样品分析中的应用进展

    Institute of Scientific and Technical Information of China (English)

    张明勇; 洪战英; 范国荣

    2011-01-01

    Dispersive liquid-liquid microextraction (DLLME) is a new sample preparation technique, which is easy and fast in operation. It has a higher enrichment factor and consumes less volume of organic solvent. The most attractive merit of DLLME is that extraction time is quite shorter than other sample preparation methods. The technique has been applied to prepare environmental samples, biological samples, food samples and others. In this paper, we summarized the basic principle and procedure of DLLME, major influencing factors and recent applications of this technique in biological samples, which might provide reference for further study on liquid-liquid microextraction.%分散液相微萃取技术(dispersive liquid-liquid microextraction,DLLME)是一种新型样品前处理技术,具有操作简便、快速、有较高的富集因子、萃取剂使用量少的优点,与其他样品前处理技术比较,最大的优势是萃取时间短.该技术已应用于环境样品、生物样品、食品样品等领域的处理中.本文根据DLLME的基本原理与步骤、主要的影响因素以及该技术在生物样品中的应用等方面进行综述,为包括DLLME在内的液相微萃取技术研究提供参考.

  8. Evaluation of different parameters affecting the liquid scintillation spectrometry measurement of gross alpha and beta index in water samples

    Energy Technology Data Exchange (ETDEWEB)

    Palomo, M. [Unitat de Radioquimica Ambiental i Sanitaria, Universitat Rovira i Virgili, Tarragona (Spain); Villa, M. [Centro de Investigacion, Tecnologia e Innovacion. Servicio Radioisotopos. Universidad de Sevilla (Spain); Casacuberta, N. [Institut de Ciencia i Tecnologia Ambientals-Departament de Fisica, Universitat Autonoma de Barcelona. Spain (Spain); Penalver, A.; Borrull, F. [Unitat de Radioquimica Ambiental i Sanitaria, Universitat Rovira i Virgili, Tarragona (Spain); Aguilar, C., E-mail: carme.aguilar@urv.cat [Unitat de Radioquimica Ambiental i Sanitaria, Universitat Rovira i Virgili, Tarragona (Spain)

    2011-09-15

    Liquid scintillation spectrometry is a fast competitive technique for the simultaneous evaluation of gross alpha and beta indexes. However, the implementation of this technique should not be considered as straightforward, and the pre-concentration methods to decrease the detection limit together with quenching and alpha, and beta crossover corrections should be carefully chosen according to the needs of the laboratory. Both aspects are being approached in this work as to find an easy and robust method for alpha/beta measurement in water samples, taking into account the quenching and alpha/beta crossover interferences effects. Results showed that most of the pre-concentration methods increased the quenching in the measurement, although HNO{sub 3} 0.05 M points to be the best solution for pre-concentration and re-dissolution of the sample as converges into low quenching and maximum recovery. Subsequently, in the measurement of water samples with different conductivities, the analysis of the raw counts to obtain gross alpha and beta indexes was carried out using different approaches to implement quenching and interference corrections. If quenching and salt content in the sample are relatively low, interference and quenching-efficiency corrections do not improve the accuracy of the results within the usual precision assumed for a result of gross alpha and beta index (25%). Special attention must be paid when corrections are applied to high quenched or saline samples and when alpha and beta activities values are different in several orders of magnitude. - Highlights: > Developed method for simultaneously quantifying gross alpha and gross beta indexes based on LSC was as accurate and precise as the results obtained from methods based on gas proportional counting and ZnS alpha counting. > Alpha/beta crossover and/or quenching corrections were applied and the results obtained did not improve accuracy within 25% dispersion, a widespread acceptance limit for gross alpha and

  9. Comparison of green sample preparation techniques in the analysis of pyrethrins and pyrethroids in baby food by liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Petrarca, Mateus Henrique; Ccanccapa-Cartagena, Alexander; Masiá, Ana; Godoy, Helena Teixeira; Picó, Yolanda

