Science.gov

Sample records for coupled plasma mass

  1. Fission Yield Measurements by Inductively Coupled Plasma Mass-Spectrometry

    SciTech Connect

    Irina Glagolenko; Bruce Hilton; Jeffrey Giglio; Daniel Cummings; Karl Grimm; Richard McKnight

    2009-11-01

    Correct prediction of the fission products inventory in irradiated nuclear fuels is essential for accurate estimation of fuel burnup, establishing proper requirements for spent fuel transportation and storage, materials accountability and nuclear forensics. Such prediction is impossible without accurate knowledge of neutron induced fission yields. Unfortunately, the accuracy of the fission yields reported in the ENDF/B-VII.0 library is not uniform across all of the data and much of the improvement is desired for certain isotopes and fission products. We discuss our measurements of cumulative fission yields in nuclear fuels irradiated in thermal and fast reactor spectra using Inductively Coupled Plasma Mass Spectrometry.

  2. Inductively Coupled Plasma Zoom-Time-of-Flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Dennis, Elise A.; Ray, Steven J.; Enke, Christie G.; Hieftje, Gary M.

    2016-03-01

    A zoom-time-of-flight mass spectrometer has been coupled to an inductively coupled plasma (ICP) ionization source. Zoom-time-of-flight mass spectrometry (zoom-TOFMS) combines two complementary types of velocity-based mass separation. Specifically, zoom-TOFMS alternates between conventional, constant-energy acceleration (CEA) TOFMS and energy-focused, constant-momentum acceleration (CMA) (zoom) TOFMS. The CMA mode provides a mass-resolution enhancement of 1.5-1.7× over CEA-TOFMS in the current, 35-cm ICP-zoom-TOFMS instrument geometry. The maximum resolving power (full-width at half-maximum) for the ICP-zoom-TOFMS instrument is 1200 for CEA-TOFMS and 1900 for CMA-TOFMS. The CMA mode yields detection limits of between 0.02 and 0.8 ppt, depending upon the repetition rate and integration time—compared with single ppt detection limits for CEA-TOFMS. Isotope-ratio precision is shot-noise limited at approximately 0.2% relative-standard deviation (RSD) for both CEA- and CMA-TOFMS at a 10 kHz repetition rate and an integration time of 3-5 min. When the repetition rate is increased to 43.5 kHz for CMA, the shot-noise limited, zoom-mode isotope-ratio precision is improved to 0.09% RSD for the same integration time.

  3. Quantitative aspects of inductively coupled plasma mass spectrometry.

    PubMed

    Bulska, Ewa; Wagner, Barbara

    2016-10-28

    Accurate determination of elements in various kinds of samples is essential for many areas, including environmental science, medicine, as well as industry. Inductively coupled plasma mass spectrometry (ICP-MS) is a powerful tool enabling multi-elemental analysis of numerous matrices with high sensitivity and good precision. Various calibration approaches can be used to perform accurate quantitative measurements by ICP-MS. They include the use of pure standards, matrix-matched standards, or relevant certified reference materials, assuring traceability of the reported results. This review critically evaluates the advantages and limitations of different calibration approaches, which are used in quantitative analyses by ICP-MS. Examples of such analyses are provided.This article is part of the themed issue 'Quantitative mass spectrometry'. PMID:27644971

  4. Quantitative aspects of inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Bulska, Ewa; Wagner, Barbara

    2016-10-01

    Accurate determination of elements in various kinds of samples is essential for many areas, including environmental science, medicine, as well as industry. Inductively coupled plasma mass spectrometry (ICP-MS) is a powerful tool enabling multi-elemental analysis of numerous matrices with high sensitivity and good precision. Various calibration approaches can be used to perform accurate quantitative measurements by ICP-MS. They include the use of pure standards, matrix-matched standards, or relevant certified reference materials, assuring traceability of the reported results. This review critically evaluates the advantages and limitations of different calibration approaches, which are used in quantitative analyses by ICP-MS. Examples of such analyses are provided. This article is part of the themed issue 'Quantitative mass spectrometry'.

  5. Inductively Coupled Plasma Mass Spectrometry Uranium Error Propagation

    SciTech Connect

    Hickman, D P; Maclean, S; Shepley, D; Shaw, R K

    2001-07-01

    The Hazards Control Department at Lawrence Livermore National Laboratory (LLNL) uses Inductively Coupled Plasma Mass Spectrometer (ICP/MS) technology to analyze uranium in urine. The ICP/MS used by the Hazards Control Department is a Perkin-Elmer Elan 6000 ICP/MS. The Department of Energy Laboratory Accreditation Program requires that the total error be assessed for bioassay measurements. A previous evaluation of the errors associated with the ICP/MS measurement of uranium demonstrated a {+-} 9.6% error in the range of 0.01 to 0.02 {micro}g/l. However, the propagation of total error for concentrations above and below this level have heretofore been undetermined. This document is an evaluation of the errors associated with the current LLNL ICP/MS method for a more expanded range of uranium concentrations.

  6. Matrix effects in inductively coupled plasma mass spectrometry

    SciTech Connect

    Chen, Xiaoshan

    1995-07-07

    The inductively coupled plasma is an electrodeless discharge in a gas (usually Ar) at atmospheric pressure. Radio frequency energy generated by a RF power source is inductively coupled to the plasma gas through a water cooled load coil. In ICP-MS the {open_quotes}Fassel{close_quotes} TAX quartz torch commonly used in emission is mounted horizontally. The sample aerosol is introduced into the central flow, where the gas kinetic temperature is about 5000 K. The aerosol is vaporized, atomized, excited and ionized in the plasma, and the ions are subsequently extracted through two metal apertures (sampler and skimmer) into the mass spectrometer. In ICP-MS, the matrix effects, or non-spectroscopic interferences, can be defined as the type of interferences caused by dissolved concomitant salt ions in the solution. Matrix effects can be divided into two categories: (1) signal drift due to the deposition of solids on the sampling apertures; and/or (2) signal suppression or enhancement by the presence of the dissolved salts. The first category is now reasonably understood. The dissolved salts, especially refractory oxides, tend to deposit on the cool tip of the sampling cone. The clogging of the orifices reduces the ion flow into the ICP-MS, lowers the pressure in the first stage of ICP-MS, and enhances the level of metal oxide ions. Because the extent of the clogging increases with the time, the signal drifts down. Even at the very early stage of the development of ICP-MS, matrix effects had been observed. Houk et al. found out that the ICP-MS was not tolerant to solutions containing significant amounts of dissolved solids.

  7. CAPILLARY ELECTROPHORESIS COUPLED ON-LINE WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY FOR ELEMENTAL SPECIATION

    EPA Science Inventory

    A novel interface to connect a capillary electrophoresis (CE) system with an inductively coupled plasma mass spectrometric (ICPMS) detector is reported here. The interface was built using a direct injection nebulizer (DIN) system. In this interface, the CE capillary was placed co...

  8. Aerosol detection efficiency in inductively coupled plasma mass spectrometry

    DOE PAGESBeta

    Hubbard, Joshua A.; Zigmond, Joseph A.

    2016-03-02

    We used an electrostatic size classification technique to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Moreover, we counted size-segregated particles with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized bymore » the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10-5 to 10-11. Free molecular heat and mass transfer theory was

  9. Aerosol detection efficiency in inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hubbard, Joshua A.; Zigmond, Joseph A.

    2016-05-01

    An electrostatic size classification technique was used to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Size-segregated particles were counted with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized by the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10- 5 to 10- 11. Free molecular heat and mass transfer theory was applied, but

  10. Capillary Electrophoresis-Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Michalke, Bernhard

    2016-01-01

    During the recent years, capillary electrophoresis (CE) has been fully established as a powerful tool in separation sciences as well as in element speciation. This road of success is based on the rapid analysis time, low sample requirements, high separation efficiency, and low operating costs of CE. Inductively coupled plasma mass spectrometry (ICP-MS) is known for superior detection and multielement capability. Consequently, the combination of both instruments is approved for analysis of complex sample types at low element concentrations which require high detection power. Also the diversity of potential applications brings CE-ICP-MS coupling into central focus of element speciation. The key to successful combination of ICP-MS as an (multi-)element selective detector for CE is the availability of a suitable and effective interface.Therefore, this chapter summarizes the most important and basic principles about coupling of capillary electrophoresis to ICP-MS. Specifically, the major requirements for interfacing are described and technical solutions are given. Such solutions include the closing of the electrical circuit from CE at the nebulization, the adoption of flow rates for efficient nebulization, the reduction of a suction flow through the capillary, caused by the nebulizer, and maintaining the high separation resolution from CE across the interface for ICP-MS detection. Additionally, detailed information is presented to determine and quantify the siphoning suction through the CE capillary by the nebulizer. Finally, two applications, namely, the manganese and selenium speciation in cerebrospinal fluid are shown as examples, providing the relevant operational parameter. PMID:27645737

  11. Uranium quantification in semen by inductively coupled plasma mass spectrometry.

    PubMed

    Todorov, Todor I; Ejnik, John W; Guandalini, Gustavo; Xu, Hanna; Hoover, Dennis; Anderson, Larry; Squibb, Katherine; McDiarmid, Melissa A; Centeno, Jose A

    2013-01-01

    In this study we report uranium analysis for human semen samples. Uranium quantification was performed by inductively coupled plasma mass spectrometry. No additives, such as chymotrypsin or bovine serum albumin, were used for semen liquefaction, as they showed significant uranium content. For method validation we spiked 2g aliquots of pooled control semen at three different levels of uranium: low at 5 pg/g, medium at 50 pg/g, and high at 1000 pg/g. The detection limit was determined to be 0.8 pg/g uranium in human semen. The data reproduced within 1.4-7% RSD and spike recoveries were 97-100%. The uranium level of the unspiked, pooled control semen was 2.9 pg/g of semen (n=10). In addition six semen samples from a cohort of Veterans exposed to depleted uranium (DU) in the 1991 Gulf War were analyzed with no knowledge of their exposure history. Uranium levels in the Veterans' semen samples ranged from undetectable (<0.8 pg/g) to 3350 pg/g. This wide concentration range for uranium in semen is consistent with known differences in current DU body burdens in these individuals, some of whom have retained embedded DU fragments.

  12. Gold fingerprinting by laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Watling, R. John; Herbert, Hugh K.; Delev, Dianne; Abell, Ian D.

    1994-02-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been applied to the characterization of the trace element composition "fingerprint" of selected gold samples from Western Australia and South Africa. By comparison of the elemental associations it is possible to relate gold to a specific mineralizing event, mine or bullion sample. This methodology facilitates identification of the provenance of stolen gold or gold used in salting activities. In this latter case, it is common for gold from a number of sources to be used in the salting process. Consequently, gold in the prospect being salted will not come from a single source and identification of multiple sources for this gold will establish that salting has occurred. Preliminary results also indicate that specific elemental associations could be used to identify the country of origin of gold. The technique has already been applied in 17 cases involving gold theft in Western Australia, where it is estimated that up to 2% of gold production is "relocated" each year as a result of criminal activities.

  13. Inductively Coupled Plasma-Mass Spectrometry and the European Discovery of America

    NASA Astrophysics Data System (ADS)

    Houk, R. S.

    2000-05-01

    The background and initial experimental results in inductively coupled plasma-mass spectrometry (ICP-MS) are juxtaposed with similar events from the voyages of Christopher Columbus, particularly with the first voyage.

  14. Serum/plasma methylmercury determination by isotope dilution gas chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Baxter, Douglas C; Faarinen, Mikko; Österlund, Heléne; Rodushkin, Ilia; Christensen, Morten

    2011-09-01

    A method for the determination of methylmercury in plasma and serum samples was developed. The method uses isotope dilution with (198)Hg-labeled methylmercury, extraction into dichloromethane, back-extraction into water, aqueous-phase ethylation, purge and trap collection, thermal desorption, separation by gas chromatography, and mercury isotope specific detection by inductively coupled plasma mass spectrometry. By spiking 2 mL sample with 1.2 ng tracer, measurements in a concentration interval of (0.007-2.9) μg L(-1) could be performed with uncertainty amplification factors <2. A limit of quantification of 0.03 μg L(-1) was estimated at 10 times the standard deviation of concentrations measured in preparation blanks. Within- and between-run relative standard deviations were <10% at added concentration levels of 0.14 μg L(-1), 0.35 μg L(-1) and 2.8 μg L(-1), with recoveries in the range 82-110%. Application of the method to 50 plasma/serum samples yielded a median (mean; range) concentration of methylmercury of 0.081 (0.091; <0.03-0.19) μg L(-1). This is the first time methylmercury has been directly measured in this kind of specimen, and is therefore the first estimate of a reference range.

  15. In situ calibration of inductively coupled plasma-atomic emission and mass spectroscopy

    DOEpatents

    Braymen, Steven D.

    1996-06-11

    A method and apparatus for in situ addition calibration of an inductively coupled plasma atomic emission spectrometer or mass spectrometer using a precision gas metering valve to introduce a volatile calibration gas of an element of interest directly into an aerosol particle stream. The present situ calibration technique is suitable for various remote, on-site sampling systems such as laser ablation or nebulization.

  16. Determination of Arsenic in Sinus Wash and Tap Water by Inductively Coupled Plasma-Mass Spectrometry

    ERIC Educational Resources Information Center

    Donnell, Anna M.; Nahan, Keaton; Holloway, Dawone; Vonderheide, Anne P.

    2016-01-01

    Arsenic is a toxic element to which humans are primarily exposed through food and water; it occurs as a result of human activities and naturally from the earth's crust. An experiment was developed for a senior level analytical laboratory utilizing an Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) for the analysis of arsenic in household…

  17. DETERMINATION OF BROMATE IN DRINKING WATERS BY ION CHROMATOGRAPHY WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

    EPA Science Inventory

    Bromate is a disinfection by-product in drinking water, formed during the ozonation of source water containing bromide. An inductively coupled plasma mass spectrometer is combined with an ion chromatograph for the analysis of bromate in drinking waters. Three chromatographic colu...

  18. Iron-Isotopic Fractionation Studies Using Multiple Collector Inductively Coupled Plasma Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Anbar, A. D.; Zhang, C.; Barling, J.; Roe, J. E.; Nealson, K. H.

    1999-01-01

    The importance of Fe biogeochemistry has stimulated interest in Fe isotope fractionation. Recent studies using thermal ionization mass spectrometry (TIMS) and a "double spike" demonstrate the existence of biogenic Fe isotope effects. Here, we assess the utility of multiple-collector inductively-coupled plasma mass spectrometry(MC-ICP-MS) with a desolvating sample introduction system for Fe isotope studies, and present data on Fe biominerals produced by a thermophilic bacterium. Additional information is contained in the original extended abstract.

  19. Evaluation of Inductively Couple Plasma-time-of-Flight Mass Spectrometry for Laser Ablation Analyses

    SciTech Connect

    S.J. Bajic; D.B. Aeschliman; D.P. Baldwin; R.S. Houk

    2003-09-30

    The purpose of this trip to LECO Corporation was to test the non-matrix matched calibration method and the principal component analysis (PCA) method on a laser ablation-inductively coupled plasma-time of flight mass spectrometry (LA-ICP-TOFMS) system. An LA-ICP-TOFMS system allows for multielement single-shot analysis as well as spatial analysis on small samples, because the TOFMS acquires an entire mass spectrum for all ions extracted simultaneously from the ICP. The TOFMS system differs from the double-focusing mass spectrometer, on which the above methods were developed, by having lower sensitivity and lower mass resolution.

  20. Optical emission spectroscopy studies of the influence of laserablated mass on dry inductively coupled plasma conditions

    SciTech Connect

    Ciocan, A.C.; Mao, X.L.; Borisov, Oleg V.; Russo, R.E.

    1997-07-01

    The amount of ablated mass can influence the temperature andexcitation characteristics of the inductively coupled plasma (ICP) andmust be taken into account to ensure accurate chemical analysis. The ICPelectron number density was investigated by using measurements of the Mgionic to atomic resonant-line ratios during laser ablation of an aluminummatrix. The ICP excitation temperature was measured by using selected Felines during laser ablation of an iron matrix. A Nd:YAG laser (3 ns pulseduration) at 266 nm was used for these ablation-sampling studies. Laserenergy, power density, and repetition rate were varied in order to changethe quantity of ablated mass into the ICP. Over the range of laseroperating conditions studied herein, the ICP was not significantlyinfluenced by the quantity of solid sample. Therefore, analyticalmeasurements can be performed accurately and fundamental studies of laserablation processes (such as ablation mass roll-off, fractionalvaporization) can be investigated using inductively coupled plasma-atomicemission spectroscopy (ICP-AES).

  1. MICROSCALE FLOW INJECTION AND MICROBORE HIGH-PERFORMANCE LIQUID CHROMATORGRAPHY COUPLED WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY VIA A HIGH-EFFICIENCY NEBULIZER

    EPA Science Inventory

    A high-effeciency nebulizer has been used for coupling microscale flow injection and microbore high-performance liquid chromatography with inductively coupled plasma mass spectrometry (ICPMS). The microscale flow injection system was configured to minimize band broadening between...

  2. UV and IR laser ablation for inductively coupled plasma mass spectrometry

    SciTech Connect

    Smith, M.R.; Koppenaal, D.W.; Farmer, O.T.

    1993-06-01

    Laser ablation particle plume compositions are characterized using inductively coupled plasma mass spectrometry (ICP/MS). This study evaluates the mass response characteristics peculiar to ICP/MS detection as a function of laser fluence and frequency. Evaluation of the ICP/MS mass response allows deductions to be made concerning how representative the laser ablation produced particle plume composition is relative to the targeted sample. Using a black glass standard, elemental fractionation was observed, primarily for alkalis and other volatile elements. The extent of elemental fractionation between the target sample and the sampled plume varied significantly as a function of laser fluences and IR and UV laser frequency.

  3. Inductively coupled plasma mass spectrometry for stable isotope metabolic tracer studies of living systems

    SciTech Connect

    Luong, E.

    1999-05-10

    This dissertation focuses on the development of methods for stable isotope metabolic tracer studies in living systems using inductively coupled plasma single and dual quadrupole mass spectrometers. Sub-nanogram per gram levels of molybdenum (Mo) from human blood plasma are isolated by the use of anion exchange alumina microcolumns. Million-fold more concentrated spectral and matrix interferences such as sodium, chloride, sulfate, phosphate, etc. in the blood constituents are removed from the analyte. The recovery of Mo from the alumina column is 82 {+-} 5% (n = 5). Isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is utilized for the quantitative ultra-trace concentration determination of Mo in bovine and human blood samples. The average Mo concentration in reference bovine serum determined by this method is 10.2 {+-} 0.4 ng/g, while the certified value is 11.5 {+-} 1.1 ng/g (95% confidence interval). The Mo concentration of one pool of human blood plasma from two healthy male donors is 0.5 {+-} 0.1 ng/g. The inductively coupled plasma twin quadrupole mass spectrometer (ICP-TQMS) is used to measure the carbon isotope ratio from non-volatile organic compounds and bio-organic molecules to assess the ability as an alternative analytical method to gas chromatography combustion isotope ratio mass spectrometry (GC-combustion-IRMS). Trytophan, myoglobin, and {beta}-cyclodextrin are chosen for the study, initial observation of spectral interference of {sup 13}C{sup +} with {sup 12}C{sup 1}H{sup +} comes from the incomplete dissociation of myoglobin and/or {beta}-cyclodextrin.

  4. In situ calibration of inductively coupled plasma-atomic emission and mass spectroscopy

    DOEpatents

    Braymen, S.D.

    1996-06-11

    A method and apparatus are disclosed for in situ addition calibration of an inductively coupled plasma atomic emission spectrometer or mass spectrometer using a precision gas metering valve to introduce a volatile calibration gas of an element of interest directly into an aerosol particle stream. The present in situ calibration technique is suitable for various remote, on-site sampling systems such as laser ablation or nebulization. 5 figs.

  5. Reduction of plyatomic ion interferences in indictively coupled plasma mass spectrometry with cryogenic desolvation

    SciTech Connect

    Alves, L.C.

    1993-09-01

    A desolvation scheme for introducing aqueous and organic samples into an argon inductively coupled plasma is described; the aerosol generated by nebulizer is heated (+140 C) and cooled ({minus}80 C) repeatedly, and the dried aerosol is then injected into the mass spectrometer. Polyatomic ions are greatly suppressed. This scheme was validated with analysis of seawater and urine reference samples. Finally, the removal of organic solvents by cryogenic desolvation was studied.

  6. Separation of actinides using capillary extraction chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Peterson, Dominic S; Montoya, Velma M

    2009-08-01

    Trace levels of actinides have been separated on capillary extraction chromatography columns. Detection of the actinides was achieved using an inductively coupled plasma mass spectrometer, which was coupled with the extraction chromatography system. In this study, we compare 30-cm long, 4.6 mm i.d. columns to capillary columns (750 microm i.d.) with lengths from 30 cm up to 150 cm. The columns that were tested were packed with TRU resin. We were able to separate a mixture of five actinides ((232)Th, (238)U, (237)Np, (239)Pu, and (241)Am). This work has application to rapid bioassay as well as automated separations of actinide materials.

  7. Speciation of volatile selenium species in plants using gas chromatography/inductively coupled plasma mass spectrometry.

    PubMed

    Meija, Juris; Montes-Bayón, Maria; Caruso, Joseph A; Leduc, Danika L; Terry, Norman

    2004-01-01

    Gas chromatography/inductively coupled plasma mass spectrometry (GC/ICP-MS) coupled with solid phase micro-extraction can provide a simple, extremely selective and sensitive technique for the analysis of volatile sulfur and selenium compounds in the headspace of growing plants. In this work, the technique was used to evaluate the volatilization of selenium in wild-type and genetically-modified Brassica juncea seedlings. By converting toxic inorganic selenium in the soil to less toxic, volatile organic selenium, B. juncea might be useful in bioremediation of selenium contaminated soil.

  8. Radionuclide determination in environmental samples by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lariviere, Dominic; Taylor, Vivien F.; Evans, R. Douglas; Cornett, R. Jack

    2006-08-01

    The determination of naturally occurring and anthropogenic radionuclides in the environment by inductively coupled plasma mass spectrometry has gained recognition over the last fifteen years, relative to radiometric techniques, as the result of improvement in instrumental performance, sample introduction equipment, and sample preparation. With the increase in instrumental sensitivity, it is now possible to measure ultratrace levels (fg range) of many radioisotopes, including those with half-lives between 1 and 1000 years, without requiring very complex sample pre-concentration schemes. However, the identification and quantification of radioisotopes in environmental matrices is still hampered by a variety of analytical issues such as spectral (both atomic and molecular ions) and non-spectral (matrix effect) interferences and instrumental limitations (e.g., abundance sensitivity). The scope of this review is to highlight recent analytical progress and issues associated with the determination of radionuclides by inductively coupled plasma mass spectrometry. The impact of interferences, instrumental limitations (e.g., degree of ionization, abundance sensitivity, detection limits) and low sample-to-plasma transfer efficiency on the measurement of radionuclides by inductively coupled plasma mass spectrometry will be described. Solutions that overcome these issues will be discussed, highlighting their pros and cons and assessing their impact on the measurement of environmental radioactivity. Among the solutions proposed, mass and chemical resolution through the use of sector-field instruments and chemical reactions/collisions in a pressurized cell, respectively, will be described. Other methods, such as unique sample introduction equipment (e.g., laser ablation, electrothermal vaporisation, high efficiency nebulization) and instrumental modifications/optimizations (e.g., instrumental vacuum, radiofrequency power, guard electrode) that improve sensitivity and performance

  9. Inductively coupled plasma mass spectrometry in the analysis of biological samples and pharmaceutical drugs

    NASA Astrophysics Data System (ADS)

    Ossipov, K.; Seregina, I. F.; Bolshov, M. A.

    2016-04-01

    Inductively coupled plasma mass spectrometry (ICP-MS) is widely used in the analysis of biological samples (whole blood, serum, blood plasma, urine, tissues, etc.) and pharmaceutical drugs. The shortcomings of this method related to spectral and non-spectral interferences are manifested in full measure in determination of the target analytes in these complex samples strongly differing in composition. The spectral interferences are caused by similarity of masses of the target component and sample matrix components. Non-spectral interferences are related to the influence of sample matrix components on the physicochemical processes taking place during formation and transportation of liquid sample aerosols into the plasma, on the value and spatial distribution of plasma temperature and on the transmission of the ion beam from the interface to mass spectrometer detector. The review is devoted to analysis of different mechanisms of appearance of non-spectral interferences and to ways for their minimization or elimination. Special attention is paid to the techniques of biological sample preparation, which largely determine the mechanisms of the influence of sample composition on the results of element determination. The ways of lowering non-spectral interferences by instrumental parameter tuning and application of internal standards are considered. The bibliography includes 189 references.

  10. Time-resolved studies of particle effects in laser ablation inductively coupled plasma-mass spectrometry

    SciTech Connect

    Perdian, D.; Bajic, S.; Baldwin, D.; Houk, R.

    2007-11-13

    Time resolved signals in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) are studied to determine the influence of experimental parameters on ICP-induced fractionation effects. Differences in sample composition and morphology, i.e., ablating brass, glass, or dust pellets, have a profound effect on the time resolved signal. Helium transport gas significantly decreases large positive signal spikes arising from large particles in the ICP. A binder for pellets also reduces the abundance and amplitude of spikes in the signal. MO{sup +} ions also yield signal spikes, but these MO{sup +} spikes generally occur at different times from their atomic ion counterparts.

  11. Chemical recoveries of technetium-99 for various procedures using inductively coupled plasma-mass spectrometry

    SciTech Connect

    Ihsanullah; East, B.W.

    1993-12-31

    The procedure for the determination of {sup 99}Tc inductively coupled plasma-mass spectrometry (ICP-MS) was based on the modification of a variety of available separation techniques. Standard Ru and Rh solutions were used for checking decontaminations and instrument response respectively. Technetium-99 and {sup 95m}Tc tracers were applied as yield monitors using ICP-MS and gamma-ray spectrometry respectively. Percent recoveries are reported for a variety of radiochemical separation procedures for water (58-83%), seaweed (10-76%), and for soil matrices (19-79%).

  12. Study of fluorocarbon plasma in 60 and 100 MHz capacitively coupled discharges using mass spectrometry

    SciTech Connect

    Ushakov, Andrey; Volynets, Vladimir; Jeong, Sangmin; Sung, Dougyong; Ihm, Yongho; Woo, Jehun; Han, Moonhyeong

    2008-09-15

    The signals of positive ions and radicals formed in the fluorocarbon plasma of the capacitively coupled plasma reactor were measured using a quadrupole mass spectrometry and optical emission actinometry. The plasma was produced at 60 and 100 MHz frequencies for the same reactor configuration and gas mixtures. Experiments were performed at 25 mTorr with a SiO{sub 2} wafer on the grounded electrode. Mass spectra of ions were measured in C{sub 4}F{sub 8}/O{sub 2}/Ar and C{sub 4}F{sub 6}/O{sub 2}/Ar gas mixtures at 500-1500 W generator powers. For 60 and 100 MHz discharges production of fluorocarbon ions and radicals is discussed. It was found that the production of heavy species increases with frequency. The high mass signals such as C{sub 3}F{sub 3}{sup +}, C{sub 2}F{sub 4}{sup +}, C{sub 2}F{sub 5}{sup +}, C{sub 3}F{sub 5}{sup +}, C{sub 4}F{sub 7}{sup +} decrease when CHF{sub 3} is added to the gas mixture. However, the signals of CF{sub x}{sup +} (x=1,2,3) do not change significantly. These results are compared to the results of polymer film deposition on the wafer. It was suggested to control the polymerization film formation by adding small amount of CHF{sub 3} to the process mixture.

  13. Elemental Bioimaging by Means of Fast Scanning Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry.

    PubMed

    Wehe, Christoph A; Thyssen, Georgina M; Herdering, Christina; Raj, Indra; Ciarimboli, Giuliano; Sperling, Michael; Karst, Uwe

    2015-08-01

    One of the most common setups for elemental bioimaging, the hyphenation of a laser ablation (LA) system and an inductively coupled plasma mass spectrometer (ICP-MS), was expanded by adding full scan mass spectrometric information as another dimension of information. While most studies deal with the analysis of typically not more than up to 10 isotopes per scan cycle, a fast scanning quadrupole mass analyzer was utilized to record the full mass spectrum of interest in this work. Mass-to-charge ratios from 6 to 250 were observed within one cycle. Besides the x- and y-position on the ablated sample and the intensity, the m/z-ratio served as fourth variable for each pixel of the obtained data, closing thereby the gap between "inorganic" and "organic" mass spectrometric imaging techniques. The benefits of this approach include an improved control of interferences, the discovery of unexpected elemental distributions, the possibility to plot isotopic ratios, and to integrate the intensities of a certain number of mass channels recorded for each isotope, thus virtually increasing sensitivity. The respective data are presented for dried droplets as well as embedded animal and human tissue slices. Limits of detection were calculated and found to be in accordance with counting statistics. A dedicated software macro was developed for data manipulation prior to common evaluation and image creation. PMID:25947196

  14. Elemental Bioimaging by Means of Fast Scanning Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Wehe, Christoph A.; Thyssen, Georgina M.; Herdering, Christina; Raj, Indra; Ciarimboli, Giuliano; Sperling, Michael; Karst, Uwe

    2015-08-01

    One of the most common setups for elemental bioimaging, the hyphenation of a laser ablation (LA) system and an inductively coupled plasma mass spectrometer (ICP-MS), was expanded by adding full scan mass spectrometric information as another dimension of information. While most studies deal with the analysis of typically not more than up to 10 isotopes per scan cycle, a fast scanning quadrupole mass analyzer was utilized to record the full mass spectrum of interest in this work. Mass-to-charge ratios from 6 to 250 were observed within one cycle. Besides the x- and y-position on the ablated sample and the intensity, the m/z-ratio served as fourth variable for each pixel of the obtained data, closing thereby the gap between "inorganic" and "organic" mass spectrometric imaging techniques. The benefits of this approach include an improved control of interferences, the discovery of unexpected elemental distributions, the possibility to plot isotopic ratios, and to integrate the intensities of a certain number of mass channels recorded for each isotope, thus virtually increasing sensitivity. The respective data are presented for dried droplets as well as embedded animal and human tissue slices. Limits of detection were calculated and found to be in accordance with counting statistics. A dedicated software macro was developed for data manipulation prior to common evaluation and image creation.

  15. Laser ablation inductively coupled plasma mass spectrometry measurement of isotope ratios in depleted uranium contaminated soils.

    PubMed

    Seltzer, Michael D

    2003-09-01

    Laser ablation of pressed soil pellets was examined as a means of direct sample introduction to enable inductively coupled plasma mass spectrometry (ICP-MS) screening of soils for residual depleted uranium (DU) contamination. Differentiation between depleted uranium, an anthropogenic contaminant, and naturally occurring uranium was accomplished on the basis of measured 235U/238U isotope ratios. The amount of sample preparation required for laser ablation is considerably less than that typically required for aqueous sample introduction. The amount of hazardous laboratory waste generated is diminished accordingly. During the present investigation, 235U/238U isotope ratios measured for field samples were in good agreement with those derived from gamma spectrometry measurements. However, substantial compensation was required to mitigate the effects of impaired pulse counting attributed to sample inhomogeneity and sporadic introduction of uranium analyte into the plasma.

  16. Laser ablation inductively coupled plasma mass spectrometry measurement of isotope ratios in depleted uranium contaminated soils.

    PubMed

    Seltzer, Michael D

    2003-09-01

    Laser ablation of pressed soil pellets was examined as a means of direct sample introduction to enable inductively coupled plasma mass spectrometry (ICP-MS) screening of soils for residual depleted uranium (DU) contamination. Differentiation between depleted uranium, an anthropogenic contaminant, and naturally occurring uranium was accomplished on the basis of measured 235U/238U isotope ratios. The amount of sample preparation required for laser ablation is considerably less than that typically required for aqueous sample introduction. The amount of hazardous laboratory waste generated is diminished accordingly. During the present investigation, 235U/238U isotope ratios measured for field samples were in good agreement with those derived from gamma spectrometry measurements. However, substantial compensation was required to mitigate the effects of impaired pulse counting attributed to sample inhomogeneity and sporadic introduction of uranium analyte into the plasma. PMID:14611049

  17. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and its Application in Life Sciences

    NASA Astrophysics Data System (ADS)

    Xu, Gu-feng; Wang, Hong-mei

    2001-08-01

    Inductively-coupled plasma mass spectrometry (ICP-MS) has made much progress since its birth in the late 1990s. This paper will give a rather systematic overview on the use of this technique in new devices and technologies related to plasma source, sample-introducing device and detecting spectrometer etc. In this overview, an emphasis will be put on the evaluation of the ICP-MS technique in combination with a series of physical, chemical and biological techniques, such as laser ablation (LA), capillary electrophoresis (CE) and high performance liquid chromatograph (HPLC), along with their representative high accuracy and high sensitivity. Finally, comprehensive and fruitful applications of the ICP-MS and its combinative techniques in the detection of trace metallic elements and isotopes in complex biological and environmental samples will be revealed.

  18. An argon-nitrogen-hydrogen mixed-gas plasma as a robust ionization source for inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Makonnen, Yoseif; Beauchemin, Diane

    2014-09-01

    Multivariate optimization of an argon-nitrogen-hydrogen mixed-gas plasma for minimum matrix effects, while maintaining analyte sensitivity as much as possible, was carried out in inductively coupled plasma mass spectrometry. In the presence of 0.1 M Na, the 33.9 ± 3.9% (n = 13 elements) analyte signal suppression on average observed in an all-argon plasma was alleviated with the optimized mixed-gas plasma, the average being - 4.0 ± 8.8%, with enhancement in several cases. An addition of 2.3% v/v N2 in the outer plasma gas, and 0.50% v/v H2 to the central channel, as a sheath around the nebulizer gas flow, was sufficient for this drastic increase in robustness. It also reduced the background from ArO+ and Ar2+ as well as oxide levels by over an order of magnitude. On the other hand, the background from NO+ and ArN+ increased by up to an order of magnitude while the levels of doubly-charged ions increased to 7% (versus 2.7% in an argon plasma optimized for sensitivity). Furthermore, detection limits were generally degraded by 5 to 15 fold when using the mixed-gas plasma versus the argon plasma for matrix-free solution (although they were better for several elements in 0.1 M Na). Nonetheless, the drastically increased robustness allowed the direct quantitative multielement analysis of certified ore reference materials, as well as the determination of Mo and Cd in seawater, without using any matrix-matching or internal standardization.

  19. Determination of rare earth elements in tomato plants by inductively coupled plasma mass spectrometry techniques.

    PubMed

    Spalla, S; Baffi, C; Barbante, C; Turetta, C; Turretta, C; Cozzi, G; Beone, G M; Bettinelli, M

    2009-10-30

    In recent years identification of the geographical origin of food has grown more important as consumers have become interested in knowing the provenance of the food that they purchase and eat. Certification schemes and labels have thus been developed to protect consumers and genuine producers from the improper use of popular brand names or renowned geographical origins. As the tomato is one of the major components of what is considered to be the healthy Mediterranean diet, it is important to be able to determine the geographical origin of tomatoes and tomato-based products such as tomato sauce. The aim of this work is to develop an analytical method to determine rare earth elements (RRE) for the control of the geographic origin of tomatoes. The content of REE in tomato plant samples collected from an agricultural area in Piacenza, Italy, was determined, using four different digestion procedures with and without HF. Microwave dissolution with HNO3 + H2O2 proved to be the most suitable digestion procedure. Inductively coupled plasma quadrupole mass spectrometry (ICPQMS) and inductively coupled plasma sector field plasma mass spectrometry (ICPSFMS) instruments, both coupled with a desolvation system, were used to determine the REE in tomato plants in two different laboratories. A matched calibration curve method was used for the quantification of the analytes. The detection limits (MDLs) of the method ranged from 0.03 ng g(-1) for Ho, Tm, and Lu to 2 ng g(-1) for La and Ce. The precision, in terms of relative standard deviation on six replicates, was good, with values ranging, on average, from 6.0% for LREE (light rare earth elements) to 16.5% for HREE (heavy rare earth elements). These detection limits allowed the determination of the very low concentrations of REE present in tomato berries. For the concentrations of REE in tomato plants, the following trend was observed: roots > leaves > stems > berries.

  20. Separation of actinides using capillary extraction chromatography-inductively coupled plasma mass spectrometry

    SciTech Connect

    Peterson, Dominic S

    2008-01-01

    Trace levels of actinides have been separated on extraction chromatography columns. Detection of the actinides was achieved using an inductively coupled plasma mass spectrometer (ICP-MS), which was coupled with the extraction chromatography system. In this study we compare 30 cm long, 4.6 mm ID columns to capillary columns (750 {micro}m ID) with lengths from 30 cm up to 150 cm. The columns that were tested were packed with TRU resin. We were able to separate a mixture of five actinides ({sup 232}Th, {sup 238}U, {sup 237}Np, {sup 239}pU, {sup 241}Am). This work has application to rapid bioassay as well as for automated separations of actinide materials.

  1. A study of the interactions between carboplatin and blood plasma proteins using size exclusion chromatography coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Xie, Ruimin; Johnson, Willie; Rodriguez, Lorna; Gounder, Murugesan; Hall, Gene S; Buckley, Brian

    2007-04-01

    To study the carboplatin-protein interaction, a sensitive method using size exclusion chromatography coupled to inductively coupled plasma mass spectrometry (SEC-ICP-MS) was developed. The complexes formed between plasma proteins and carboplatin were monitored and identified with this method. Composite blood plasma samples from patients who were undergoing chemotherapy were analyzed, and carboplatin was found to bind plasma proteins. In addition, blank plasma samples were spiked with carboplatin and were analyzed as a time course study, and the results confirmed that carboplatin formed complexes with plasma proteins, primarily albumin and gamma-globulin. To further substantiate the study, these two proteins were incubated with carboplatin. The binding between carboplatin and these proteins was then characterized qualitatively and quantitatively. In addition to a one-to-one binding of Pt to protein, protein aggregation was observed. The kinetics of the binding process of carboplatin to albumin and gamma-globulin was also studied. The initial reaction rate constant of carboplatin binding to albumin was determined to be 0.74 M(-1) min(-1), while that for gamma-globulin was 1.01 M(-1) min(-1), which are both lower than the rate constant of the cisplatin-albumin reaction previously reported.

  2. [Nonradioactive iodine-labeled antibodies-inductively coupled plasma mass spectrometry for immunoassay].

    PubMed

    Li, Jing-Xi; Wang, Xiao-Ru; Zhuang, Zhi-Xia; Cui, Wei-Gang

    2010-03-01

    In the present study, the system of nonradioactive iodine-labeled-antibodies linking inductively coupled plasma mass spectrometry for immunoassay was reported. The goat-anti-Escherichia coli and goat anti rabbit were considered as simulant antigen and antibody respectively in order to establish a new method of immunoassay by inductively coupled plasma mass spectrometry which has the advantage of high sensitivity, low detection limit and preferable linearity range. During the experiment, the N-bromosuccinimide, a mild oxidant, was used to oxidize the non-radioactive iodine (127 I) that labeled the protein. The method of nonradioactive iodine labeled protein was established and the best labeling condition was explored. The compound of I was purified by Sephadex G50 column chromatography, then the stability and activity were examined. The results showed that the labeling program was simple, reaction time was within two minutes, the labeling yield achieved 63.12% and none of I shed from the compound after 96 hours. The simulant antigen and antibody reacted on polystyrene microtiter plate and the I was detected by ICP-MS, the detection limit of the method was 0.12 mg x L(-1), relative standard deviation (n = 9) was less than 3% and the linearly dependent coefficient was 0.998 7. This system can also be used in analysis of other protein, nucleic acid and so on.

  3. Continuum flow sampling mass spectrometer for elemental analysis with an inductively coupled plasma ion source

    SciTech Connect

    Olivares, J.A.

    1985-01-01

    The sampling of ions from an atmospheric pressure inductively coupled plasma for mass spectrometry (ICP-MS) with a supersonic nozzle and skimmer is shown to follow similar behavior found for neutral beam studies and of ion extraction from other plasmas and flames. The dependence of count rates for metal oxide and doubly charged ions on ICP operating parameters, and sampling interface configuration are discussed for this instrument. A simple method is described for the approximate measurement of the ion energy distribution in ICP-MS. The average ion kinetic energy, kinetic energy spread, and maximum kinetic energy are evaluated from a plot of ion signal as a function of retarding voltage applied to the quadrupole mass analyzer. The effects of plasma operating parameters on ion signals and energies are described. The interference on the ionization of cobalt by five salts, NaCl, MgCl/sub 2/, NH/sub 4/I, NH/sub 4/Br and NH/sub 4/Cl, in an ICP is first considered theoretically and subsequently the theoretical trends are established experimentally by ICP-MS. The interference trends are found to be in the order of the most easily ionized element in the matrix salt, i.e., Na > Mg > I > Br > Cl.

  4. Radionuclide detection by inductively coupled plasma mass spectrometry: A comparison of atomic and radiation detection method

    SciTech Connect

    Smith, M.R.; Wyse, E.J.; Koppenaal, D.W.

    1991-04-01

    Radionuclide detection by mass spectrometric techniques offers inherent advantages over conventional radiation detection methods. Since radionuclides decay at variable rates (half-lives) and via various nuclear transformations (i.e. emission of alpha, beta, and/or gamma radiation) their determination via radiation detection depends not only on decay systematics but also on detector technology. Radionuclide detection by direct atom measurement, however, is dependent only on technique sensitivity and is indifferent to decay mode. Evaluation of inductively coupled plasma mass spectrometry (ICP/MS) indicates this method to be superior conventional radiation detection techniques for many radionuclides. This work discusses factors which influence detection by both methods. Illustrative applications of ICP/MS to the ultra-trace determination of several radionuclides, including {sup 129}I, are presented. 20 refs., 6 figs., 1 tab.

  5. High Resolution Studies of the Origins of Polyatomic Ions in Inductively Coupled Plasma-Mass Spectrometry

    SciTech Connect

    Ferguson, Jill Wisnewski

    2006-01-01

    The inductively coupled plasma (ICP) is an atmospheric pressure ionization source. Traditionally, the plasma is sampled via a sampler cone. A supersonic jet develops behind the sampler, and this region is pumped down to a pressure of approximately one Torr. A skimmer cone is located inside this zone of silence to transmit ions into the mass spectrometer. The position of the sampler and skimmer cones relative to the initial radiation and normal analytical zones of the plasma is key to optimizing the useful analytical signal [1]. The ICP both atomizes and ionizes the sample. Polyatomic ions form through ion-molecule interactions either in the ICP or during ion extraction [l]. Common polyatomic ions that inhibit analysis include metal oxides (MO+), adducts with argon, the gas most commonly used to make up the plasma, and hydride species. While high resolution devices can separate many analytes from common interferences, this is done at great cost in ion transmission efficiency--a loss of 99% when using high versus low resolution on the same instrument [2]. Simple quadrupole devices, which make up the bulk of ICP-MS instruments in existence, do not present this option. Therefore, if the source of polyatomic interferences can be determined and then manipulated, this could potentially improve the figures of merit on all ICP-MS devices, not just the high resolution devices often utilized to study polyatomic interferences.

  6. [Analysis of Trace Inorganic Elements in Castor Oil by Inductively Coupled Plasma Mass Spectrometry].