    2017-05-12

    A new selective and sensitive liquid chromatography triple quadrupole mass spectrometry method was developed for simultaneous analysis of natural pyrethrins and synthetic pyrethroids residues in baby food. In this study, two sample preparation methods based on ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME) and salting-out assisted liquid-liquid extraction (SALLE) were optimized, and then, compared regarding the performance criteria. Appropriate linearity in solvent and matrix-based calibrations, and suitable recoveries (75-120%) and precision (RSD values≤16%) were achieved for selected analytes by any of the sample preparation procedures. Both methods provided the analytical selectivity required for the monitoring of the insecticides in fruit-, cereal- and milk-based baby foods. SALLE, recognized by cost-effectiveness, and simple and fast execution, provided a lower enrichment factor, consequently, higher limits of quantification (LOQs) were obtained. Some of them too high to meet the strict legislation regarding baby food. Nonetheless, the combination of ultrasound and DLLME also resulted in a high sample throughput and environmental-friendly method, whose LOQs were lower than the default maximum residue limit (MRL) of 10μgkg(-1) set by European Community for baby foods. In the commercial baby foods analyzed, cyhalothrin and etofenprox were detected in different samples, demonstrating the suitability of proposed method for baby food control. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. A new polymeric ionic liquid-based magnetic adsorbent for the extraction of inorganic anions in water samples.

    Science.gov (United States)

    Chen, Lei; Huang, Xiaojia; Zhang, Yong; Yuan, Dongxing

    2015-07-17

    In this work, a novel type of polymeric ionic liquid (PIL)-based magnetic adsorbent was successfully synthesized and applied for the extraction and determination of seven inorganic anions in water samples by coupling with ion chromatography. The new adsorbent was synthesized by simple free radical copolymerization of 1-ally-3-vinylimidazolium chloride, ethylene glycol dimethacrylate and silica-coated magnetite. The adsorbent exhibited well-defined core-shell structure and good magnetic response ability. Furthermore, due to the presence of abundant anion-exchange groups in the PIL, the adsorbent displayed expected extraction performance for anions including F(-), Cl(-), Br(-), NO2(-), NO3(-), PO4(3-) and SO4(2-). Various experimental parameters that could affect the extraction performance, such as the amount of adsorbent, desorption solvent, extraction and desorption time, the pH value of sample solution were investigated in detail. Under the optimized conditions, low limits of detection (S/N=3) and quantification limits (S/N=10) of the proposed method for the target anions were achieved within the range of 0.061-0.73μg/L and 0.19-2.41μg/L, respectively. The repeatability was investigated by evaluating the intra-day, inter-day precisions and batch-to-batch reproducibility with relative standard deviations (RSDs) lower than 11%. At the same time, the method also showed high extraction speed, simplicity, practicality and low cost for the extraction inorganic anions. Finally, the proposed method was used to detect anions in different water samples successfully. The recoveries were in the range of 71.0-111%, and the RSDs were below 12% in the all cases.

  11. Order-parameter-aided temperature-accelerated sampling for the exploration of crystal polymorphism and solid-liquid phase transitions

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Tang-Qing, E-mail: tangqing.yu@nyu.edu; Vanden-Eijnden, Eric, E-mail: eve2@cims.nyu.edu [Courant Institute of Mathematical Sciences, New York University, New York, New York 10012 (United States); Chen, Pei-Yang; Chen, Ming [Department of Chemistry, New York University, New York, New York 10003 (United States); Samanta, Amit [Program in Applied and Computational Mathematics, Princeton University, Princeton, New Jersey 08544, USA and Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Tuckerman, Mark, E-mail: mark.tuckerman@nyu.edu [Courant Institute of Mathematical Sciences, New York University, New York, New York 10012 (United States); Department of Chemistry, New York University, New York, New York 10003 (United States); NYU-ECNU Center for Computational Chemistry at NYU Shanghai, Shanghai 200062 (China)