    PubMed

    Li, Tan-ping; Xie, Hua-lin; Nie, Xi-du

    2015-10-01

    A method for the determination of Na, Mg, Si, P, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Hg and Pb in castor oil after direct dilution with ethanol by inductively coupled plasma mass spectrometry (ICP-MS) was established. The sample was diluted by ethanol before ICP-MS determination. The condensation and deposition of high concentrations of carbon in mass cone interface and ion lens, which will decrease the sensitivity of element analysis, were avoided effectively by introducing O2 to plasma. The mass spectral interferences were eliminated by octopole reaction system (ORS). The matrix effects were calibrated to using Sc, Ge, Rh and Ir as internal standard elements. Au standard solution, which could form amalgam alloy with Hg, was dropped to eliminate the memory effect of Hg. The results show that the correlation coefficient for analyte is no less than 0.999 5, the detection limits is in the range of 0.06 - 20.1 ng x L(-1), the recovery is in the range of 990.4% - 110.2%, and the RSD is less than 4.8%. This method was very fast, simple and accurate to simultaneously analyze multi-elements in castor oil.

  7. Scandium analysis in silicon-containing minerals by inductively coupled plasma tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Whitty-Léveillé, Laurence; Drouin, Elisabeth; Constantin, Marc; Bazin, Claude; Larivière, Dominic

    2016-04-01

    This article reports on the development of a new method for the accurate and precise determination of the amount of scandium, Sc, in silicon-containing minerals, based on the use of tandem quadrupole inductively coupled plasma mass spectrometry (ICP-MS/MS). The tandem quadrupole instrument enables new mass filtering configurations, which can reduce polyatomic interferences during the determination of Sc in mineral matrices. He and O2 were used and compared as collision and reaction gases for the removal of interferences at m/z 45 and 61. Using helium gas was ineffective to overcome all of the spectral interferences observed at m/z 45 and particularly for Si-based interferences. However, conversion of Sc+ ions into ScO+ ions (after bombardment with O2 in the octopole reaction system coupled with the use of the instrument in MS/MS mass-shift mode) provided interference-free conditions and sufficiently low limits of detection, down to 3 ng L- 1, to accurately detect Sc. The accuracy of the proposed methodology was assessed by analyzing five different reference materials (BX-N, OKA-2, NIM-L, SY-3 and GH).

  8. Determination of the rare-earth elements in geological materials by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Lichte, F.E.; Meier, A.L.; Crock, J.G.

    1987-01-01

    A method of analysis of geological materials for the determination of the rare-earth elements using the Inductively coupled plasma mass spectrometric technique (ICP-MS) has been developed. Instrumental parameters and factors affecting analytical results have been first studied and then optimized. Samples are analyzed directly following an acid digestion, without the need for separation or preconcentration with limits of detection of 2-11 ng/g, precision of ?? 2.5% relative standard deviation, and accuracy comparable to inductively coupled plasma emission spectrometry and instrumental neutron activation analysis. A commercially available ICP-MS instrument is used with modifications to the sample introduction system, torch, and sampler orifice to reduce the effects of high salt content of sample solutions prepared from geologic materials. Corrections for isobaric interferences from oxide ions and other diatomic and triatomic ions are made mathematically. Special internal standard procedures are used to compensate for drift in metahmetal oxide ratios and sensitivity. Reference standard values are used to verify the accuracy and utility of the method.

  9. Investigation of a measure of robustness in inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Makonnen, Yoseif; Beauchemin, Diane

    2015-01-01

    In industrial/commercial settings where operators often have minimal expertise in inductively coupled plasma (ICP) mass spectrometry (MS), there is a prevalent need for a response factor indicating robust plasma conditions, which is analogous to the Mg II/Mg I ratio in ICP optical emission spectrometry (OES), whereby a Mg II/Mg I ratio of 10 constitutes robust conditions. While minimizing the oxide ratio usually corresponds to robust conditions, there is no specific target value that is widely accepted as indicating robust conditions. Furthermore, tuning for low oxide ratios does not necessarily guarantee minimal matrix effects, as they really address polyatomic interferences. From experiments, conducted in parallel for both MS and OES, there were some element pairs of similar mass and very different ionization potential that were exploited for such a purpose, the rationale being that, if these elements were ionized to the same extent, then that could be indicative of a robust plasma. The Be II/Li I intensity ratio was directly related to the Mg II/Mg I ratio in OES. Moreover, the 9Be+/7Li+ ratio was inversely related to the CeO+/Ce+ and LaO+/La+ oxide ratios in MS. The effects of different matrices (i.e. 0.01-0.1 M Na) were also investigated and compared to a conventional argon plasma optimized for maximum sensitivity. The suppression effect of these matrices was significantly reduced, if not eliminated in the case of 0.01 M Na, when the 9Be+/7Li+ ratio was around 0.30 on the Varian 820 MS instrument. Moreover, a very similar ratio (0.28) increased robustness to the same extent on a completely different ICP-MS instrument (PerkinElmer NEXION). Much greater robustness was achieved using a mixed-gas plasma with nitrogen in the outer gas and either nitrogen or hydrogen as a sheathing gas, as the 9Be+/7Li+ ratio was then around 1.70. To the best of our knowledge, this is the first report on using a simple analyte intensity ratio, 9Be+/7Li+, to gauge plasma robustness.

  10. Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry

    SciTech Connect

    Perdian, David C.

    2009-01-01

    Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.

  11. Separation Of Uranium And Plutonium Isotopes For Measurement By Multi Collector Inductively Coupled Plasma Mass Spectroscopy

    SciTech Connect

    Martinelli, R E; Hamilton, T F; Williams, R W; Kehl, S R

    2009-03-29

    Uranium (U) and plutonium (Pu) isotopes in coral soils, contaminated by nuclear weapons testing in the northern Marshall Islands, were isolated by ion-exchange chromatography and analyzed by mass spectrometry. The soil samples were spiked with {sup 233}U and {sup 242}Pu tracers, dissolved in minerals acids, and U and Pu isotopes isolated and purified on commercially available ion-exchange columns. The ion-exchange technique employed a TEVA{reg_sign} column coupled to a UTEVA{reg_sign} column. U and Pu isotope fractions were then further isolated using separate elution schemes, and the purified fractions containing U and Pu isotopes analyzed sequentially using multi-collector inductively coupled plasma mass spectrometer (MCICP-MS). High precision measurements of {sup 234}U/{sup 235}U, {sup 238}U/{sup 235}U, {sup 236}U/{sup 235}U, and {sup 240}Pu/{sup 239}Pu in soil samples were attained using the described methodology and instrumentation, and provide a basis for conducting more detailed assessments of the behavior and transfer of uranium and plutonium in the environment.

  12. Laser-ablation sampling for inductively coupled plasma distance-of-flight mass spectrometry

    SciTech Connect

    Gundlach-Graham, Alexander W.; Dennis, Elise; Ray, Steven J.; Enke, Christie G.; Barinaga, Charles J.; Koppenaal, David W.; Hieftje, Gary M.

    2015-01-01

    An inductively coupled plasma distance-of-flight mass spectrometer (ICP-DOFMS) has been coupled with laser-ablation (LA) sample introduction for the elemental analysis of solids. ICP-DOFMS is well suited for the analysis of laser-generated aerosols because it offers both high-speed mass analysis and simultaneous multi-elemental detection. Here, we evaluate the analytical performance of the LA-ICP-DOFMS instrument, equipped with a microchannel plate-based imaging detector, for the measurement of steady-state LA signals, as well as transient signals produced from single LA events. Steady-state detection limits are 1 mg g1, and absolute single-pulse LA detection limits are 200 fg for uranium; the system is shown capable of performing time-resolved single-pulse LA analysis. By leveraging the benefits of simultaneous multi-elemental detection, we also attain a good shot-to-shot reproducibility of 6% relative standard deviation (RSD) and isotope-ratio precision of 0.3% RSD with a 10 s integration time.

  13. Assessment of the analytical capabilities of inductively coupled plasma-mass spectrometry

    USGS Publications Warehouse

    Taylor, H.E.; Garbarino, J.R.

    1988-01-01

    A thorough assessment of the analytical capabilities of inductively coupled plasma-mass spectrometry was conducted for selected analytes of importance in water quality applications and hydrologic research. A multielement calibration curve technique was designed to produce accurate and precise results in analysis times of approximately one minute. The suite of elements included Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Se, Sr, V, and Zn. The effects of sample matrix composition on the accuracy of the determinations showed that matrix elements (such as Na, Ca, Mg, and K) that may be present in natural water samples at concentration levels greater than 50 mg/L resulted in as much as a 10% suppression in ion current for analyte elements. Operational detection limits are presented.

  14. Inductively Coupled Plasma: Fundamental Particle Investigations with Laser Ablation and Applications in Magnetic Sector Mass Spectrometry

    SciTech Connect

    Saetveit, Nathan Joe

    2008-01-01

    Particle size effects and elemental fractionation in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) are investigated with nanosecond and femtosecond laser ablation, differential mobility analysis, and magnetic sector ICP-MS. Laser pulse width was found to have a significant influence on the LA particle size distribution and the elemental composition of the aerosol and thus fractionation. Emission from individual particles from solution nebulization, glass, and a pressed powder pellet are observed with high speed digital photography. The presence of intact particles in an ICP is shown to be a likely source of fractionation. A technique for the online detection of stimulated elemental release from neural tissue using magnetic sector ICP-MS is described. Detection limits of 1 μg L-1 or better were found for P, Mn, Fe, Cu, and Zn in a 60 μL injection in a physiological saline matrix.

  15. Stable isotope dilution analysis of hydrologic samples by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Garbarino, J.R.; Taylor, H.E.

    1987-01-01

    Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

  16. Analysis of iodine in food samples by inductively coupled plasma-mass spectrometry.

    PubMed

    Todorov, Todor I; Gray, Patrick J

    2016-01-01

    This work shows a method for the determination of iodine in a variety of food samples and reference materials using inductively coupled plasma-mass spectrometry (ICP-MS) following alkaline extraction. Optimisation of the addition of organic carbon showed that a minimum of 3% 2-propanol was necessary for a constant ratio of iodine to internal standard. The limit of quantification (LOQ), calculated as 30σ for the method, was 36 ng g(-1) in solid food samples. For method validation, seven standard reference materials (SRM) and 21 fortified food samples were used. The precision (%RSD) of the measurements was in the 2-7% range. Accuracies for the SRMs were 85-105%, while the fortified food samples showed 81-119% recoveries, including a number of samples fortified at 50% of the LOQ.

  17. Determination of total iodine in food samples using inductively coupled plasma-mass spectrometry.

    PubMed

    Benkhedda, Karima; Robichaud, André; Turcotte, Stéphane; Béraldin, Franca J; Cockell, Kevin A

    2009-01-01

    A method was developed and validated for the extraction and determination of total iodine (I) in food composite samples, representing different foods available on the Canadian market, by inductively coupled plasma-mass spectrometry (ICP-MS). Prior to analysis, samples were digested in a closed microwave system using a mixture of nitric acid and perchloric acid. The detection limit for iodine determination was 29 nglg and precisions of 10 and 1.3% were obtained for 10 replicate measurements of 100 and 1000 ng/g standards, respectively. The method was validated using Certified Reference Materials and spike recovery measurements in food samples and was applied for the determination of iodine in a variety of food composite samples from the Canadian Total Diet Study. The high sample throughput of ICP-MS makes the method suitable for analysis of large numbers of food samples with varying matrixes, such as for Total Diet Studies.

  18. Pulsed radio-frequency discharge inductively coupled plasma mass spectrometry for oxide analysis

    NASA Astrophysics Data System (ADS)

    Li, Weifeng; Yin, Zhibin; Hang, Wei; Li, Bin; Huang, Benli

    2016-08-01

    A direct solid sampling technique has been developed based on a pulsed radio-frequency discharge (RFD) in mixture of N2 and Ar environment at atmospheric pressure. With an averaged input power of 65 W, a crater with the diameter of 80 μm and depth of 50 μm can be formed on sample surface after discharge for 1 min, suggesting the feasibility of the pulsed RFD for sampling nonconductive solids. Combined with inductively coupled plasma mass spectrometry (ICPMS), this technique allows to measure elemental composition of solids directly with relative standard deviation (RSD) of ~ 20%. Capability of quantitative analysis was demonstrated by the use of soil standards and artificial standards. Good calibration linearity and limits of detection (LODs) in range of 10- 8-10- 9 g/g were achieved for most elements.

  19. Osmium isotopic ratio measurements by inductively coupled plasma source mass spectrometry

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.; Date, A.R.

    1987-04-01

    The isotopic composition of nanogram quantities of osmium was measured by using an inductively coupled plasma source mass spectrometer. Sensitivity was enhanced a factor of approx.100 by the use of an osmium tetraoxide vapor generator rather than nebulization of solution. For samples less than or equal to5 ng, the ratios /sup 190/Os//sup 192/Os, /sup 189/Os//sup 192/Os, and /sup 188/Os//sup 192/Os were determined to better than +/- 0.5% (1sigma/sub m/) precision. For the minor isotopes, the ratios /sup 187/Os//sup 192/Os and /sup 186/Os//sup 192/Os were determined to +/-1%, and /sup 184/Os//sup 192/Os (4 x 10/sup -4/) was determined to approx.10%. Isotope ratios for common osmium are reported.

  20. Accurate determination of silver nanoparticles in animal tissues by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Veverková, Lenka; Hradilová, Šárka; Milde, David; Panáček, Aleš; Skopalová, Jana; Kvítek, Libor; Petrželová, Kamila; Zbořil, Radek

    2014-12-01

    This study examined recoveries of silver determination in animal tissues after wet digestion by inductively coupled plasma mass spectrometry. The composition of the mineralization mixture for microwave assisted digestion was optimized and the best recoveries were obtained for mineralization with HNO3 and addition of HCl promptly after digestion. The optimization was performed on model samples of chicken meat spiked with silver nanoparticles and a solution of ionic silver. Basic calculations of theoretical distribution of Ag among various silver-containing species were implemented and the results showed that most of the silver is in the form of soluble complexes AgCl2- and AgCl32 - for the optimized composition of the mineralization mixture. Three animal tissue certified reference materials were then analyzed to verify the trueness and precision of the results.

  1. [Study on the determination of 14 inorganic elements in coffee by inductively coupled plasma mass spectrometry].

    PubMed

    Nie, Xi-Du; Fu, Liang

    2013-07-01

    Samples of coffee were digested by microwave digestion, and inorganic elements amounts of Na, Mg, P, Ca, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Mo and Pb in sample solutions were determined by inductively coupled plasma mass spectrometry (ICP-MS). HNO3 + H2O2 was used to achieve the complete decomposition of the organic matrix in a closed-vessel microwave oven. The working parameters of the instrument were optimized. The results showed that the relative standard deviation (RSD) was less than 3.84% for all the elements, and the recovery was found to be 92.00% -106.52% by adding standard recovery experiment. This method was simple, sensitive and precise and can perform simultaneous multi-elements determination of coffee, which could satisfy the sample examination request and provide scientific rationale for determining inorganic elements of coffee.

  2. Heavy metals in aromatic spices by inductively coupled plasma-mass spectrometry.

    PubMed

    Bua, Daniel Giuseppe; Annuario, Giovanni; Albergamo, Ambrogina; Cicero, Nicola; Dugo, Giacomo

    2016-09-01

    Objective of this study was to determine the content of Cd, Hg, As and Pb in common spices traded in the Italian market, using inductively coupled plasma-mass spectrometry (ICP-MS). The results were compared with the maximum limits established by the national Legislative Decree (LD) no. 107 implementing the Council Directive 88/388/EEC and by international organisations, such as Food and Agriculture Organization (FAO) and World Health Organization (WHO). Food safety for spices was assessed considering the tolerable weekly intake (TWI) and the provisional tolerable weekly intake (PTWI), respectively, for Cd and Hg and the 95% lower confidence limit of the benchmark dose of 1% extra risk (BMDL01) for As and Pb. Investigated elements in all samples were within the maximum limits as set by the national and international normative institutions. Nevertheless, the heavy metal content of some spices exceeded the PTWI, TWI and BMDL01, which needs attention when considering consumer's health.

  3. Determination of elemental content off rocks by laser ablation inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Lichte, F.E.

    1995-01-01

    A new method of analysis for rocks and soils is presented using laser ablation inductively coupled plasma mass spectrometry. It is based on a lithium borate fusion and the free-running mode of a Nd/YAG laser. An Ar/N2 sample gas improves sensitivity 7 ?? for most elements. Sixty-three elements are characterized for the fusion, and 49 elements can be quantified. Internal standards and isotopic spikes ensure accurate results. Limits of detection are 0.01 ??g/g for many trace elements. Accuracy approaches 5% for all elements. A new quality assurance procedure is presented that uses fundamental parameters to test relative response factors for the calibration.

  4. Online Coupling of Flow-Field Flow Fractionation and Single Particle Inductively Coupled Plasma-Mass Spectrometry: Characterization of Nanoparticle Surface Coating Thickness and Aggregation State

    EPA Science Inventory

    Surface coating thickness and aggregation state have strong influence on the environmental fate, transport, and toxicity of engineered nanomaterials. In this study, flow-field flow fractionation coupled on-line with single particle inductively coupled plasma-mass spectrometry i...

  5. Fundamental studies of the plasma extraction and ion beam formation processes in inductively coupled plasma mass spectrometry

    SciTech Connect

    Niu, Hongsen

    1995-02-10

    The fundamental and practical aspects are described for extracting ions from atmospheric pressure plasma sources into an analytical mass spectrometer. Methodologies and basic concepts of inductively coupled plasma mass spectrometry (ICP-MS) are emphasized in the discussion, including ion source, sampling interface, supersonic expansion, slumming process, ion optics and beam focusing, and vacuum considerations. Some new developments and innovative designs are introduced. The plasma extraction process in ICP-MS was investigated by Langmuir measurements in the region between the skimmer and first ion lens. Electron temperature (T{sub e}) is in the range 2000--11000 K and changes with probe position inside an aerosol gas flow. Electron density (n{sub e}) is in the range 10{sup 8}--10{sup 10} {sup {minus}cm }at the skimmer tip and drops abruptly to 10{sup 6}--10{sup 8} cm{sup {minus}3} near the skimmer tip and drops abruptly to 10{sup 6}--10{sup 8} cm{sup {minus}3} downstream further behind the skimmer. Electron density in the beam leaving the skimmer also depends on water loading and on the presence and mass of matrix elements. Axially resolved distributions of electron number-density and electron temperature were obtained to characterize the ion beam at a variety of plasma operating conditions. The electron density dropped by a factor of 101 along the centerline between the sampler and skimmer cones in the first stage and continued to drop by factors of 10{sup 4}--10{sup 5} downstream of skimmer to the entrance of ion lens. The electron density in the beam expansion behind sampler cone exhibited a 1/z{sup 2} intensity fall-off (z is the axial position). An second beam expansion originated from the skimmer entrance, and the beam flow underwent with another 1/z{sup 2} fall-off behind the skimmer. Skimmer interactions play an important role in plasma extraction in the ICP-MS instrument.

  6. Representative sampling using single-pulse laser ablation withinductively coupled plasma mass spectroscopy

    SciTech Connect

    Liu, Haichen; Mao, Xianglei; Russo, Richard E.

    2001-04-02

    Single pulse laser ablation sampling with inductively coupled plasma mass spectrometry (ICP-MS) was assessed for accurate chemical analysis. Elemental fractionation (e.g. Pb/U), the quantity of ablated mass (crater volume), ICP-MS intensity and the particle contribution (spike signal) during single pulse ablation of NIST 610 glass were investigated. Pb/U fractionation significantly changed between the first and second laser pulse and showed strong irradiance dependence. The Pb/U ratio obtained by the first pulse was usually higher than that of the second pulse, with the average value close to the representative level. Segregation during laser ablation is proposed to explain the composition change between the first and second pulse. Crater volume measurements showed that the second pulse produced significantly more ablated mass. A roll-off of the crater depth occurred at {approx}750 GW/cm{sup 2}. The absolute ICP-MS intensity from the second pulse showed no correlation with crater depth. Particle induced spikes on the transit signal showed irradiance and elemental species dependence.

  7. Recent developments in inductively coupled plasma source magnetic sector multiple collector mass spectrometry

    NASA Astrophysics Data System (ADS)

    Halliday, A. N.; Lee, Der-Chuen; Christensen, J. C.; Jones, C. E.; Hall, C. M.; Yi, Wen; Teagle, D.; Walder, A. J.

    This paper describes advances in isotopic measurements that have been made with an inductively coupled plasma source magnetic sector multiple collector mass spectrometer and presents results of new experiments aimed at further evaluating the instrument's capability. It is shown using standard solutions that trace element ratios such as Rb/Sr can be measured precisely without isotope dilution by comparison with reference solutions of known composition. Similarly, using a new wide flight tube, Pb isotopic compositions and U/Pb ratios can be accurately measured simultaneously without isotope dilution. The effects of deliberately inducing changes in the running conditions (RF power) are shown to be significant for measuring trace element ratios but not for mass bias and interference corrected isotopic compositions. Finally, it is demonstrated that precise and accurate isotopic compositions of elements as refractory as W can be determined relatively easily by solution nebulization and even by direct laser ablation of complex silicates. Isobaric interferences in such experiments are negligible. These experiments serve to highlight the remarkable potential that this new field offers for hitherto difficult isotopic measurements in nuclear, earth, environmental and medical sciences. Isotopic measurements can be made that are reproducible at high precision through a range of running conditions, even in the presence of isobaric interferences. The ability to correct for mass discrimination accurately using a second element of similar mass, the very high sensitivity for elements that are otherwise difficult to ionize, the demonstrated capability for laser ablation work and the ability to measure through a wide mass range simultaneously give this instrument major advantages over other more traditional techniques of isotopic measurement.

  8. Recent developments in inductively coupled plasma source magnetic sector multiple collector mass spectrometry

    SciTech Connect

    Halliday, A.N.; Lee, Der-Chuen; Christensen, J.C.; Jones, C.E.; Hall, C.M.; Yi, Wen; Teagle, D.; Walder, A.J.; Freedman, P.A.

    1994-11-01

    This paper describes advances in isotopic measurements that have been made with an inductively coupled plasma source magnetic sector multiple collector mass spectrometer and presents results of new experiments aimed at further evaluating the instrument`s capability. It is shown using standard solutions that trace element ratios such as Rb/Sr can be measured precisely without isotope dilution by comparison with reference solutions of known composition. Similarly, using a new wide flight tube, Pb isotopic compositions and U/Pb ratios can be accurately measured simultaneously without isotope dilution. The effects of deliberately inducing changes in the running conditions (RF power) are shown to be significant for measuring trace element ratios but not for mass bias and interference corrected isotopic compositions. Finally, it is demonstrated that precise and accurate isotopic compositions of elements as refractory as W can be determined relatively easily by solution nebulization and even by direct laser ablation of complex silicates. Isobaric interferences in such experiments are negligible. These experiments serve to highlight the remarkable potential that this new field offers for hitherto difficult isotopic measurements in nuclear, earth, environmental and medical sciences. Isotopic measurements can be made that are reproducible at high precision through a range of running conditions, even in the presence of isobaric interferences. The ability to correct for mass discrimination accurately using a second element of similar mass, the very high sensitivity for elements that are otherwise difficult to ionize, the demonstrated capability for laser ablation work and the ability to measure through a wide mass range simultaneously give this instrument major advantages over other more traditional techniques of isotopic measurement.

  9. Rapid determination of uranium isotopes in urine by inductively coupled plasma-mass spectrometry.

    PubMed

    Shi, Y; Dai, X; Collins, R; Kramer-Tremblay, S

    2011-08-01

    Following a radiological or nuclear emergency involving uranium exposure, rapid analytical methods are needed to analyze the concentration of uranium isotopes in human urine samples for early dose assessment. The inductively coupled plasma mass spectrometry (ICP-MS) technique, with its high sample throughput and high sensitivity, has advantages over alpha spectrometry for uranium urinalysis after minimum sample preparation. In this work, a rapid sample preparation method using an anion exchange chromatographic column was developed to separate uranium from the urine matrix. A high-resolution sector field ICP-MS instrument, coupled with a high sensitivity desolvation sample introduction inlet, was used to determine uranium isotopes in the samples. The method can analyze up to 24 urine samples in two hours with the limits of detection of 0.0014, 0.10, and 2.0 pg mL(-1) for (234)U, (235)U, and (238)U, respectively, which meet the requirement for isotopic analysis of uranium in a radiation emergency.

  10. Determination of selenium urinary metabolites by high temperature liquid chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Terol, A; Ardini, F; Basso, A; Grotti, M

    2015-02-01

    The coupling of high temperature liquid chromatography (HTLC) and inductively coupled plasma mass spectrometry (ICPMS) for the determination of selenium metabolites in urine samples is reported for the first time. In order to achieve "ICPMS-friendly" chromatographic conditions, the retention on a graphite stationary phase of the major selenium urinary metabolites using only plain water with 2% methanol as the mobile phase was investigated. Under the optimal conditions (T=80°C, Ql=1.2 mL min(-1)), methyl 2-acetamido-2-deoxy-1-seleno-β-d-galactopyranoside (selenosugar 1), methyl 2-acetamido-2-deoxy-1-seleno-β-d-glucosopyranoside (selenosugar 2) and trimethylselenonium ion were efficiently separated in less than 7 min, without any interferences due to other common selenium species (selenite, selenate, selenocystine and selenomethionine) or detectable effect of the urine matrix. The limits of detection were 0.3-0.5 ng Se mL(-1), and the precision of the analytical procedure was better than 3% (RSD%, n=5). The HTLC-ICPMS method was applied to the analysis of urine samples from two volunteers before and after ingestion of Brazil nuts or selenium supplements. The developed procedure proved to be adequate for the analytical task, providing results consistent with previous studies. PMID:25582485

  11. Rapid determination of uranium isotopes in urine by inductively coupled plasma-mass spectrometry.

    PubMed

    Shi, Y; Dai, X; Collins, R; Kramer-Tremblay, S

    2011-08-01

    Following a radiological or nuclear emergency involving uranium exposure, rapid analytical methods are needed to analyze the concentration of uranium isotopes in human urine samples for early dose assessment. The inductively coupled plasma mass spectrometry (ICP-MS) technique, with its high sample throughput and high sensitivity, has advantages over alpha spectrometry for uranium urinalysis after minimum sample preparation. In this work, a rapid sample preparation method using an anion exchange chromatographic column was developed to separate uranium from the urine matrix. A high-resolution sector field ICP-MS instrument, coupled with a high sensitivity desolvation sample introduction inlet, was used to determine uranium isotopes in the samples. The method can analyze up to 24 urine samples in two hours with the limits of detection of 0.0014, 0.10, and 2.0 pg mL(-1) for (234)U, (235)U, and (238)U, respectively, which meet the requirement for isotopic analysis of uranium in a radiation emergency. PMID:21709502

  12. Sulfur analysis by inductively coupled plasma-mass spectrometry: A review

    NASA Astrophysics Data System (ADS)

    Giner Martínez-Sierra, J.; Galilea San Blas, O.; Marchante Gayón, J. M.; García Alonso, J. I.

    2015-06-01

    In recent years the number of applications of sulfur (S) analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. In this article we describe in some depth the application of ICP-MS for S analysis with emphasis placed on the sulfur-specific detection by hyphenated techniques such as LC, GC, CE and LA coupled on-line to ICP-MS. The different approaches available for sulfur isotope ratio measurements by ICP-MS are also detailed. Particular attention has been paid to the quantification of peptides/proteins and the analysis of metallopeptides/metalloproteins via sulfur by LC-ICP-MS. Likewise, the speciation analysis of metal-based pharmaceuticals and metallodrugs and non-metal selective detection of pharmaceuticals via S are highlighted. Labeling procedures for metabolic applications are also included. Finally, the measurement of natural variations in S isotope composition with multicollector ICP-MS instruments is also covered in this review.

  13. Atomic Mineral Characteristics of Indonesian Osteoporosis by High-Resolution Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Noor, Zairin; Sumitro, Sutiman Bambang; Hidayat, Mohammad; Rahim, Agus Hadian; Sabarudin, Akhmad; Umemura, Tomonari

    2012-01-01

    Clinical research indicates that negative calcium balance is associated with low bone mass, rapid bone loss, and high fracture rates. However, some studies revealed that not only calcium is involved in bone strengthening as risk factor of fracture osteoporosis. Thus, in this report, the difference of metallic and nonmetallic elements in osteoporosis and normal bones was studied by high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). The influence of these elements on bone metabolic processes is also discussed. Inclusion criteria of bone samples consist of postmenopausal woman, trabecular bone fracture, normal and osteoporosis BMD value, and no history of previous disease. The results showed that the concentration of B, Al, S, V, Co, Mo, Te, Ba, La, Ni, As, and Ca/P ratio is higher in osteoporosis than normal. These atomic minerals have negative role to imbalance between bone resorption and bone formation activity. Conversely, concentrations of Na, Mg, P, K, Ca, Cr, Pd, Ag, Mn, Fe, Cu, Zn, Rb, Sr, Pb, and Se are lower in osteoporosis than in normal bones. Among these atoms, known to have important roles in bone structure, we found involvement of atomic mineral and calcium which are considerable to contribute to osteoporotic phenomena. PMID:22654598

  14. Studies of selenium and xenon in inductively coupled plasma mass spectrometry

    SciTech Connect

    Bricker, T.

    1994-07-27

    Since its development, inductively coupled plasma mass spectrometry (ICP-MS) has been a widely used analytical technique. ICP-MS offers low detection limits, easy determination of isotope ratios, and simple mass spectra from analyte elements. ICP-MS has been successfully employed for many applications including geological, environmental, biological, metallurgical, food, medical, and industrial. One specific application important to many areas of study involves elemental speciation by using ICP-MS as an element specific detector interfaced to liquid chromatography. Elemental speciation information is important and cannot be obtained by atomic spectrometric methods alone which measure only the total concentration of the element present. Part 1 of this study describes the speciation of selenium in human serum by size exclusion chromatography (SEC) and detection by ICP-MS. Although ICP-MS has been widely sued, room for improvement still exists. Difficulties in ICP-MS include noise in the background, matrix effects, clogging of the sampling orifice with deposited solids, and spectral interference caused by polyatomic ions. Previous work has shown that the addition of xenon into the central channel of the ICP decreases polyatomic ion levels. In Part 2 of this work, a fundamental study involving the measurement of the excitation temperature is carried out to further understand xenon`s role in the reduction of polyatomic ions. 155 refs.

  15. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles. PMID:21111176

  16. Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

    PubMed

    Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

    2010-12-15

    Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles.

  17. Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

  18. Plutonium determination in seawater by inductively coupled plasma mass spectrometry: A review.

    PubMed

    Cao, Liguo; Bu, Wenting; Zheng, Jian; Pan, Shaoming; Wang, Zhongtang; Uchida, Shigeo

    2016-05-01

    Knowing the concentration and isotopic ratio of Pu in seawater is of critical importance for assessing Pu contamination and investigating oceanic processes. In recent decades, the concentration of (239+240)Pu in seawater, particularly for surface seawater, has presented an exponential decreasing trend with time; thus determination of Pu in seawater has become a challenge nowadays. Here, we have summarized and critically discussed a variety of reported analytical methods for Pu determination in seawater sample based on inductively coupled plasma mass spectrometry (ICP-MS) analytical technique for rapid ultra-trace detection of Pu. Generally, pretreatments for seawater sample include co-precipitation, valence adjustment and chemical separation and purification procedures, all of which are comprehensively reviewed. Overall, the selected anion-exchange, extraction resins and operation condition are important for decontamination of interference from matrix elements and achieving satisfactory chemical yields. In addition, other mass spectrometric and radiometric detections are briefly addressed and compared with the focus on assessing ICP-MS. Finally, we discuss some issues and prospects in determination and application of Pu isotopes in seawater samples for future research. PMID:26946007

  19. Alleviation of interferences and reduction of sample memory in inductively coupled plasma mass spectrometry

    SciTech Connect

    Smith, F.G.

    1991-06-27

    A simple variation sample preparation and introduction allows the measurement of chlorine isotope ratios by inductively coupled plasma mass spectroscopy (ICP-MS). Dissolution of the sample in D{sub 2}O rather than H{sub 2}O attenuates the major polyatomic ion {sup 36}ArH{sup +} and frees m/z = 37 for determination of {sup 37}Cl{sup +}. The isotope ratio {sup 35}Cl/{sup 37}Cl in a 50 mg L{sup {minus}1} solution of Cl as LiCl is determined with a relative standard deviation (RDS) of 0.21%. A method for the determination of boron is a variety of biological samples is described. Sample material is fused with Na{sub 2}CO{sub 3} and boron is separated from matrix components by using Amberlite IRA-743 boron selective ion-exchange resin. Boron is eluted with 1% HNO{sub 3} and samples are introduced to an ICP-mass spectrometer with a direct injection nebulizer (DIN). Xenon is added at 10 or 37 mL min{sup {minus}1} to the aerosol gas flow of an argon ICP-mass spectrometer. Addition of Xe substantially reduces polyatomic ions such as N{sub 2}{sup +}, HN{sub 2}{sup +}, NO{sup +}, ArH{sup +}, ClO{sup +}, ArC{sup +}, ClOH{sup +}, ArN{sup +}, and ArO{sup +} and facilitates the measurement of Si, K, V, Cr, and Fe. Isotope ratios are determined with RSDs from 0.6% to 1.6%. 210 refs., 14 figs., 19 tabs.

  20. Determination of plutonium in urine: evaluation of electrothermal vaporization inductively coupled plasma mass spectroscopy

    SciTech Connect

    Pietrzak, R.; Kaplan, E.

    1996-11-01

    Mass spectroscopy has the distinct advantage of detecting atoms rather than radioactive decay products for nuclides of low specific activity. Electrothermal vaporization (ETV) is an efficient means of introducing small volumes of prepared samples into an inductively coupled mass spectrometer to achieve the lowest absolute detection limits. The operational characteristics and capabilities of electrothermal vaporization inductively coupled mass spectrometer mass spectroscopy were evaluated. We describe its application as a detection method for determining Pu in urine, in conjunction with a preliminary separation technique to avoid matrix suppression of the signal.

  1. Speciation of cisplatin in environmental water samples by hydrophilic interaction liquid chromatography coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Vidmar, Janja; Martinčič, Anže; Milačič, Radmila; Ščančar, Janez

    2015-06-01

    Cisplatin is still widely used for treatment of numerous types of tumours. Different speciation methods have been applied to study behaviour of the intact drug and its individual biotransformation species in various clinical samples. These methods are mainly based on electrophoresis, size exclusion (SEC) or ion chromatography (IC) techniques coupled to inductively coupled plasma mass spectrometry (ICP-MS). Hydrophilic interaction liquid chromatography (HILIC), which is a common technique for separation of polar substances, was rarely applied for separation of cisplatin and its hydrolysed metabolites. There is also a lack of information available on the occurrence of cisplatin and its hydrolysed complexes in the environmental waters. In the present study the concentrations of Pt were determined in hospital wastewaters by ICP-MS. A procedure for separation of cisplatin and its aqueous hydrolysed complexes by the use of HILIC column was optimized. Quantification of separated Pt species was performed by isotope dilution (ID)-ICP-MS procedure. Low limits of detection (LODs) and quantification (LOQs) were obtained for cisplatin and its hydrolysed complexes ranging from 0.0273 to 0.1726 ng Pt/mL and from 0.0909 to 0.5753 ng Pt/mL, respectively. Good repeatability of the procedure with relative standard deviation (RSD) lower than ±2.3% was obtained. The column recoveries, which ranged from 95 to 101%, indicated that the procedure developed enabled quantitative speciation analysis of aqueous cisplatin complexes. The ZIC-HILIC-ID-ICP-MS procedure was successfully applied in speciation of cisplatin in spiked hospital wastewater samples.

  2. Quantitative Characterization of Gold Nanoparticles by Coupling Thin Layer Chromatography with Laser Ablation Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Yan, Neng; Zhu, Zhenli; Jin, Lanlan; Guo, Wei; Gan, Yiqun; Hu, Shenghong

    2015-06-16

    Metal nanoparticles (NPs) determination has recently attracted considerable attention because of the continuing boom of nanotechnology. In this study, a novel method for separation and quantitative characterization of NPs in aqueous suspension was established by coupling thin layer chromatography (TLC) with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Gold nanoparticles (AuNPs) of various sizes were used as the model system. It was demonstrated that TLC not only allowed separation of gold nanoparticles from ionic gold species by using acetyl acetone/butyl alcohol/triethylamine (6:3:1, v/v) as the mobile phase, but it also achieved the separation of differently sized gold nanoparticles (13, 34, and 47 nm) by using phosphate buffer (0.2 M, pH = 6.8), Triton X-114 (0.4%, w/v), and EDTA (10 mM) as the mobile phase. Various experimental parameters that affecting TLC separation of AuNPs, such as the pH of the phosphate buffer, the coating of AuNPs, the concentrations of EDTA and Triton X-114, were investigated and optimized. It was found that separations of AuNPs by TLC displayed size dependent retention behavior with good reproducibility, and the retardation factors (R(f) value) increased linearly with decreasing nanoparticle size. The analytical performance of the present method was evaluated under optimized conditions. The limits of detection were in the tens of pg range, and repeatability (RSD, n = 7) was 6.3%, 5.9%, and 8.3% for 30 ng of 13 nm AuNPs, 34 nm AuNPs, and 47 nm AuNPs, respectively. The developed TLC-LA-ICP-MS method has also been applied to the analysis of spiked AuNPs in lake water, river water, and tap water samples.

  3. Controlled Dissolution of Surface Layers for Elemental Analysis by Inductively Coupled Plasma-Mass Spectrometry

    SciTech Connect

    Lorge, Susan Elizabeth

    2007-01-01

    Determining the composition of thin layers is increasingly important for a variety of industrial materials such as adhesives, coatings and microelectronics. Secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES), glow discharge mass spectrometry (GDMS), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are some of the techniques that are currently employed for the direct analysis of the sample surface. Although these techniques do not suffer from the contamination problems that often plague sample dissolution studies, they do require matrix matched standards for quantification. Often, these standards are not readily available. Despite the costs of clean hoods, Teflon pipette tips and bottles, and pure acids, partial sample dissolution is the primary method used in the semiconductor industry to quantify surface impurities. Specifically, vapor phase decomposition (VPD) coupled to ICP-MS or total reflection x-ray fluorescence (TXRF) provides elemental information from the top most surface layers at detection sensitivities in the 107-1010atoms/cm2 range. The ability to quantify with standard solutions is a main advantage of these techniques. Li and Houk applied a VPD-like technique to steel. The signal ratio of trace element to matrix element was used for quantification. Although controlled dissolution concentrations determined for some of the dissolved elements agreed with the certified values, concentrations determined for refractory elements (Ti, Nb and Ta) were too low. LA-ICP-MS and scanning electron microscopy (SEM) measurements indicated that carbide grains distributed throughout the matrix were high in these refractory elements. These elements dissolved at a slower rate than the matrix element, Fe. If the analyte element is not removed at a rate similar to the matrix element a true

  4. Determination of trace elements in granites by inductively coupled plasma mass spectrometry.

    PubMed

    Liang, Q; Jing, H; Gregoire, D C

    2000-03-01

    Proposed is a simple and reliable method for the dissolution of granite and the determination of 38 elements by inductively coupled plasma mass spectrometry. One hundred milligrams of sample are digested with 1 ml of HF and 0.5 ml of HNO(3) in screw top PTFE-lined stainless steel bombs at 190 degrees C for 12 h. Insoluble residues are dissolved using 8 ml of 40% HNO(3) (v/v) heated to 110 degrees C for 3 h. Six granite standard reference materials (GSR-1, JG-2, G-2, NIM-G, SG-3, SG-1a) were studied. Analytical calibration was accomplished using aqueous standard solutions. Rhodium was used as an internal standard to correct for matrix effects and instrument drift. We report data for: Li, Be, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Cs, Ba, Hf, Ta, W, Pb, Th, U and 14 of the rare earth elements. The recoveries for most of these elements in granite ranged from 90 to 110%.

  5. Suppression of analyte signal by various concomitant salts in inductively coupled plasma mass spectrometry

    SciTech Connect

    Olivares, J.A.; Houk, R.S.

    1986-01-01

    The interference on the ionization of cobalt by five salts, NaCl, MgCl/sub 2/, NH/sub 4/I, NH/sub 4/Br, and NH/sub 4/Cl, in an inductively coupled plasma (ICP) is first looked at theoretically, and subsequently the theoretical trends are established experimentally by mass spectrometry (ICP-MS). The interference trends are found to be in the order of the most easily ionized element in the matrix salt, i.e., Na > Mg > I > Br > Cl. Quantitatively the theoretical values for the amount of salt needed to produce a particular interference are 1-2 orders of magnitude higher than the experimentally determined values. The results reported here indicate that ICP-MS is somewhat more susceptible to ionization suppression effects than ICP atomic emission spectrometry. It is also found that the most easily ionized element in the salt dominates the matrix ion spectrum observed from the ICP in the order mentioned above. Total ion current measurements by ICP-MC at solute levels above 1% are complicated by orifice plugging and transport loss of the salt and analyte in the desolvation system for the ultrasonic nebulizer used. 27 references, 7 figures, 3 tables.

  6. Determination of total iodine in foods and dietary supplements using inductively coupled plasma-mass spectrometry.

    PubMed

    Sullivan, Darryl; Zywicki, Richard

    2012-01-01

    A method was developed and validated for the determination of total iodine in a wide variety of food products and dietary supplements. The method involves a unique sample digestion with a KOH solution in an oven or by using an open-vessel microwave system. After digestion, a stabilizer is added and the solution is taken to volume, then filtered and analyzed either directly or after dilution. The amount of iodine is determined with inductively coupled plasma-mass spectrometry (ICP-MS). The method was validated by experiments to determine its precision, accuracy, linearity, specificity, ruggedness, and robustness. The LOQ of this method is 25-50 microg/kg. The method demonstrated an average RSD of 2.27% during analysis of milk powder and 4.30% during analysis of a dietary supplement tablet reference material. The accuracy of the method as determined with these same reference materials was 100 and 94.2%, respectively. The method has been used successfully on commodity foods, processed foods, dairy products, pet food, infant formula, animal feed, mineral premixes, and a variety of dietary supplements.

  7. Iodine speciation in biological samples by capillary electrophoresis-inductively coupled plasma mass spectrometry.

    PubMed

    Michalke, B; Schramel, P

    1999-09-01

    A hyphenation of capillary electrophoresis (CE) to inductively coupled plasma mass spectrometry (ICP-MS) was employed for the speciation of iodine. The separation method used a buffer sandwich of phosphate (pH 2.3), NaOH, sodium dodecyl sulfate (SDS) and borate buffer (pH 8.3) for stacking, aiming at sufficient separation of iodide, iodate, thyroxine (T4) and triiodothyronine (T3). These four iodine species were separated within 15 min and subsequently detected during a pressure-driven detection step (baseline-separated) at 19.5, 29.1, 36.6 and 42.2 s. The detection limits were determined at 0.08 microg I/L (iodide), 0.3 microg I/L (iodate), 3.5 microg I/L (thyroxine) and 2.5 microg I/L (triiodothyronine). This method was applied on iodine speciation in human serum ("healthy" and after thyroid gland operation) and urine. The serum from the healthy person contained iodide (13 microg I/L), T4 (61 microg I/L) and T3 (7.5 microg I/L), whereas the serum from the thyroid-operated person lacked T3. As no "free" I-hormones are known in serum, the role of the thyroid hormone binding globulin (TBG) was investigated. We found that spiked T4 or T3 immediately bound to TBG. Investigations on human urine showed only a peak for iodide.