    2014-06-07

    The problem of predicting polymorphism in atomic and molecular crystals constitutes a significant challenge both experimentally and theoretically. From the theoretical viewpoint, polymorphism prediction falls into the general class of problems characterized by an underlying rough energy landscape, and consequently, free energy based enhanced sampling approaches can be brought to bear on the problem. In this paper, we build on a scheme previously introduced by two of the authors in which the lengths and angles of the supercell are targeted for enhanced sampling via temperature accelerated adiabatic free energy dynamics [T. Q. Yu and M. E. Tuckerman, Phys. Rev. Lett. 107, 015701 (2011)]. Here, that framework is expanded to include general order parameters that distinguish different crystalline arrangements as target collective variables for enhanced sampling. The resulting free energy surface, being of quite high dimension, is nontrivial to reconstruct, and we discuss one particular strategy for performing the free energy analysis. The method is applied to the study of polymorphism in xenon crystals at high pressure and temperature using the Steinhardt order parameters without and with the supercell included in the set of collective variables. The expected fcc and bcc structures are obtained, and when the supercell parameters are included as collective variables, we also find several new structures, including fcc states with hcp stacking faults. We also apply the new method to the solid-liquid phase transition in copper at 1300 K using the same Steinhardt order parameters. Our method is able to melt and refreeze the system repeatedly, and the free energy profile can be obtained with high efficiency.

  12. Luminescent determination of quinolones in milk samples by liquid chromatography/post-column derivatization with terbium oxide nanoparticles.

    Science.gov (United States)

    Yánez-Jácome, G S; Aguilar-Caballos, M P; Gómez-Hens, A

    2015-07-31

    The usefulness of terbium oxide nanoparticles (Tb4O7NPs) as post-column derivatizing reagent for the liquid chromatographic determination of residues of quinolone antibiotics in milk samples has been studied. Seven quinolones of veterinary use have been chosen as model analytes to develop this method. The derivatization step is based on the formation of luminescent chelates of quinolones with Tb4O7NPs, which are monitored at λex=340nm and λem=545nm. Another relevant feature of the method is that the use of a 10-cm column and a ternary mixture of methanol, acetonitrile and acetic acid as mobile phase in gradient elution mode allow the chromatographic separation of the quinolones in about 13min, whereas previously described chromatographic methods require about 20min. The dynamic ranges of the calibration graphs and limits of detection are, respectively: 65-900ngmL(-1) and 35ngmL(-1) for marbofloxacin, 7.2-900ngmL(-1) and 2.5ngmL(-1) for ciprofloxacin, 6-900ngmL(-1) and 2ngmL(-1) for danofloxacin, 50-900ngmL(-1) and 20ngmL(-1) for enrofloxacin, 35-900ngmL(-1) and 12ngmL(-1) for sarafloxacin, 5-900ngmL(-1) and 2ngmL(-1) for oxolinic acid, and 7-900ngmL(-1) and 2.5ngmL(-1) for flumequine. The precision, established at two concentration levels of each analyte and expressed as the percentage of the relative standard deviation is in the range of 1.9-8.1% using standards, and of 3.4-10.7% in the presence of milk samples. The method has been satisfactorily applied to the analysis of skimmed, semi-skimmed and whole milk samples, with recoveries ranging from 89.0 to 106.5%.

  13. High-resolution liquid- and solid-state nuclear magnetic resonance of nanoliter sample volumes using microcoil detectors

    Science.gov (United States)

    Kentgens, A. P. M.; Bart, J.; van Bentum, P. J. M.; Brinkmann, A.; van Eck, E. R. H.; Gardeniers, J. G. E.; Janssen, J. W. G.; Knijn, P.; Vasa, S.; Verkuijlen, M. H. W.

    2008-02-01

    The predominant means to detect nuclear magnetic resonance (NMR) is to monitor the voltage induced in a radiofrequency coil by the precessing magnetization. To address the sensitivity of NMR for mass-limited samples it is worthwhile to miniaturize this detector coil. Although making smaller coils seems a trivial step, the challenges in the design of microcoil probeheads are to get the highest possible sensitivity while maintaining high resolution and keeping the versatility to apply all known NMR experiments. This means that the coils have to be optimized for a given sample geometry, circuit losses should be avoided, susceptibility broadening due to probe materials has to be minimized, and finally the B1-fields generated by the rf coils should be homogeneous over the sample volume. This contribution compares three designs that have been miniaturized for NMR detection: solenoid coils, flat helical coils, and the novel stripline and microslot designs. So far most emphasis in microcoil research was in liquid-state NMR. This contribution gives an overview of the state of the art of microcoil solid-state NMR by reviewing literature data and showing the latest results in the development of static and micro magic angle spinning (microMAS) solenoid-based probeheads. Besides their mass sensitivity, microcoils can also generate tremendously high rf fields which are very useful in various solid-state NMR experiments. The benefits of the stripline geometry for studying thin films are shown. This geometry also proves to be a superior solution for microfluidic NMR implementations in terms of sensitivity and resolution.