  8. Improving sensitivity for microchip electrophoresis interfaced with inductively coupled plasma mass spectrometry using parallel multichannel separation.

    PubMed

    Cheng, Heyong; Liu, Jinhua; Xu, Zigang; Wang, Yuanchao; Ye, Meiying

    2016-08-26

    We reported sensitivity enhancement using multichannel parallel separation for microchip electrophoresis hyphenated with inductively coupled plasma mass spectrometry (MCE-ICP-MS) in this study. By using 2-20 array lanes for parallel separation, the sensitivity of the MCE-ICP-MS system was proportionally improved by 2-20 folds. No significantly adverse effect of parallel separation on column efficiency and resolution was observed. Rapid separation of Hg(2+) and methylmercuric (MeHg) ion within 36s under an electric field of 800Vcm(-1) was achieved in the 2-cm twenty-channels with a background electrolyte of 5mmolL(-1) borate buffer (pH 9.2). Detection limits of Hg(2+) and MeHg by the proposed system were decreased to 6.8-7.1ngL(-1). Good agreement between determined values and certified values of a certified reference fish was obtained with recoveries ranged between 94-98%. All results prove its advantages including high sensitivity, high efficiency and low operation cost, which are beneficial to routine analysis of metal speciation in environmental, biological and food fields. PMID:27488720

  9. Antimony speciation by inductively coupled plasma mass spectrometry using solid phase extraction cartridges.

    PubMed

    Yu, Chunhai; Cai, Qiantao; Guo, Zhong-Xian; Yang, Zhaoguang; Khoo, Soo Beng

    2002-10-01

    A novel and simple method for inorganic antimony speciation is described based on selective solid phase extraction (SPE) separation of antimony(III) and highly sensitive inductively coupled plasma mass spectrometric (ICP-MS) detection of total antimony and antimony(V) in the aqueous phase of the sample. Non-polar SPE cartridges, such as the Isolute silica-based octyl (C8) sorbent-containing cartridge, selectively retained the Sb(III) complex with ammonium pyrrolidine dithiocarbamate (APDC), while the uncomplexed Sb(V) remained as a free species in the solution and passed through the cartridge. The Sb(III) concentration was calculated as the difference between total antimony and Sb(V) concentrations. The detection limit was 1 ng L(-1) antimony. Factors affecting the separation and detection of antimony species were investigated. Acidification of samples led to partial or complete retention of Sb(V) on C8 cartridge. Foreign ions tending to complex with Sb(III) or APDC did not interfere with the retention behavior of the Sb(III)-APDC complex. This method has been successfully applied to antimony speciation of various types of water samples.

  10. Inductively coupled plasma-mass spectrometry: An emerging method for analysis of long-lived radionuclides

    SciTech Connect

    Ross, R.R.; Noyce, J.R.; Lardy, M.M.

    1993-12-31

    Inductively coupled plasma-mass spectrometry (ICP-MS) is a relatively new technique that can analyze for most of the elements in the periodic table at parts per billion (ng/mL) to parts per trillion (pg/mL). Already in use several years for trace analysis of stable isotopes, ICP-MS is becoming a powerful, complementary method to the counting of decay radiations for the analysis of radionuclides. Most radionuclides with half-lives longer than approximately 1x10{sup 3} years can be quantitatively detected on ICP-MS instruments that have an electrothermal vaporization unit for the injection of sample aliquants. Radionuclides with half-lives greater than approximately 1x10{sup 4} years can be measured routinely with greater sensitivity and more quickly by ICP-MS than by radiation counting. Examples from the literature of applying ICP-MS to radionuclides are the bioassay of uranium in urine, measurement of {sup 237}Np in soil and silt, and analysis for {sup 99}Tc in sea water, seaweed, and marine sediment. This paper discusses the instrumentation, advantages and limitations, and present and potential applications of ICP-MS for radionuclide measurements.

  11. Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry

    SciTech Connect

    Ebert, Christopher Hysjulien

    2012-01-01

    This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows that MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.

  12. Determination of metals in Brazilian soils by inductively coupled plasma mass spectrometry.

    PubMed

    de Carvalho, Rui M; dos Santos, Jéssica A; Silva, Jessee A S; do Prado, Thiago G; da Fonseca, Adriel Ferreira; Chaves, Eduardo S; Frescura, Vera L A

    2015-08-01

    The concentration of metals in Brazilian soil under no-tillage (NT) and an area under native vegetation (NV) was determined by inductively coupled plasma mass spectrometry. The applied method was based on microwave-assisted acid digestion using HNO3, HCl, H2O2, and HF. The accuracy of the method was evaluated by analyzing two certified reference materials (BCR-142 and RS-3). The relative standard deviation for all target elements was below 8% indicating an adequate precision and the limit of detection ranged from 0.03 μg g(-1) (Cd) to 24.0 μg g(-1) (Fe). The concentrations of Al, As, Ba, Cd, Cu, Fe, Mg, Mn, Ni, Pb, Sr, and Zn in the different layers (0-10, 10-20, 20-40, and 40-60 cm) were determined in two types of soils, located in Paraná State in Brazil. The soil layers analysis revealed a different behavior of metals concentrations in soil samples under NT and NV. The obtained results showed a clear impact of anthropogenic action with respect to specific metals due to many years of uncontrolled application rates of limestone and phosphate fertilizers.

  13. [Matrix effects in inductively coupled plasma mass spectrometry by use of organic solvents].

    PubMed

    Cao, S; Chen, H; Zeng, X

    2000-08-01

    Matrix effects arising from ethanol, propanol, glycerol, acetic acid, ethylenediamine and triethanolamine in inductively coupled plasma mass spectrometry have been studied. Addition of ethanol, propanol, glycerol, acetic acid, ethylenediamine and triethanolamine into solution has an enhancement effect on the signal intensity of analyte with ionization potential between 9 and 11 eV. The ethylenediamine and triethanolamine have higher enhancement effect on the signal intensity of Hg than that of ethanol, propanol, glycerol and acetic acid. Addition of ethylenediamine and triethanolamine into solution has a suppression effect on the signal intensity of Pb and Sr. The mechanism of the enhancement or suppression was investigated. The signal enhancement of Hg in the presence of ethylenediamine and triethanolamine is not caused by improved degree of ionization of Hg and nebulization efficiency. The suppression effects of Pb and Sr in the presence of ethylenediamine and triethanolamine are due to decrease of atomization efficiency of these elements. A method for the determination of Hg in the biological standard samples by ICP-MS was developed.

  14. Pulsed microdischarge with inductively coupled plasma mass spectrometry for elemental analysis on solid metal samples.

    PubMed

    Li, Weifeng; Yin, Zhibin; Cheng, Xiaoling; Hang, Wei; Li, Jianfeng; Huang, Benli

    2015-05-01

    Pulsed microdischarge employed as source for direct solid analysis was investigated in N2 environment at atmospheric pressure. Compared with direct current (DC) microdischarge, it exhibits advantages with respect to the ablation and emission of the sample. Comprehensive evidence, including voltage-current relationship, current density (j), and electron density (ne), suggests that pulsed microdischarge is in the arc regime while DC microdischarge belongs to glow. Capability in ablating metal samples demonstrates that pulsed microdischarge is a viable option for direct solid sampling because of the enhanced instantaneous energy. Using optical spectrometer, only common emission lines of N2 can be acquired in DC mode, whereas primary atomic and ionic lines of the sample are obtained in the case of pulsed mode. Calculations show a significant difference in N2 vibrational temperatures between DC and pulsed microdischarge. Combined with inductively coupled plasma mass spectrometry (ICPMS), pulsed microdischarge exhibits much better performances in calibration linearity and limits of detection (LOD) than those of DC discharge in direct analysis of samples of different matrices. To improve transmission efficiency, a mixture of Ar and N2 was employed as discharge gas as well as carrier gas in follow-up experiments, facilitating that LODs of most elements reached ng/g. PMID:25851038

  15. Determination of metals in marine species by microwave digestion and inductively coupled plasma mass spectrometry analysis

    NASA Astrophysics Data System (ADS)

    Yang, Karl X.; Swami, Kamal

    2007-10-01

    A microwave digestion method suitable for determination of multiple elements in marine species was developed, with the use of cold vapor atomic spectrometry for the detection of Hg, and inductively coupled plasma mass spectrometry for all of the other elements. An optimized reagent mixture composed of 2 ml of HNO 3, 2 ml of H 2O 2 and 0.3 ml of HF used in microwave digestion of about 0.15 g (dry weight) of sample was found to give the best overall recoveries of metals in two standard reference materials. In the oyster tissue standard reference material (SRM 1566b), recoveries of Na, Al, K, V, Co, Zn, Se, Sr, Ag, Cd, Ni, and Pb were between 90% and 110%; Mg, Mn, Fe, Cu, As, and Ba recoveries were between 85% and 90%; Hg recovery was 81%; and Ca recovery was 64%. In a dogfish certified reference material (DORM-2), the recoveries of Al, Cr, Mn, Se, and Hg were between 90% and 110%; Ni, Cu, Zn, and As recoveries were about 85%; and Fe recovery was 112%. Method detection limits of the elements were established. Metal concentrations in flounder, scup, and blue crab samples collected from coastal locations around Long Island and in the Hudson River estuary were determined.

  16. Inductively-coupled plasma mass spectrometry in proteomics, metabolomics and metallomics studies.

    PubMed

    Mounicou, Sandra; Szpunar, Joanna; Lobinski, Ryszard

    2010-01-01

    The potential of inductively-coupled plasma mass spectrometry (ICP-MS) and its complementarity to soft- ionization MS techniques are discussed in the context of the analysis for biomolecules. ICP-MS offers detection limits in the attomolar range, regardless of the molecular environment of the target element. The sensitivity is hardly affected by the sample matrix, chromatographic mobile phase, or co-eluted compounds. The abundance sensitivity over six decades and the linear dynamic range over nine decades make simultaneous multi-isotopic analysis routinely possible. The manuscript discusses the state-of-the-art of ICP-MS for the detection of proteins in gel electrophoresis and of peptides in 2D high-performance liquid chromatography. The possibilities of quantification to the degree of some post-translational modifications are highlighted. Attention is also paid to the role of ICP-MS in protein quantification via metal-coded labeling and to the use of differentially-labeled antibodies for the multiplexed biomarker analysis. The key role of ICP-MS in the emerging area of metallomics is briefly discussed.

  17. Depleted uranium analysis in blood by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Todorov, T.I.; Xu, H.; Ejnik, J.W.; Mullick, F.G.; Squibb, K.; McDiarmid, M.A.; Centeno, J.A.

    2009-01-01

    In this study we report depleted uranium (DU) analysis in whole blood samples. Internal exposure to DU causes increased uranium levels as well as change in the uranium isotopic composition in blood specimen. For identification of DU exposure we used the 235U/238U ratio in blood samples, which ranges from 0.00725 for natural uranium to 0.002 for depleted uranium. Uranium quantification and isotopic composition analysis were performed by inductively coupled plasma mass spectrometry. For method validation we used eight spiked blood samples with known uranium concentrations and isotopic composition. The detection limit for quantification was determined to be 4 ng L-1 uranium in whole blood. The data reproduced within 1-5% RSD and an accuracy of 1-4%. In order to achieve a 235U/238U ratio range of 0.00698-0.00752% with 99.7% confidence limit a minimum whole blood uranium concentration of 60 ng L??1 was required. An additional 10 samples from a cohort of veterans exposed to DU in Gulf War I were analyzed with no knowledge of their medical history. The measured 235U/ 238U ratios in the blood samples were used to identify the presence or absence of DU exposure within this patient group. ?? 2009 The Royal Society of Chemistry.

  18. Using inductively coupled plasma-mass spectrometry for calibration transfer between environmental CRMs.

    PubMed

    Turk, G C; Yu, L L; Salit, M L; Guthrie, W F

    2001-06-01

    Multielement analyses of environmental reference materials have been performed using existing certified reference materials (CRMs) as calibration standards for inductively coupled plasma-mass spectrometry. The analyses have been performed using a high-performance methodology that results in comparison measurement uncertainties that are significantly less than the uncertainties of the certified values of the calibration CRM. Consequently, the determined values have uncertainties that are very nearly equivalent to the uncertainties of the calibration CRM. Several uses of this calibration transfer are proposed, including, re-certification measurements of replacement CRMs, establishing traceability of one CRM to another, and demonstrating the equivalence of two CRMs. RM 8704, a river sediment, was analyzed using SRM 2704, Buffalo River Sediment, as the calibration standard. SRM 1632c, Trace Elements in Bituminous Coal, which is a replacement for SRM 1632b, was analyzed using SRM 1632b as the standard. SRM 1635, Trace Elements in Subbituminous Coal, was also analyzed using SRM 1632b as the standard.

  19. Laser ablation inductively coupled plasma mass spectrometry imaging of metals in experimental and clinical Wilson's disease.

    PubMed

    Boaru, Sorina Georgiana; Merle, Uta; Uerlings, Ricarda; Zimmermann, Astrid; Flechtenmacher, Christa; Willheim, Claudia; Eder, Elisabeth; Ferenci, Peter; Stremmel, Wolfgang; Weiskirchen, Ralf

    2015-04-01

    Wilson's disease is an autosomal recessive disorder in which the liver does not properly release copper into bile, resulting in prominent copper accumulation in various tissues. Affected patients suffer from hepatic disorders and severe neurological defects. Experimental studies in mutant mice in which the copper-transporting ATPase gene (Atp7b) is disrupted revealed a drastic, time-dependent accumulation of hepatic copper that is accompanied by formation of regenerative nodes resembling cirrhosis. Therefore, these mice represent an excellent exploratory model for Wilson's disease. However, the precise time course in hepatic copper accumulation and its impact on other trace metals within the liver is yet poorly understood. We have recently established novel laser ablation inductively coupled plasma mass spectrometry protocols allowing quantitative metal imaging in human and murine liver tissue with high sensitivity, spatial resolution, specificity and quantification ability. By use of these techniques, we here aimed to comparatively analyse hepatic metal content in wild-type and Atp7b deficient mice during ageing. We demonstrate that the age-dependent accumulation of hepatic copper is strictly associated with a simultaneous increase in iron and zinc, while the intrahepatic concentration and distribution of other metals or metalloids is not affected. The same findings were obtained in well-defined human liver samples that were obtained from patients suffering from Wilson's disease. We conclude that in Wilson's disease the imbalances of hepatic copper during ageing are closely correlated with alterations in intrahepatic iron and zinc content.

  20. Arsenic speciation in soil using high performance liquid chromatography/inductively coupled plasma/mass spectrometry

    SciTech Connect

    Bass, D.A.; Yaeger, J.S.; Parish, K.J.; Crain, J.S.; Kiely, J.T.; Gowdy, M.J.; Mohrman, G.B.; Besmer, M.G.

    1996-08-01

    A method has been developed to identify and quantify As(III), As(V), and organoarsenic compounds in soil samples from the Rocky Mountain Arsenal (RMA) by high performance liquid chromatography/inductively coupled plasma/mass spectrometry (HPLC/ICP/MS). The soils were extracted using tetrabutylammonium hydroxide (TBAH) and sonication. The percentages of As(III), As(V), and organoarsenic species extracted from soil samples were 30, 50, and 100 respectively. The arsenic species were not altered during the extraction process. They were separated by reversed-phase, ion-pairing, HPLC using a microbore Inertsil-ODS{trademark} column. The HPLC column effluent was introduced into an ICP/MS system using a direct injection nebulizer (DIN). Detection limits of less than 1 pg were readily obtained for each arsenic species. Internal standards are recommended to increase accuracy and precision. Soil samples spiked with arsenic oxide, sodium arsenate, dimethylarsinic acid (DMAA), and chlorovinyl arsenious acid (CVAA) were extracted, identified and quantified with the HPLC/ICP/MS system. The soil samples were analyzed in support of the analytical needs of a thermal desorption treatability study being conducted at the RMA.

  1. Determination of iodine in seafood by inductively coupled plasma/mass spectrometry.

    PubMed

    Julshamn, K; Dahl, L; Eckhoff, K

    2001-01-01

    A method was developed for determination of total iodine content in different standard reference materials (SRMs) and seafood products by inductively coupled plasma/mass spectrometry (ICP/MS). If iodine is present as iodide and nitric acid is used in the wet digestion system, the observed signal is not stable when iodine is measured by ICP/MS at m/z 127. To stabilize the iodine signal, 3% ammonia solution (1 + 1, v/v) was added to the digest. The limit of quantitation of the method, defined as 6 times the standard deviation in the blank solution (n = 20) was estimated to be 15 mg/kg (using 0.2 g dry mass and a dilution factor of 50). The precision, expressed as repeatability of the iodine concentration, varied between 3.2 and 12% in SRMs, with concentrations of 4.70-0.17 mg/kg dry matter. The described method was compared with a method using tetramethylammonium hydroxide extraction. Both methods showed good precision and trueness by analyses of SRMs. The 2 methods were used to determine iodine in seafood from the Barents Sea, the Norwegian Sea, and the North Sea. The results showed great variation between different fish species as well as between individuals within a species. The lowest values of iodine were recorded in muscle of ling (Molva molva) with a mean of 0.07 mg/kg fresh weight and a variation between 0.03 and 0.11 mg/kg fresh weight. The highest values were found in cod (Gadus morhua) from the Barents Sea, with a mean of 2.5 mg/kg and a variation between 0.7 and 12.7 mg/kg fresh weight.

  2. Enhancement of ion transmission and reduction of background and interferences in inductively coupled plasma mass spectrometry

    SciTech Connect

    Hu, Ke

    1992-06-09

    An inductively coupled plasma - mass spectrometer (ICP-MS) (four stages of differential pumping) is described. The large sampling orifice (1.31 mm dia.) improves signals for metal ions and resists plugging. The ion lens deflects ions off center and then back on center into the differential pumping orifice; there is no photon stop in the center. Ion trajectories calculations SIMION show that only those ions that leave the skimmer on center are transmitted, whereas most other lenses used in ICP-MS transmit only ions that leave the skimmer off axis. Background with the Daly detector is 4 counts s{sup {minus}1}. This ICP-MS yields low levels of many troublesome polyatomic ions. Signals from refractory metal oxide ions are about 1% of the corresponding metal ion signals. Grounding the first electrode of the ion lens reduces matrix effects to {approx_lt} 20% loss in signal for Co{sup +}, Y{sup +} or Cs{sup +} in presence of 10 mM Sr, Tm or Pb. This latter lens setting causes only 30% loss in sensitivity compared to biassing the first lens. Matrix effects can also be mitigated by re-adjusting the voltage on the first lens with matrix present. Floating the metal cones at various potentials can improve the ion transmission by a factor of at least four to six. Also, floating the cones extends the upper end of linearity. Net result is more sensitivity and higher ion beam intensity than with a grounded skimmer and sampler. Furthermore, mass discrimination can be reduced.

  3. Enhancement of ion transmission and reduction of background and interferences in inductively coupled plasma mass spectrometry

    SciTech Connect

    Hu, Ke.

    1992-06-09

    An inductively coupled plasma - mass spectrometer (ICP-MS) (four stages of differential pumping) is described. The large sampling orifice (1.31 mm dia.) improves signals for metal ions and resists plugging. The ion lens deflects ions off center and then back on center into the differential pumping orifice; there is no photon stop in the center. Ion trajectories calculations SIMION show that only those ions that leave the skimmer on center are transmitted, whereas most other lenses used in ICP-MS transmit only ions that leave the skimmer off axis. Background with the Daly detector is 4 counts s{sup {minus}1}. This ICP-MS yields low levels of many troublesome polyatomic ions. Signals from refractory metal oxide ions are about 1% of the corresponding metal ion signals. Grounding the first electrode of the ion lens reduces matrix effects to {approx lt} 20% loss in signal for Co{sup +}, Y{sup +} or Cs{sup +} in presence of 10 mM Sr, Tm or Pb. This latter lens setting causes only 30% loss in sensitivity compared to biassing the first lens. Matrix effects can also be mitigated by re-adjusting the voltage on the first lens with matrix present. Floating the metal cones at various potentials can improve the ion transmission by a factor of at least four to six. Also, floating the cones extends the upper end of linearity. Net result is more sensitivity and higher ion beam intensity than with a grounded skimmer and sampler. Furthermore, mass discrimination can be reduced.

  4. Multi-Collector Inductively Coupled Plasma Mass Spectrometer – Operational Performance Report

    SciTech Connect

    Matthew Watrous; Anthony Appelhans; Robert Hague; John Olson; Tracy Houghton

    2013-06-01

    The INL made an assessment of the commercially available inductively coupled plasma mass spectrometers (ICPMS) for actinide analysis; emphasizing low detection limits for plutonium. INL scientists subsequently determined if plutonium was present on a swipe, at a 10 million atom decision level. This report describes the evaluation of ICPMS instruments and the operational testing of a new process for the dissolution, separation and analysis via ICPMS of swipes for plutonium and uranium. The swipe dissolution, plutonium and uranium isolation, separation and purification are wet chemistry methods following established procedures. The ICPMS is a commercially available multi-collector magnetic sector mass spectrometer that utilizes five ion counting detectors operating simultaneously. The instrument includes a sample introduction system allowing for sample volumes of < 1 mL to be reproducibly injected into the instrument with minimal waste of the sample solution, while maximizing the useable signal. The performance of the instrument was measured using SRM 996 (244Pu spike) at concentrations of 12 parts per quadrillion (ppq, fg/mL) and with SRM 4350B Columbia River Sediment samples spiked onto swipes at the 10 million atom level. The measured limit of detection (LOD, defined as 3s) for 239Pu is 310,000 atoms based upon the instrument blank data. The limit of quantification (LOQ defined as 10 s) for 239Pu is 105,000 atoms. The measured limit of detection for 239Pu from the SRM 4350B spiked onto a swipe was 2.7 million atoms with the limit of quantification being 9.0 million atoms.