  14. Multiresidue determination of veterinary drugs in aquaculture fish samples by ultra high performance liquid chromatography coupled to tandem mass spectrometry.

    Science.gov (United States)

    Lopes, Renata Pereira; Reyes, Rocío Cazorla; Romero-González, Roberto; Vidal, José Luis Martínez; Frenich, Antonia Garrido

    2012-05-01

    A simple, selective and fast multiresidue method was developed for the determination of 32 veterinary drug residues belonging to several families, in gilthead sea bream (Sparus aurata) by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The extraction was based on modified QuEChERS (quick, easy, cheap, effective, rugged and safe) procedure, using as extraction solution a mixture of acetonitrile and methanol (75:25, v/v), and it reduces sample handling, increasing sample throughput in relation to current methodologies. The developed method was validated and mean recovery ranged from 69% to 125% (at 10, 25, 50 and 100 μg/kg). Intra and interday precision, estimated as the same levels and expressed as relative standard deviation, RSD, were lower than 20% and 30%, respectively. Limits of detection (LODs) and quantification (LOQs) were lower than 7.5 and 25 μg/kg, respectively, except for danofloxacin, oxytetracycline and tetracycline (LOD and LOQ of 15.0 and 50 μg/kg, respectively). Decision limit (CC(α)) and detection capability (CC(β)) were also calculated and ranged from 16.7 μg/kg (levamisole) to 605.0 (flumequine) μg/kg and from 23.5 μg/kg (levamisole) to 611.5 μg/kg (flumequine), respectively. The expanded uncertainty, U, was also evaluated ant it was below 25% at 100 μg/kg level, except for tetracycline (28%). Finally, the method was applied to ten samples obtained from local supermarkets in Almería (Spain) and traces of some compounds were detected.

  15. Ultrasound-assisted magnetic solid-phase extraction based ionic liquid-coated Fe3O4@graphene for the determination of nitrobenzene compounds in environmental water samples.

    Science.gov (United States)

    Cao, Xiaoji; Shen, Lingxiao; Ye, Xuemin; Zhang, Feifei; Chen, Jiaoyu; Mo, Weimin

    2014-04-21

    An ultrasound-assisted magnetic solid-phase extraction procedure with the [C7MIM][PF6] ionic liquid-coated Fe3O4-grafted graphene nanocomposite as the magnetic adsorbent has been developed for the determination of five nitrobenzene compounds (NBs) in environmental water samples, in combination with high performance liquid chromatography-photodiode array detector (HPLC-PDA). Several significant factors that affect the extraction efficiency, such as the types of magnetic nanoparticle and ionic liquid, the volume of ionic liquid and the amount of magnetic nanoparticles, extraction time, ionic strength, and solution pH, were investigated. With the assistance of ultrasound, adsorbing nitrobenzene compounds by ionic liquid and self-aggregating ionic liquid onto the surface of the Fe3O4-grafted graphene proceeded synchronously, which made the extraction achieved the maximum within 20 min using only 144 μL [C7MIM][PF6] and 3 mg Fe3O4-grafted graphene. Under the optimized conditions, satisfactory linearities were obtained for all NBs with correlation coefficients larger than 0.9990. The mean recoveries at two spiked levels ranged from 80.35 to 102.77%. Attributed to the convenient magnetic separation, the Fe3O4-grafted graphene could be recycled many times. The proposed method was demonstrated to be feasible, simple, solvent-saving and easy to operate for the trace analysis of NBs in environmental water samples.