  5. Speciation of arsenic in marine food (Anemonia sulcata) by liquid chromatography coupled to inductively coupled plasma mass spectrometry and organic mass spectrometry.

    PubMed

    Contreras-Acuña, M; García-Barrera, T; García-Sevillano, M A; Gómez-Ariza, J L

    2013-03-22

    Arsenic species have been investigated in Anemonia sulcata, which is frequently consumed food staple in Spain battered in wheat flour and fried with olive oil. Speciation in tissue extracts was carried out by anion/cation exchange chromatography with inductively coupled plasma mass spectrometry (HPLC-(AEC/CEC)-ICP-MS). Three methods for the extraction of arsenic species were investigated (ultrasonic bath, ultrasonic probe and focused microwave) and the optimal one was applied. Arsenic speciation was carried out in raw and cooked anemone and the dominant species are dimethylarsinic acid (DMA(V)) followed by arsenobetaine (AB), As(V), monomethylarsonic acid (MA(V)), tetramethylarsonium ion (TETRA) and trimethylarsine oxide (TMAO). In addition, arsenocholine (AsC), glyceryl phosphorylarsenocholine (GPAsC) and dimethylarsinothioic acid (DMAS) were identified by liquid chromatography coupled to triple quadrupole mass spectrometry (HPLC-MS). These results are interesting since GPAsC has been previously reported in marine organisms after experimental exposure to AsC, but not in natural samples. In addition, this paper reports for the first time the identification of DMAS in marine food.

  6. Speciation of arsenic in marine food (Anemonia sulcata) by liquid chromatography coupled to inductively coupled plasma mass spectrometry and organic mass spectrometry.

    PubMed

    Contreras-Acuña, M; García-Barrera, T; García-Sevillano, M A; Gómez-Ariza, J L

    2013-03-22

    Arsenic species have been investigated in Anemonia sulcata, which is frequently consumed food staple in Spain battered in wheat flour and fried with olive oil. Speciation in tissue extracts was carried out by anion/cation exchange chromatography with inductively coupled plasma mass spectrometry (HPLC-(AEC/CEC)-ICP-MS). Three methods for the extraction of arsenic species were investigated (ultrasonic bath, ultrasonic probe and focused microwave) and the optimal one was applied. Arsenic speciation was carried out in raw and cooked anemone and the dominant species are dimethylarsinic acid (DMA(V)) followed by arsenobetaine (AB), As(V), monomethylarsonic acid (MA(V)), tetramethylarsonium ion (TETRA) and trimethylarsine oxide (TMAO). In addition, arsenocholine (AsC), glyceryl phosphorylarsenocholine (GPAsC) and dimethylarsinothioic acid (DMAS) were identified by liquid chromatography coupled to triple quadrupole mass spectrometry (HPLC-MS). These results are interesting since GPAsC has been previously reported in marine organisms after experimental exposure to AsC, but not in natural samples. In addition, this paper reports for the first time the identification of DMAS in marine food. PMID:23422896

  7. Investigations into the origins of polyatomic ions in inductively coupled plasma-mass spectrometry

    SciTech Connect

    McIntyre, Sally M.

    2010-01-01

    An inductively coupled plasma-mass spectrometer (ICP-MS) is an elemental analytical instrument capable of determining nearly all elements in the periodic table at limits of detection in the parts per quadrillion and with a linear analytical range over 8-10 orders of magnitude. Three concentric quartz tubes make up the plasma torch. Argon gas is spiraled through the outer tube and generates the plasma powered by a looped load coil operating at 27.1 or 40.6 MHz. The argon flow of the middle channel is used to keep the plasma above the innermost tube through which solid or aqueous sample is carried in a third argon stream. A sample is progressively desolvated, atomized and ionized. The torch is operated at atmospheric pressure. To reach the reduced pressures of mass spectrometers, ions are extracted through a series of two, approximately one millimeter wide, circular apertures set in water cooled metal cones. The space between the cones is evacuated to approximately one torr. The space behind the second cone is pumped down to, or near to, the pressure needed for the mass spectrometer (MS). The first cone, called the sampler, is placed directly in the plasma plume and its position is adjusted to the point where atomic ions are most abundant. The hot plasma gas expands through the sampler orifice and in this expansion is placed the second cone, called the skimmer. After the skimmer traditional MS designs are employed, i.e. quadrupoles, magnetic sectors, time-of-flight. ICP-MS is the leading trace element analysis technique. One of its weaknesses are polyatomic ions. This dissertation has added to the fundamental understanding of some of these polyatomic ions, their origins and behavior. Although mainly continuing the work of others, certain novel approaches have been introduced here. Chapter 2 includes the first reported efforts to include high temperature corrections to the partition functions of the polyatomic ions in ICP-MS. This and other objections to preceeding

  8. Fast quantification of endogenous carbohydrates in plasma using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Zhu, Bangjie; Liu, Feng; Li, Xituo; Wang, Yan; Gu, Xue; Dai, Jieyu; Wang, Guiming; Cheng, Yu; Yan, Chao

    2015-01-01

    Endogenous carbohydrates in biosamples are frequently highlighted as the most differential metabolites in many metabolomics studies. A simple, fast, simultaneous quantitative method for 16 endogenous carbohydrates in plasma has been developed using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry. In order to quantify 16 endogenous carbohydrates in plasma, various conditions, including columns, chromatographic conditions, mass spectrometry conditions, and plasma preparation methods, were investigated. Different conditions in this quantified analysis were performed and optimized. The reproducibility, precision, recovery, matrix effect, and stability of the method were verified. The results indicated that a methanol/acetonitrile (50:50, v/v) mixture could effectively and reproducibly precipitate rat plasma proteins. Cold organic solvents coupled with vortex for 1 min and incubated at -20°C for 20 min were the most optimal conditions for protein precipitation and extraction. The results, according to the linearity, recovery, precision, matrix effect, and stability, showed that the method was satisfactory in the quantification of endogenous carbohydrates in rat plasma. The quantified analysis of endogenous carbohydrates in rat plasma performed excellently in terms of sensitivity, high throughput, and simple sample preparation, which met the requirement of quantification in specific expanded metabolomic studies after the global metabolic profiling research.

  9. Determination of minor elements in steelmaking flue dusts using laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Coedo, A G; Padilla, I; Dorado, M T

    2005-07-15

    Element determination in solid waste products from the steel industry usually involves the time-consuming step of preparing a solution of the solid. Laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the analysis of Cr, Ni, Cu, As, Cd and Sn, elements of importance from the point of view of their impact on the environment, in electric arc furnace flue dust (EAFD). A simple method of sample preparation as pressed pellets using a mixture of cellulose and paraffin as binder material was applied. Calibration standards were prepared spiking multielement solution standards to a 1:1 ZnO+Fe(2)O(3) synthetic matrix. The wet powder was dried and mechanically homogenised. Quantitative analysis were based on external calibration using a set of matrix matched calibration standards with Rh as a internal standard. Results obtained using only one-point for calibration without matrix matched, needing less time for standardization and data processing, are also presented. Data are calculated for flue dust reference materials: CRM 876-1 (EAFD), AG-6203 (EAFD), AG-6201 (cupola dust) and AG-SX3705 (coke ashes), and for two representative electrical arc furnace flue dusts samples from Spanish steelmaking companies: MS-1 and MS-2. For the reference materials, an acceptable agreement with certificate values was achieved, and the results for the MS samples matched with those obtained from conventional nebulization solutions (CN). The analytical precision was found to be better than 7% R.S.D. both within a single pellet and between several pellets of the same sample for all the elements.

  10. Iodine determination in food samples using inductively coupled plasma isotope dilution mass spectrometry.

    PubMed

    Rädlinger, G; Heumann, K G

    1998-06-01

    Two different sample treatment methods are used in connection with inductively coupled plasma isotope dilution mass spectrometry for accurate and precise determinations of iodine traces in food samples. 129I-enriched iodate is applied as a spike compound for the isotope dilution step. Extraction of iodine by tetramethylammonium hydroxide (TMAH) solution at high temperatures in a closed vessel is one of the sample treatment methods. The other one is a complete decomposition of the sample with a mixture of perchloric acid and nitric acid using microwave assistance. By analyzing different certified reference materials (three milk powders with different iodine levels, BCR CRM 63, 150, and 151; bovine liver BCR CRM 185), the accuracy of ICP-IDMS with both sample treatment methods could be demonstrated. The relative standard deviation was typically in the range of 0.6-2.8% for iodine concentrations between 0.1 microgram g-1 and 5 micrograms g-1. The detection limit was 8 ng g-1 using sample weights of 0.8 g. In a round robin test, using two different types of infant food samples, the results of the two ICP-IDMS methods and of an ICP-MS method without the isotope dilution technique, but applying the TMAH extraction procedure, agree very well with the mean of results of all participating laboratories also using ICP-MS/TMAH. However, the ICP-IDMS method is faster, more precise, widely independent of matrix effects, and, therefore, relatively accurate, which makes this method especially attractive for use as a routine method.

  11. Slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry for steelmaking flue dust analysis

    NASA Astrophysics Data System (ADS)

    Coedo, A. G.; Dorado, T.; Padilla, I.; Maibusch, R.; Kuss, H.-M.

    2000-02-01

    A commercial atomic absorption graphite furnace (AAGF), with a self-made adapter and valve system, was used as a slurry sampling cell for electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS). The system was applied to the determination of As, Sn, Sb, Se, Te, Bi, Cd, V, Ti and Mo in steelmaking flue dusts. Experimental conditions with respect to ETV and ICP-MS operating parameters were optimized. Compared to aqueous solutions, slurry samples were found to present better analyte transport. Microgram amounts of Rh were used to reduce the difference in analyte response in sensitivity for aqueous solutions of the tested analytes. No such increasing effect was observed for slurry samples and aqueous standards. An added quantity of Rh acting as modifier/carrier resulted in an increase for the same analytes in matrix-slurry solutions, even the addition of an extra Rh quantity has resulted in a decrease in the signals. The effect of Triton X-100 (used as a dispersant agent) on analyte intensity and precision was also studied. External calibration from aqueous standards spiked with 100 μg ml -1 Rh was performed to quantified 0.010 g/100 ml slurry samples. Results are presented for a certified reference electrical arc furnace flue dust (EAF): CRM-876-1 (Bureau of Analysis Samples Ltd., Cleveland, UK), a reference sample of coke ashes X-3705 (from AG der Dillinger Hüttenwerke, Germany), and a representative sample of EAF flue dust from a Spanish steelmaking company (CENIM-1). For the two reference materials an acceptable agreement with certificate values was achieved, and the results for the CENIM sample matched with those obtained from conventional nebulization solution.

  12. Acquisition of a High-resolution Inductively Coupled Plasma Mass Spectrometer for Cosmochemical and Geochemical Research

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.

    2004-01-01

    The primary goal of our research in this program is to develop new techniques for the analysis of volatile trace elements in very small samples using inductively coupled plasma mass spectrometry (ICP-MS) in preparation for samples returned by the Stardust mission. The instrument that will serve as the basis of our experiments is the ELEMENT2 high-resolution ICP-MS. We have spent the past year designing the laboratory to house this instrument as well as space to store and prepare samples returned by the Stardust mission. Unfortunately, the location that we had initially selected for the instrument turned out to be insufficient for our needs. This was determined almost eight months into the first year of our funding cycle, after extensive work including the production of engineering drawings. However, during this time the Lunar and Planetary Laboratory was selected to lead Phoenix, the first Mars Scout mission. As a result of this award LPL purchased a new, 50,000 square foot building. We have acquired 1400 square feet of laboratory space in this new facility. Four-hundred square feet will be used for a class-100 clean room. This area is designated for storage and preparation of extraterrestrial materials. The additional 1000 square feet will house the ELEMENT2 ICP-MS and peripheral devices. This is an enormous amount of space for this instrument, but it provides plenty of room for expansion in the future. The ICP-MS and the clean room facilities have been purchased. The instrument has been delivered. The startup time for this instrument is relatively short and we expect to be collecting our first data by mid-summer.

  13. Photochemical vapor generation of lead for inductively coupled plasma mass spectrometric detection

    NASA Astrophysics Data System (ADS)

    Duan, Hualing; Zhang, Ningning; Gong, Zhenbin; Li, Weifeng; Hang, Wei

    2016-06-01

    Photochemical vapor generation (PCVG) of lead was successfully achieved with a simplified and convenient system, in which only low molecular weight organic acid and a high-efficiency photochemical reactor were needed. The reactor was used to generate lead volatile species when a solution of lead containing a small amount of low molecular weight organic acid was pumped through. Several factors, including the concentration of acetic acid, the concentration of hydrochloride acid, and the irradiation time of UV light were optimized. Under the optimal conditions, including the addition of 0.90% (v/v) acetic acid and 0.03% (v/v) hydrochloride acid, and irradiation time of 28 s, intense and repeatable signal of lead volatile species was successfully obtained and identified with inductively coupled plasma mass spectrometry (ICPMS). In addition, the effects from inorganic anions and transition metal ions, including Cl-, NO3-, SO42 -, Cu2 +, Fe3 +, Co2 + and Ni2 +, were investigated, which suggests that their suppression to the PCVG of lead was in the order of Cl- < SO42 - < NO3- for anions and Ni2 +, Co2 + < Fe3 + < Cu2 + for transition metal ions. Under optimized conditions, relative standard derivation (RSD) of 4.4% was achieved from replicate measurements (n = 5) of a standard solution of 0.1 μg L- 1 lead. And, the limit of quantitation (LOQ, 10σ) of 0.012 μg L- 1 lead was obtained using this method and the method blank could be easily controlled down to 0.023 μg L- 1. To validate applicability of this method, it was also employed for the determination of lead in tap water, rain water and lake water.

  14. Documenting utility of paddlefish otoliths for quantification of metals using inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Long, James M.; Schaffler, James J.

    2013-01-01

    RATIONALE The otoliths of the inner ear of fishes record the environment of their surrounding water throughout their life. For paddlefish (Polyodon spathula), otoliths have not been routinely used by scientists since their detriments were outlined in the early 1940s. We sought to determine if paddlefish otoliths were useful for resolving elemental information contained within. METHODS Adult paddlefish were collected from two wild, self-sustaining populations in Oklahoma reservoirs in the Arkansas River basin. Juveniles were obtained from a hatchery in the Red River basin of Oklahoma. Otoliths were removed and laser ablation, inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify eight elements (Li, Mg, Mn, Rb, Sr, Y, Ba, and Pb) along the core and edge portions, which were analyzed for differences between otolith regions and among paddlefish sources. RESULTS Differences were found among samples for six of the eight elements examined. Otoliths from Red River basin paddlefish born in a hatchery had significantly lower amounts of Mg and Mn, but higher levels of Rb than otoliths from wild paddlefish in the Arkansas River basin. Concentrations of Y, Sr, and Ba were reduced on the edges of adult paddlefish from both reservoirs compared with the cores. CONCLUSIONS This research shows the utility of using an ICP-MS analysis of paddlefish otoliths. Future research that seeks to determine sources of paddlefish production, such as which reservoir tributaries are most important for reproduction or what proportion of the population is composed of wild versus hatchery-produced individuals, appears promising. Published in 2013. This article is a U.S. Government work and is in the public domain in the USA.

  15. Analysis of metal pollutants in the Houston Ship Channel by inductively coupled plasma/mass spectrometry.

    PubMed

    Saleh, M A; Wilson, B L

    1999-09-01

    Trace metal pollutants in the surface water of the Houston Ship Channel were determined using inductively coupled plasma/mass spectrometry (ICP/MS). Metal concentrations varied according to sampling sites. Barium, cobalt, chromium, molybdenum, silver, beryllium, antimony, lead, and mercury concentrations were relatively similar throughout the channel averaging 83.25, 0.55, 6. 31, 6.66, 0.02, 0.017, 3.61, 0.68, and 0.055 microg/L, respectively. Titanium, manganese, copper, zinc, nickel, and selenium concentrations were found to be higher at stations closer to the Galveston Bay (as the water is turning from relatively fresh water to sea water) with concentration ranges of 102.5-351.7, 0.3-25, 0. 3-25, 30-280, 16-77, 6.2-26.5, and 0.0-6.2 microg/L, respectively. Aluminum was found to be much higher at the Buffalo Bayou station (341 microg/L) followed by the San Jacinto station (104 microg/L) with an average of 42 microg/L in the other two stations. Vanadium was found to be unusually high at the Washburn Tunnel station (116 microg/L) and at much lower concentrations in the other three stations, averaging 6.5 microg/L. Iron was also higher at the Buffalo Bayou station (143 microg/L) but was absent at the Lynchburg Ferries station. Arsenic was not found at the Lynchburg and San Jacinto stations. However, arsenic had similar concentrations of 1. 983 and 1.835 microg/L at Buffalo Bayou and Washburn Tunnel, respectively. Cadmium was higher at the Lynchburg Ferries station (3. 3 microg/L) and ranged from 0.3 to 0.96 microg/L in the other locations. Thallium was not found in any of the stations.

  16. Ultracentrifugation and inductively coupled plasma mass spectrometry for metal-protein equilibrium studies

    NASA Astrophysics Data System (ADS)

    Arnquist, Isaac J.; Holcombe, James A.

    2012-10-01

    The coupling of separation by preparative ultracentrifugation and metal detection by inductively coupled plasma mass spectrometry (ICP-MS) has been explored for metal-protein equilibrium determinations. This study characterizes the stoichiometry as well as apparent (Kapp) and intrinsic (Kint) binding affinities of the metal-protein association for a model protein. In particular, the affinity of Cu2 + for the high affinity binding site in bovine serum albumin (BSA) is determined. Once equilibrium is established between Cu2 + and BSA, preparative ultracentrifugation moves the metalloprotein away from the meniscus, leaving unbound equilibrium copper in the protein free solution. Since the initial (total) concentrations of purified BSA and Cu2 + can be determined, the free copper concentration at equilibrium can also be determined by taking a small aliquot above the sedimenting boundary for analysis using ICP-MS. This analysis allows for the determination of free Cu2 + ion, which is identical to the equilibrium concentration prior to ultracentrifugation. From these data Kapp and Kint were determined at two different conditions, 100 mM Tris(hydroxymethyl)aminomethane (Tris) at pH 9.53 and pH 7.93. log Kapp values of 17.6 and 14.6 were determined at pH 9.53 and pH 7.93, respectively. Furthermore, pH-independent log Kint values of - 1.43 and - 1.04 were determined at pH 9.53 and 7.93, respectively. While the log Kint at pH 9.53 was in good agreement with literature values obtained from alternative methods, Kint at pH 7.93 was about 2.5 × larger than previously reported. BSA undergoes a structural rearrangement between pH 7-9, and the generally accepted pH-dependency of protein tertiary structure may be responsible for the variations in the "intrinsic" binding constant. The Cu-BSA binding affinity was also monitored in 100 mM Tris 0.1% sodium dodecyl sulfate (SDS) solution at pH 7.93 in order to determine the effect of a denaturant on metal binding. Results for both log

  17. Fractionation analysis of manganese in Turkish hazelnuts (Corylus avellana L.) by inductively coupled plasma-mass spectrometry.

    PubMed

    Erdemir, Umran Seven; Gucer, Seref

    2014-11-01

    In this study, an analytical fractionation scheme based on water, diethyl ether, n-hexane, and methanol extractions has been developed to identify manganese-bound fractions. Additionally, in vitro simulated gastric and intestinal digestion, n-octanol extraction, and activated carbon adsorption were used to interpret the manganese-bound structures in hazelnuts in terms of bioaccessibility. The total content of manganese in the samples was determined by inductively coupled plasma-mass spectrometry after microwave-assisted digestion, and additional validation was performed using atomic absorption spectroscopy. Water fractions were further evaluated by high-performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry for the identification of water-soluble manganese fractions in hazelnut samples. The limits of detection and quantification were 3.6 and 12.0 μg L(-1), respectively, based on peak height.

  18. Determination of arsenic in gold by flow injection inductively coupled plasma mass spectrometry with matrix removal by reductive precipitation

    NASA Astrophysics Data System (ADS)

    Becotte-Haigh, Paul; Tyson, Julian F.; Denoyer, Eric; Hinds, Michael W.

    1996-12-01

    Arsenic was determined in gold by flow injection hydride generation inductively coupled plasma-mass spectrometry following a batch mode reductive precipitation removal of the interfering gold matrix. A solution of potassium iodide, L-ascorbic acid, and hydrochloric acid was used as the reluctant. The recovery of gold by precipitation and filtration was 99 ± 3%. The detection limit for arsenic in gold was 55 ng g -1 in the solid. The concentration of arsenic that was determined in the Royal Canadian Mint gold sample FAU-10 was 29.7 μg g -1 in the solid; this value was indistinguishable, with 95% confidence, from values determined at the Royal Canadian Mint by graphite furnace atomic absorption spectrometry and by inductively coupled plasma-mass spectrometry. The standard deviation for four replicate determinations of the arsenic in FAU-10 was 0.972 μg g -1 in the solid.

  19. {sup 99}Tc bioassay by inductively coupled plasma mass spectrometry (ICP-MS)

    SciTech Connect

    Lewis, L.A.

    1998-05-01

    A means of analyzing {sup 99}Tc in urine by inductively coupled plasma mass spectrometry (ICP-MS) has been developed. Historically, {sup 99}Tc analysis was based on the radiometric detection of the 293 keV E{sub Max} beta decay product by liquid scintillation or gas flow proportional counting. In a urine matrix, the analysis of{sup 99}Tc is plagued with many difficulties using conventional radiometric methods. Difficulties originate during chemical separation due to the volatile nature of Tc{sub 2}O{sub 7} or during radiation detection due to color or chemical quenching. A separation scheme for {sup 99}Tc detection by ICP-MS is given and is proven to be a sensitive and robust analytical alternative. A comparison of methods using radiometric and mass quantitation of {sup 99}Tc has been conducted in water, artificial urine, and real urine matrices at activity levels between 700 and 2,200 dpm/L. Liquid scintillation results based on an external standard quench correction and a quench curve correction method are compared to results obtained by ICP-MS. Each method produced accurate results, however the precision of the ICP-MS results is superior to that of liquid scintillation results. Limits of detection (LOD) for ICP-MS and liquid scintillation detection are 14.67 and 203.4 dpm/L, respectively, in a real urine matrix. In order to determine the basis for the increased precision of the ICP-MS results, the detection sensitivity for each method is derived and measured. The detection sensitivity for the {sup 99}Tc isotope by ICP-MS is 2.175 x 10{sup {minus}7} {+-} 8.990 x 10{sup {minus}9} and by liquid scintillation is 7.434 x 10{sup {minus}14} {+-} 7.461 x 10{sup {minus}15}. A difference by seven orders of magnitude between the two detection systems allows ICP-MS samples to be analyzed for a period of 15 s compared to 3,600 s by liquid scintillation counting with a lower LOD.

  20. Multi-elemental analysis of aqueous geochemical samples by quadrupole inductively coupled plasma-mass spectrometry (ICP-MS)

    USGS Publications Warehouse

    Wolf, Ruth E.; Adams, Monique

    2015-01-01

    Typically, quadrupole inductively coupled plasma-mass spectrometry (ICP-MS) is used to determine as many as 57 major, minor, and trace elements in aqueous geochemical samples, including natural surface water and groundwater, acid mine drainage water, and extracts or leachates from geological samples. The sample solution is aspirated into the inductively coupled plasma (ICP) which is an electrodeless discharge of ionized argon gas at a temperature of approximately 6,000 degrees Celsius. The elements in the sample solution are subsequently volatilized, atomized, and ionized by the ICP. The ions generated are then focused and introduced into a quadrupole mass filter which only allows one mass to reach the detector at a given moment in time. As the settings of the mass analyzer change, subsequent masses are allowed to impact the detector. Although the typical quadrupole ICP-MS system is a sequential scanning instrument (determining each mass separately), the scan speed of modern instruments is on the order of several thousand masses per second. Consequently, typical total sample analysis times of 2–3 minutes are readily achievable for up to 57 elements.

  1. Measurement of low radioactivity background in a high voltage cable by high resolution inductively coupled plasma mass spectrometry

    SciTech Connect

    Vacri, M. L. di; Nisi, S.; Balata, M.

    2013-08-08

    The measurement of naturally occurring low level radioactivity background in a high voltage (HV) cable by high resolution inductively coupled plasma mass spectrometry (HR ICP MS) is presented in this work. The measurements were performed at the Chemistry Service of the Gran Sasso National Laboratory. The contributions to the radioactive background coming from the different components of the heterogeneous material were separated. Based on the mass fraction of the cable, the whole contamination was calculated. The HR ICP MS results were cross-checked by gamma ray spectroscopy analysis that was performed at the low background facility STELLA (Sub Terranean Low Level Assay) of the LNGS underground lab using HPGe detectors.

  2. Langmuir Probe and Mass Spectroscopic Measurements in Inductively Coupled CF4 Plasmas

    NASA Technical Reports Server (NTRS)

    Rao, M. V. V. S.; Sharma, Surendra; Cruden, B. A.; Meyyappan, M.

    2001-01-01

    Abstract Electron and ion energy distribution functions and other plasma parameters such as plasma potential (V(sub p)) , electron temperature (T(sub e)), and electron and ion number densities (n (sub e) and n(sub i)) in low pressure CF4 plasmas have been measured. The experiments were conducted in a GEC cell using an inductively coupled plasma (ICP) device powered by a 13.56 MHz radio-frequency (rf) power source. The measurements were made at 300 W of input rf power at 10, 30 and 50 mTorr gas pressures. Langmuir probe measurements suggest that n(sub e), n(sub i) and V(sub p) remain constant over 60% of the central electrode area, beyond which they decrease. Within the limits of experimental error (+/- 0.25 eV), T(sub e) remains nearly constant over the electrode area. T(sub e) and V(sub p) increase with a decrease in pressure. n(sub e) and n(sub i) are not affected as significantly as T(sub e) or V(sub p) by variation in the gas pressure. The electron energy distribution function (EEDF) measurements indicate a highly non-Maxwellian plasma. CF3+ is the most dominant ion product of the plasma, followed by CF2+ and CF+. The concentrations of CF2+ and CF+ are much larger than that is possible from direct electron impact ionization of the parent gas. The cross-section data suggest that the direct electron impact ionization of fragment neutrals and negative ion production by electron attachment may be responsible for increase of the minor ions.

  3. Determination of Rare Earth Elements in Green River Shale By Inductively Coupled Plasma Mass Spectrometry Using a Desolvating Nebulizer System

    NASA Astrophysics Data System (ADS)

    Smith, F.; Clarke, D.; Moody, S.

    2014-12-01

    In this work, inductively coupled plasma mass spectrometry (ICP-MS) is applied to a geological sample for the determination of rare earth elements (REEs) using a specialized nebulizer system. The low flow desolvating nebulizer has been shown to decrease metal oxide formation which leads to a reduction in mass spectral interferences. Traditional nebulizers and spray chambers may be suitable for similar sample types, but reduction of water vapor loading to the plasma can improve REE detection limits for quadrupole-based ICP-MS. The Green River formation holds the largest oil shale deposits in the world and understanding the elemental composition of these samples is important in its study. A certified reference material, USGS Green River Shale (SGR-1), was microwave digested prior to analysis, and recoveries of REEs compared to historical values are discussed.

  4. Quantification of artemisinin in human plasma using liquid chromatography coupled to tandem mass spectrometry

    PubMed Central

    Lindegardh, N.; Tarning, J.; Toi, P.V.; Hien, T.T.; Farrar, J.; Singhasivanon, P.; White, N.J.; Ashton, M.; Day, N.P.J.

    2009-01-01

    A liquid chromatographic tandem mass spectroscopy method for the quantification of artemisinin in human heparinised plasma has been developed and validated. The method uses Oasis HLB™ μ-elution solid phase extraction 96-well plates to facilitate a high throughput of 192 samples a day. Artesunate (internal standard) in a plasma–water solution was added to plasma (50 μL) before solid phase extraction. Artemisinin and its internal standard artesunate were analysed by liquid chromatography and MS/MS detection on a Hypersil Gold C18 (100 mm × 2.1 mm, 5 μm) column using a mobile phase containing acetonitrile–ammonium acetate 10 mM pH 3.5 (50:50, v/v) at a flow rate of 0.5 mL/min. The method has been validated according to published FDA guidelines and showed excellent performance. The within-day, between-day and total precisions expressed as R.S.D., were lower than 8% at all tested quality control levels including the upper and lower limit of quantification. The limit of detection was 0.257 ng/mL for artemisinin and the calibration range was 1.03–762 ng/mL using 50 μL plasma. The method was free from matrix effects as demonstrated both graphically and quantitatively. PMID:19162422

  5. Time-resolved inductively coupled plasma mass spectrometry measurements with individual, monodisperse drop sample introduction.

    PubMed

    Dziewatkoski, M P; Daniels, L B; Olesik, J W

    1996-04-01

    Individual ion clouds, each produced in the ICP from a single drop of sample, were monitored using time-resolved mass spectrometry and optical emission spectrometry simultaneously. The widths of the ion clouds in the plasma as a function of distance from the point of initial desolvated particle vaporization in the ICP were estimated. The Li(+) cloud width (full width at halfmaximum) varied from 85 to 272 μs at 3 and 10 mm from the apparent vaporization point, respectively. The Sr(+) cloud width varied from 97 to 142 μs at 5 and 10 mm from the apparent vaporization point, respectively. The delays between optical and mass spectrometry signals were used to measure gas velocities in the ICP. The velocity data could then be used to convert ion cloud peak widths in time to cloud sizes in the ICP. Li(+) clouds varied from 2.1 to 6.6 mm (full width at half-maximum) and Sr(+) clouds varied from 2.4 to 3.5 mm at the locations specified above. Diffusion coefficients were estimated from experimental data to be 88, 44, and 24 cm(2)/s for Li(+), Mg(+), and Sr(+), respectively. The flight time of ions from the sampling orifice of the mass spectrometer to the detector were mass dependent and varied from 13 to 21 μs for Mg(+) to 93 to 115 μs for Pb(+).

  6. Quantitative determination of mass-resolved ion densities in H{sub 2}-Ar inductively coupled radio frequency plasmas

    SciTech Connect

    Sode, M.; Schwarz-Selinger, T.; Jacob, W.

    2013-03-07

    Inductively coupled H{sub 2}-Ar plasmas are characterized by an energy-dispersive mass spectrometer (plasma monitor), a retarding field analyzer, optical emission spectroscopy, and a Langmuir probe. A procedure is presented that allows determining quantitatively the absolute ion densities of Ar{sup +}, H{sup +}, H{sub 2}{sup +}, H{sub 3}{sup +}, and ArH{sup +} from the plasma monitor raw signals. The calibration procedure considers the energy and mass-dependent transmission of the plasma monitor. It is shown that an additional diagnostic like a Langmuir probe or a retarding field analyzer is necessary to derive absolute fluxes with the plasma monitor. The conversion from fluxes into densities is based on a sheath and density profile model. Measurements were conducted for a total gas pressure of 1.0 Pa. For pure H{sub 2} plasmas, the dominant ion is H{sub 3}{sup +}. For mixed H{sub 2}-Ar plasmas, the ArH{sup +} molecular ion is the most dominant ion species in a wide parameter range. The electron density, n{sub e}, is around 3 Multiplication-Sign 10{sup 16} m{sup -3} and the electron temperature, T{sub e}, decreases from 5 to 3 eV with increasing Ar content. The dissociation degree was measured by actinometry. It is around 1.7% nearly independent on Ar content. The gas temperature, estimated by the rotational distribution of the Q-branch lines of the H{sub 2} Fulcher-{alpha} diagonal band (v Prime =v Double-Prime =2) is estimated to (540 {+-} 50) K.

  7. Improvements on high-precision measurement of bromine isotope ratios by multicollector inductively coupled plasma mass spectrometry.

    PubMed

    Wei, Hai-Zhen; Jiang, Shao-Yong; Zhu, Zhi-Yong; Yang, Tao; Yang, Jing-Hong; Yan, Xiong; Wu, He-Pin; Yang, Tang-Li

    2015-10-01

    A new, feasible procedure for high-precision bromine isotope analysis using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is described. With a combination of HR mass resolution mode and accurate optimization of the Zoom Optics parameters (Focus Quad: -1.30; Zoom Quad: 0.00), the challenging problem of the isobaric interferences ((40)Ar(38)ArH(+) and (40)Ar(40)ArH(+)) in the measurement of bromine isotopes ((79)Br(+), (81)Br(+)) has been effectively solved. The external reproducibility of the measured (81)Br/(79)Br ratios in the selected standard reference materials ranged from ±0.03‰ to ±0.14‰, which is superior to or equivalent to the best results from previous contributions. The effect of counter cations on the Br(+) signal intensity and the instrumental-induced mass bias was evaluated as the loss of HBr aerosol in nebulizer and potential diffusive isotope fractionations.

  8. Elemental labelling combined with liquid chromatography inductively coupled plasma mass spectrometry for quantification of biomolecules: A review

    PubMed Central

    Kretschy, Daniela; Koellensperger, Gunda; Hann, Stephan

    2012-01-01

    This article reviews novel quantification concepts where elemental labelling is combined with flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS) or liquid chromatography inductively coupled plasma mass spectrometry (LC–ICP-MS), and employed for quantification of biomolecules such as proteins, peptides and related molecules in challenging sample matrices. In the first sections an overview on general aspects of biomolecule quantification, as well as of labelling will be presented emphasizing the potential, which lies in such methodological approaches. In this context, ICP-MS as detector provides high sensitivity, selectivity and robustness in biological samples and offers the capability for multiplexing and isotope dilution mass spectrometry (IDMS). Fundamental methodology of elemental labelling will be highlighted and analytical, as well as biomedical applications will be presented. A special focus will lie on established applications underlining benefits and bottlenecks of such approaches for the implementation in real life analysis. Key research made in this field will be summarized and a perspective for future developments including sophisticated and innovative applications will given. PMID:23062431

  9. Optical emission spectroscopy studies of the influence of laser ablated mass on dry inductively coupled plasma conditions

    NASA Astrophysics Data System (ADS)

    Ciocan, A. C.; Mao, X. L.; Borisov, Oleg V.; Russo, R. E.

    1998-03-01

    The amount of ablated mass can influence the temperature and excitation characteristics of the inductively coupled plasma (ICP) and must be taken into account to ensure accurate chemical analysis. The ICP electron number density was investigated by using measurements of the Mg ionic to atomic resonant-line ratios during laser ablation of an aluminum matrix. The ICP excitation temperature was measured by using selected Fe lines during laser ablation of an iron matrix. A Nd:YAG laser (3 ns pulse duration) at 266 nm was used for these ablation-sampling studies. Laser energy, power density, and repetition rate were varied in order to change the quantity of ablated mass into the ICP. Over the range of laser operating conditions studied herein, the ICP was not significantly influenced by the quantity of solid sample. Therefore, analytical measurements can be performed accurately and fundamental studies of laser ablation processes (such as ablation mass roll-off, fractional vaporization) can be investigated using inductively coupled plasma-atomic emission spectroscopy (ICP-AES).

  10. Determination of 20 trace elements and arsenic species for a realgar-containing traditional Chinese medicine Niuhuang Jiedu tablets by direct inductively coupled plasma-mass spectrometry and high performance liquid chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Jin, Pengfei; Liang, Xiaoli; Xia, Lufeng; Jahouh, Farid; Wang, Rong; Kuang, Yongmei; Hu, Xin

    2016-01-01

    Niuhuang Jiedu tablet (NHJDT) is a realgar-containing traditional Chinese medicine. A direct inductively coupled plasma-mass spectrometry (ICP-MS) method for the simultaneous determination of 20 trace elements (Mg, K, Ca, Na, Fe, As, Zn, Sr, Ba, Cu, Mn, Ni, Pb, V, Cr, Se, Co, Mo, Cd, Hg) in NHJDT, as well as in water, gastric fluid and intestinal fluid was established. Meanwhile, a high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) method was developed for the determination of arsenite (As(III)), arsenate (As(V)), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and for the identification of arsenobetaine (AsB) and arsenocholine (AsC) in these extracts. Both methods were fully validated in the respect of linearity, sensitivity, precision, stability and accuracy. The reliability of the ICP-MS method was further evaluated using a certified standard reference material prepared from dried tomato leaves (NIST, SRM 1572a). The analysis showed that some manufacturers formulated lower amount of realgar than required in the Chinese Pharmacopoeia (ChP) in their preparations. In addition, almost same extraction profiles for total As and inorganic As were found in water and in gastrointestinal fluids, while higher extraction rates for other 19 elements were observed in gastrointestinal fluids. Our findings show that the toxicities of Hg, Cu, Cd and Pb in NHJDP are low, while the real As toxicity in NHJDT should be deeply investigated.

  11. Perspectives on Geospace Plasma Coupling

    SciTech Connect

    Baker, Daniel N.

    2011-01-04

    There are a large variety of fascinating and instructive aspects to examining the coupling of mass and energy from the solar wind into the Earth's magnetosphere. Past research has suggested that magnetic reconnection (in a fluid sense) on the day-side magnetopause plays the key role in controlling the energy coupling. However, both linear and nonlinear coupling processes involving kinetic effects have been suggested through various types of innovative data analysis. Analysis and modeling results have also indicated a prominent role for multi-scale processes of plasma coupling. Examples include evidence of control by solar wind turbulence in the coupling sequence and localized (finite gyroradius) effects in dayside plasma transport. In this paper we describe several solar wind-magnetosphere coupling scenarios. We particularly emphasize the study of solar wind driving of magnetospheric substorm, and related geomagnetic disturbances.

  12. Characterization of a Second-generation Focal-plane Camera Coupled to an Inductively Coupled Plasma Mattauch-Herzog Geometry Mass Spectrograph

    SciTech Connect

    Schilling, G D.; Andrade, Francisco J.; Barnes, James H.; Sperline, Roger P.; Denton, M BONNER.; Barinaga, Charles J.; Koppenaal, David W.; Hieftje, Gary M.

    2006-07-01

    A second-generation Faraday-strip array detector has been coupled to an inductively coupled plasma Mattauch- Herzog geometry mass spectrograph, thereby offering simultaneous acquisition of a range of mass-to-charge ratios. The second-generation device incorporates narrower, more closely spaced collectors than the earlier system. Furthermore, the new camera can acquire signal on all collectors at a frequency greater than 2 kHz and has the ability to independently adjust the gain level of each collector. Each collector can also be reset independently. With these improvements, limits of detection in the hundreds of picograms per liter for metals in solution have been obtained. Some additional features, such as a broader linear dynamic range (over 7 orders of magnitude), greater resolving power (up to 600), and improved isotope ratio accuracy were attained. In addition, isotope ratio precision as low as 0.018% RSD was achieved.

  13. Development and evaluation of high resolution quadrupole mass analyzer and an inductively coupled plasma-Mach disk

    SciTech Connect

    Amad, Ma'an Hazem

    1999-12-10

    By definition a plasma is an electrically conducting gaseous mixture containing a significant concentration of cations and electrons. The Inductively Coupled Plasma (ICP) is an electrodeless discharge in a gas at atmospheric pressure. This discharge is an excellent one for vaporizing, atomizing, and ionizing elements. The early development of the ICP began in 1942 by Babat and then by Reed in the early 1960s. This was then followed by the pioneering work of Fassel and coworkers in the late 1960s. Commercial ICP spectrometers were introduced in the mid 1970s. A major breakthrough in the area of ICP took place in the early 1980s when the ICP was shown to be an excellent ion source for mass spectrometry.

  14. Multielemental analysis of prehistoric animal teeth by laser-induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry

    SciTech Connect

    Galiova, Michaela; Kaiser, Jozef; Fortes, Francisco J.; Novotny, Karel; Malina, Radomir; Prokes, Lubomir; Hrdlicka, Ales; Vaculovic, Tomas; Nyvltova Fisakova, Miriam; Svoboda, Jiri; Kanicky, Viktor; Laserna, Javier J.

    2010-05-01

    Laser-induced breakdown spectroscopy (LIBS) and laser ablation (LA) inductively coupled plasma (ICP) mass spectrometry (MS) were utilized for microspatial analyses of a prehistoric bear (Ursus arctos) tooth dentine. The distribution of selected trace elements (Sr, Ba, Fe) was measured on a 26 mmx15 mm large and 3 mm thick transverse cross section of a canine tooth. The Na and Mg content together with the distribution of matrix elements (Ca, P) was also monitored within this area. The depth of the LIBS craters was measured with an optical profilometer. As shown, both LIBS and LA-ICP-MS can be successfully used for the fast, spatially resolved analysis of prehistoric teeth samples. In addition to microchemical analysis, the sample hardness was calculated using LIBS plasma ionic-to-atomic line intensity ratios of Mg (or Ca). To validate the sample hardness calculations, the hardness was also measured with a Vickers microhardness tester.

  15. Coupling of a gas chromatograph to a simultaneous-detection inductively coupled plasma mass spectrograph for speciation of organohalide and organometallic compounds

    SciTech Connect

    Barnes, James H.; Schilling, G; Sperline, Roger; Denton, M Bonner B.; Young, Erick T.; Barinaga, Charles J.; Koppenaal, David W.; Hieftje, Gary M.

    2004-06-01

    A gas chromatograph (GC) has been coupled to an inductively coupled plasma Mattauch-Herzog geometry mass spectrograph (ICP-MHMS) equipped with a novel detector array. In its current state of development the detector array, termed the focal plan camera (FPC), permits the simultaneous monitoring of up to 15 m/z values. A heated line was used to transfer the capillary-column effluent from the GC to the ICP torch, though due to instrument operating conditions, the transfer line was terminated 50 mm ahead of the ICP torch. Minimal tailing was observed, with the most severe effect seen for high-boiling analytes. With the coupling, absolute limits of detection are in the tens to hundreds of femtogram regime for organometallic species and in the single pictogram regime for halogenated hydrocarbons.

  16. Analysis of potassium iodate reduction in tissue homogenates using high performance liquid chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Cao, Xiaoxiao; Ma, Wei; Liu, Liejun; Xu, Jing; Wang, Haiyan; Li, Xiuwei; Wang, Jiangqing; Zhang, Jianhua; Wang, Zexi; Gu, Yunyou

    2015-10-01

    Potassium iodate (KIO3) and potassium iodide (KI) are the major salt iodization agents used worldwide. Unlike iodide (I(-)), iodate (IO3(-)) should be reduced to I(-) before it can be effectively used by the thyroid. In this study, we developed a new method for analyzing IO3(-) and I(-) in tissue homogenates using high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). We further applied the method to demonstrate the KIO3 reduction process by tissues in vitro. The effects of KIO3 on the total antioxidative activity (TAA) and reduced nicotinamide adenine dinucleotide phosphate (NADPH) were also investigated here. Finally, we found that IO3(-) can be reduced to I(-) by tissue homogenates and IO3(-) irreversibly decreases the antioxidant capability of tissues. Our studies suggest that KIO3 might have a big effect on the redox balance of tissue and would further result in oxidative stress of organisms.

  17. The potential of inductively coupled plasma mass spectrometry detection for high-performance liquid chromatography combined with accurate mass measurement of organic pharmaceutical compounds.

    PubMed

    Axelsson, B O; Jörnten-Karlsson, M; Michelsen, P; Abou-Shakra, F

    2001-01-01

    Quantification of unknown components in pharmaceutical, metabolic and environmental samples is an important but difficult task. Most commonly used detectors (like UV, RI or MS) require standards of each analyte for accurate quantification. Even if the chemical structure or elemental composition is known, the response from these detectors is difficult to predict with any accuracy. In inductively coupled plasma mass spectrometry (ICP-MS) compounds are atomised and ionised irrespective of the chemical structure(s) incorporating the element of interest. Liquid chromatography coupled with inductively coupled plasma mass spectrometry (LC/ICP-MS) has been shown to provide a generic detection for structurally non-correlated compounds with common elements like phosphorus and iodine. Detection of selected elements gives a better quantification of tested 'unknowns' than UV and organic mass spectrometric detection. It was shown that the ultrasonic nebuliser did not introduce any measurable dead volume and preserves the separation efficiency of the system. ICP-MS can be used in combination with many different mobile phases ranging from 0-100% organic modifier. The dynamic range was found to exceed 2.5 orders of magnitude. The application of LC/ICP-MS to pharmaceutical drugs and formulations has shown that impurities can be quantified below the 0.1 mol-% level.

  18. Calibration of laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for the quantitative analysis of solid samples

    SciTech Connect

    Leach, J.

    1999-02-12

    Inductively coupled plasma mass spectrometry (ICP-MS) has become the method of choice for elemental and isotopic analysis. Several factors contribute to its success. Modern instruments are capable of routine analysis at part per trillion levels with relative detection limits in part per quadrillion levels. Sensitivities in these instruments can be as high as 200 million counts per second per part per million with linear dynamic ranges up to eight orders of magnitude. With standards for only a few elements, rapid semiquantitative analysis of over 70 elements in an individual sample can be performed. Less than 20 years after its inception ICP-MS has shown to be applicable to several areas of science. These include geochemistry, the nuclear industry, environmental chemistry, clinical chemistry, the semiconductor industry, and forensic chemistry. In this introduction, the general attributes of ICP-MS will be discussed in terms of instrumentation and sample introduction. The advantages and disadvantages of current systems are presented. A detailed description of one method of sample introduction, laser ablation, is given. The paper also gives conclusions and suggestions for future work. Chapter 2, Quantitative analysis of solids by laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for calibration, has been removed for separate processing.

  19. Methyl mercury in nail clippings in relation to fish consumption analysis with gas chromatography coupled to inductively coupled plasma mass spectrometry: a first orientation.

    PubMed

    Krystek, Petra; Favaro, Paulo; Bode, Peter; Ritsema, Rob

    2012-08-15

    For the identification of human exposure to one of the most toxic compounds, which is methyl mercury (MeHg(+)), fingernail clippings were selected as the matrix of interest. Within this pilot study, six samples from different origins and from people with different food consumption patterns were chosen. Species-analysis of MeHg(+) was performed according to the following procedure: dissolution of the sample material in tetramethylammonium hydroxide (TMAH), derivatisation of MeHg(+) with sodium tetraethylborate (NaBEt(4)), extraction into iso-octane and measurement with gas chromatography hyphenated to inductively coupled plasma mass spectrometry (GC-ICPMS) for the quantification MeHg(+).

  20. Validation of determination of plasma metabolites derived from thyme bioactive compounds by improved liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Rubió, Laura; Serra, Aida; Macià, Alba; Borràs, Xenia; Romero, Maria-Paz; Motilva, Maria-José

    2012-09-15

    In the present study, a selective and sensitive method, based on microelution solid-phase extraction (μSPE) plate and ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) was validated and applied to determine the plasma metabolites of the bioactive compounds of thyme. For validation process, standards of the more representative components of the phenolic and monoterpene fractions of thyme were spiked in plasma samples and then the quality parameters of the method were studied. Extraction recoveries (%R) of the studied compounds were higher than 75%, and the matrix effect (%ME) was lower than 18%. The LODs ranged from 1 to 65 μg/L, except for the thymol sulfate metabolite, which was 240 μg/L. This method was then applied for the analysis of rat plasma obtained at different times, from 0 to 6h, after an acute intake of thyme extract (5 g/kg body weight). Different thyme metabolites were identified and were mainly derived from rosmarinic acid (coumaric acid sulfate, caffeic acid sulfate, ferulic acid sulfate, hydroxyphenylpropionic acid sulfate, dihydroxyphenylpropionic acid sulfate and hydroxybenzoic acid) and thymol (thymol sulfate and thymol glucuronide). The most abundant thyme metabolites generated were hydroxyphenylpropionic acid sulfate and thymol sulfate, their respective concentrations in plasma being 446 and 8464 μM 1h after the intake of the thyme extract.

  1. Validation of determination of plasma metabolites derived from thyme bioactive compounds by improved liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Rubió, Laura; Serra, Aida; Macià, Alba; Borràs, Xenia; Romero, Maria-Paz; Motilva, Maria-José

    2012-09-15

    In the present study, a selective and sensitive method, based on microelution solid-phase extraction (μSPE) plate and ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) was validated and applied to determine the plasma metabolites of the bioactive compounds of thyme. For validation process, standards of the more representative components of the phenolic and monoterpene fractions of thyme were spiked in plasma samples and then the quality parameters of the method were studied. Extraction recoveries (%R) of the studied compounds were higher than 75%, and the matrix effect (%ME) was lower than 18%. The LODs ranged from 1 to 65 μg/L, except for the thymol sulfate metabolite, which was 240 μg/L. This method was then applied for the analysis of rat plasma obtained at different times, from 0 to 6h, after an acute intake of thyme extract (5 g/kg body weight). Different thyme metabolites were identified and were mainly derived from rosmarinic acid (coumaric acid sulfate, caffeic acid sulfate, ferulic acid sulfate, hydroxyphenylpropionic acid sulfate, dihydroxyphenylpropionic acid sulfate and hydroxybenzoic acid) and thymol (thymol sulfate and thymol glucuronide). The most abundant thyme metabolites generated were hydroxyphenylpropionic acid sulfate and thymol sulfate, their respective concentrations in plasma being 446 and 8464 μM 1h after the intake of the thyme extract. PMID:22939267

  2. Measurement of femtogram quantities of protactinium in silicate rock samples by multicollector inductively coupled plasma mass spectrometry.

    PubMed

    Regelous, Marcel; Turner, Simon P; Elliott, Tim R; Rostami, Kia; Hawkesworth, Chris J

    2004-07-01

    We describe a new method for the chemical separation and analysis of Pa in silicate rock samples by isotope dilution. Our new technique has the following advantages over previous methods: (a) The initial separation of Pa from the rock matrix is carried out using anionic exchange resin and HCl-HF mixtures, avoiding the need to remove F(-) quantitatively from the sample solution prior to this step, (b) Efficient ionization of Pa is achieved using a multicollector inductively coupled plasma mass spectrometer, so that smaller sample sizes and shorter measurement times are required, compared to previous methods using thermal ionization mass spectrometry or alpha spectrometry. (c) Plasma ionization requires less efficient separation of the high field strength elements from Pa, thus reducing reagent volumes, blanks, and sample preparation times. Instrumental mass fractionation can be corrected for using admixed U of known isotopic composition. Using this method, Pa concentrations can be measured to a precision of approximately 0.5% and an accuracy of approximately 1% using only a few tens of femtograms of Pa.

  3. Measurement of femtogram quantities of protactinium in silicate rock samples by multicollector inductively coupled plasma mass spectrometry.

    PubMed

    Regelous, Marcel; Turner, Simon P; Elliott, Tim R; Rostami, Kia; Hawkesworth, Chris J

    2004-07-01

    We describe a new method for the chemical separation and analysis of Pa in silicate rock samples by isotope dilution. Our new technique has the following advantages over previous methods: (a) The initial separation of Pa from the rock matrix is carried out using anionic exchange resin and HCl-HF mixtures, avoiding the need to remove F(-) quantitatively from the sample solution prior to this step, (b) Efficient ionization of Pa is achieved using a multicollector inductively coupled plasma mass spectrometer, so that smaller sample sizes and shorter measurement times are required, compared to previous methods using thermal ionization mass spectrometry or alpha spectrometry. (c) Plasma ionization requires less efficient separation of the high field strength elements from Pa, thus reducing reagent volumes, blanks, and sample preparation times. Instrumental mass fractionation can be corrected for using admixed U of known isotopic composition. Using this method, Pa concentrations can be measured to a precision of approximately 0.5% and an accuracy of approximately 1% using only a few tens of femtograms of Pa. PMID:15228328

  4. Distance-of-Flight Mass Spectrometry with IonCCD Detection and an Inductively Coupled Plasma Source

    NASA Astrophysics Data System (ADS)

    Dennis, Elise A.; Ray, Steven J.; Enke, Christie G.; Gundlach-Graham, Alexander W.; Barinaga, Charles J.; Koppenaal, David W.; Hieftje, Gary M.

    2016-03-01

    Distance-of-flight mass spectrometry (DOFMS) is demonstrated for the first time with a commercially available ion detector—the IonCCD camera. Because DOFMS is a velocity-based MS technique that provides spatially dispersive, simultaneous mass spectrometry, a position-sensitive ion detector is needed for mass-spectral collection. The IonCCD camera is a 5.1-cm long, 1-D array that is capable of simultaneous, multichannel ion detection along a focal plane, which makes it an attractive option for DOFMS. In the current study, the IonCCD camera is evaluated for DOFMS with an inductively coupled plasma (ICP) ionization source over a relatively short field-free mass-separation distance of 25.3-30.4 cm. The combination of ICP-DOFMS and the IonCCD detector results in a mass-spectral resolving power (FWHM) of approximately 900 and isotope-ratio precision equivalent to or slightly better than current ICP-TOFMS systems. The measured isotope-ratio precision in % relative standard deviation (%RSD) was ≥0.008%RSD for nonconsecutive isotopes at 10-ppm concentration (near the ion-signal saturation point) and ≥0.02%RSD for all isotopes at 1-ppm. Results of DOFMS with the IonCCD camera are also compared with those of two previously characterized detection setups.

  5. Matrix effects of calcium on high-precision sulfur isotope measurement by multiple-collector inductively coupled plasma mass spectrometry.

    PubMed

    Liu, Chenhui; Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

    2016-05-01

    Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been successfully applied in the rapid and high-precision measurement for sulfur isotope ratios in recent years. During the measurement, the presence of matrix elements would affect the instrumental mass bias for sulfur and these matrix-induced effects have aroused a lot of researchers' interest. However, these studies have placed more weight on highlighting the necessity for their proposed correction protocols (e.g., chemical purification and matrix-matching) while less attention on the key property of the matrix element gives rise to the matrix effects. In this study, four groups of sulfate solutions, which have different concentrations of sulfur (0.05-0.60mM) but a constant sequence of atomic calcium/sulfur ratios (0.1-50), are investigated under wet (solution) and dry (desolvation) plasma conditions to make a detailed evaluation on the matrix effects from calcium on sulfur isotope measurement. Based on a series of comparative analyses, we indicated that, the matrix effects of calcium on both measured sulfur isotope ratios and detected (32)S signal intensities are dependent mainly on the absolute calcium concentration rather than its relative concentration ratio to sulfur (i.e., atomic calcium/sulfur ratio). Also, for the same group of samples, the matrix effects of calcium under dry plasma condition are much more significant than that of wet plasma. This research affords the opportunity to realize direct and relatively precise sulfur isotope measurement for evaporite gypsum, and further provides some suggestions with regard to sulfur isotope analytical protocols for sedimentary pore water.

  6. A simple method for methylmercury, inorganic mercury and ethylmercury determination in plasma samples by high performance liquid chromatography-cold-vapor-inductively coupled plasma mass spectrometry.

    PubMed

    de Souza, Samuel S; Campiglia, Andres Dobal; Barbosa, Fernando

    2013-01-25

    A simple and sensitive method with a fast sample preparation procedure is proposed for the determination of mercury species in plasma/serum. The method combines online high-performance liquid chromatography separation, Hg cold-vapor formation and inductively coupled plasma mass spectrometry detection. Prior to analysis, plasma (250 μL) was accurately pipetted into 15 mL conical tubes. Then, an extractant solution containing mercaptoethanol, L-cysteine and HCl was added to the samples following sonication for 10 min. Quantitative mercury extraction was achieved with the proposed procedure. Separation of mercury species was accomplished in less than 8 min on a C8 reverse phase column with a mobile phase containing 3% v/v methanol + 97% v/v (0.5% v/v 2-mercaptoethanol + 0.05% v/v formic acid). The method detection limits were found to be 12 ng L(-1), 5 ng L(-1) and 4 ng L(-1) for inorganic mercury, ethylmercury and methylmercury, respectively. Method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from NIST. Additional validation was provided by the analysis of a secondary reference serum sample from the INSQ-Canada. Finally, the method was successfully applied for the speciation of mercury in plasma samples collected from volunteers exposed to methylmercury through fish consumption. For the first time to our knowledge, levels of different species of Hg in plasma samples from riverside populations exposed to MeHg were determined.

  7. Determination of multiple human arsenic metabolites employing high performance liquid chromatography inductively coupled plasma mass spectrometry.

    PubMed

    Stice, Szabina; Liu, Guangliang; Matulis, Shannon; Boise, Lawrence H; Cai, Yong

    2016-01-15

    During the metabolism of different arsenic-containing compounds in human, a variety of metabolites are produced with significantly varying toxicities. Currently available analytical methods can only detect a limited number of human metabolites in biological samples during one run due to their diverse characteristics. In addition, co-elution of species is often unnoticeable with most detection techniques leading to inaccurate metabolic profiles and assessment of toxicity. A high performance liquid chromatography inductively coupled mass spectrometry (HPLC-ICP-MS) method was developed that can identify thirteen common arsenic metabolites possibly present in human with special attention dedicated to thiolated or thiol conjugated arsenicals. The thirteen species included in this study are arsenite (As(III)), arsino-glutathione (As(GS)3), arsenate (As(V)), monomethylarsonous acid (MMA(III)), monomethylarsino-glutathione (MMA(III)(GS) 2), monomethylarsonic acid (MMA(V)), dimethylarsinous acid (DMA(III) (from DMA(III)I)), S-(dimethylarsinic)cysteine (DMA(III) (Cys)), dimethylarsino-glutathione (DMA(III)(GS)), dimethylarsinic acid (DMA(V)), dimethylmonothioarsinic acid (DMMTA(V)), dimethyldithioarsinic acid (DMDTA(V)), dimethylarsinothioyl glutathione (DMMTA(V)(GS)). The developed method was applied for the analysis of cancer cells that were incubated with darinaparsin (DMA(III)(GS)), a novel chemotherapeutic agent for refractory malignancies, and the arsenic metabolic profile obtained was compared to results using a previously developed method. This method provides a useful analytical tool which is much needed in unequivocally identifying the arsenicals formed during the metabolism of environmental arsenic exposure or therapeutic arsenic administration.

  8. Determination of platinum and rhodium in environmental matrixes by solid sampling-electrothermal vaporization-inductively coupled plasma mass spectrometry.

    PubMed

    Vanhaecke, F; Resano, M; Pruneda-Lopez, M; Moens, L

    2002-12-01

    Electrothermal vaporization from a graphite furnace was used in combination with inductively coupled plasma mass spectrometry (ICPMS) for the determination of Pt and Rh in environmental matrixes. Solid samples of tunnel dust, grass, and atmospheric aerosol collected on a cellulose filter could be analyzed directly, such that sample dissolution-which is not self-evident for the determination of platinum group metals-could be avoided. By heating the graphite furnace according to a multistep temperature program, spectral interferences were avoided, since a "dry" plasma was obtained, while "parent" ions such as Cu, Zn, and Pb, giving origin to interfering molecular ions, were vaporized during the thermal pretreatment step. For tunnel dust, the most demanding sample matrix, a mixture of HCl and HF was used as a modifier to stimulate the vaporization of matrix components during the thermal pretreatment step and, hence, to alleviate matrix-induced analyte signal suppression during the actual vaporization step. Calibration was accomplished by means of single standard addition with an aqueous standard solution. The results obtained agreed within the experimental uncertainty with the corresponding reference values (certified values or results obtained using pneumatic nebulization ICPMS), while relative standard deviations of < or = 15% were typical for both Pt and Rh. In all samples, a Pt/Rh ratio of approximately 6-8 was established. For a typical sample mass of 2 mg, limits of detection were 0.35 ng/g for Pt and 0.05 ng/g for Rh.

  9. Comparing the precision of selenium isotope ratio measurements using collision cell and sector field inductively coupled plasma mass spectrometry.

    PubMed

    Elwaer, Nagmeddin; Hintelmann, Holger

    2008-03-15

    The performance of two different types of inductively coupled plasma mass spectrometry (ICP-MS) instruments for resolving spectral overlaps on Se isotopes was compared by means of selenium isotopic ratio measurements. Examined were a quadrupole-based, hexapole collisions cell CC-ICP-MS and a double-focusing sector field SF-ICP-MS. Due to the importance of precise and accurate isotope ratio determination in environmental, clinical and nutritional studies, a thorough investigation of the critical instrumental parameters of each technique was performed. A hydride generation system was coupled with SF-ICP-MS to maintain high signal-to-noise ratios (S/N) at high mass resolution. However, 80Se+ was not completely separated from the argon dimer (40)Ar2+ at m/z=80, even in high-resolution mode. The same hydride generation system was coupled to a collision cell instrument and it was found that argon dimers are significantly reduced using a mixture of H2 and He gas with the cell. A lower mass bias of 2.5% per amu was determined for measured Se isotopes using the SF-ICP-MS instrument compared 3.6% observed for the CC-ICP-MS instrument. Under optimized conditions, the precision for Se isotope ratio measurements of both instruments was evaluated and compared measuring NIST-3149 Se standard solution. On average, the uncertainty determined by repeated measurements over the span of three individual measuring sessions in a period of 3 weeks ranged from 0.06% to 0.15% and 0.09% to 0.30% R.S.D. for the various isotope ratios using the CC-ICP-MS and SF-ICP-MS instrument, respectively. The detection limits (3) for total Se were determined by measuring 82Se and found to be 1.7 and 4.0 ng L(-1) for the CC-ICP-MS and SF-ICP-MS, respectively. PMID:18371869

  10. Identification of gunshot residues in fabric targets using sector field inductively coupled plasma mass spectrometry technique and ternary graphs.

    PubMed

    Freitas, João Carlos D; Sarkis, Jorge E Souza; Negrini Neto, Osvaldo; Viebig, Sônia Bocamino

    2012-03-01

    During criminal investigations involving firearms, the detection of gunshot residues (GSRs) is one of the most important evidences. In the present study, a new method to identify trace evidences of GSRs, deposited around the bullet entrance hole, in different types of fabrics used as targets, is described. The experiments were carried out using a 0.38-inch caliber revolver, and 9-mm and 0.40-inch caliber pistols. Testimonies of 2.25 cm(2) of the fabrics were cut around the bullet entrance and digested with 10% nitric acid. Antimony, barium, and lead were analyzed in the remaining solution using a sector field inductively coupled plasma mass spectrometer. The concentrations of the elements were detected at levels up to few microgram per square centimeter. The use of ternary graphics allowed us to identify specific patterns of distribution for blank samples and the clear distinction between the revolver and pistols used.

  11. Detection of gunshot residue in blowfly larvae and decomposing porcine tissue using inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Lagoo, Lisa; Schaeffer, Luther S; Szymanski, David W; Smith, Ruth Waddell

    2010-05-01

    Blowfly larvae and porcine tissue contaminated with gunshot residue (GSR) were collected during summer and winter months, over a 37-day and a 60-day sampling period, respectively. Wound samples were microwave-digested and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) for the detection of antimony, barium, and lead. During summer, the 37-day sampling period encompassed all stages of decomposition, except skeletonization. The three elements were detected in larvae only on days 3 and 4 after death but were detected at significant levels in tissue samples throughout the entire sampling period. In winter, no significant decomposition was observed throughout the 60-day sampling. Although temperatures were too low for blowfly activity, the three elements were detected in the tissue samples at relatively constant, significant levels. Hence, GSR determination in tissue was more dependent on decomposition stage rather than time since death.

  12. Determination of bromine and tin compounds in plastics using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    İzgi, Belgin; Kayar, Murat

    2015-07-01

    The polybrominated flame retardants and organotin compounds were screened in terms of bromine and tin content using laser ablation inductively coupled plasma mass spectrometry in plastics. The calibration standards were prepared using the fused-disk technique, and all samples were investigated under optimal conditions. Using a central composite experimental design, laser parameters, laser energy, pulse rate, scan rate and spot size were identified. The detection limits of the method were 1000 mgkg(-1) and 1600 mgkg(-1) for bromide and tin, whereas the relative standard deviation (%) values of the analysis were 9% and 6% (n=3) for ERM EC681k with 770 ± 70 mgkg(-1) Br and 86 ± 6 mgkg(-1) Sn respectively, and 106-115% of Br and 102-104% of Sn were observed for the tetrabromobisphenol A and butyltin trichloride spike plastics, respectively.

  13. Investigating Uranium Concentrations in Groundwaters in the State of Idaho Using Kinetic Phosphorescence Analysis and Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Tkavadze, Levan; Dunker, Roy E; Brey, Richard R; Dudgeon, John

    2016-11-01

    The determination of uranium concentrations in natural water samples is of great interest due to the environmental consequences of this radionuclide. In this study, 380 groundwater samples from various locations within the state of Idaho were analyzed using two different techniques. The first method was Kinetic Phosphorescence Analysis (KPA), which gives the total uranium concentrations in water samples. The second analysis method was inductively coupled plasma mass spectrometry (ICP- MS). This method determines the total uranium concentration as well as the separate isotope concentrations of uranium. The U/U isotopic ratio was also measured for each sample to confirm that there was no depleted or enriched uranium present. The results were compared and mapped separately from each other. The study also found that in some areas of the state, natural uranium concentrations are relatively high. PMID:27682901

  14. Determination of selenium species in human urine by high performance liquid chromatography and inductively coupled plasma mass spectrometry.

    PubMed

    Quijano, M A; Gutiérrez, A M; Pérez-Conde, M C; Cámara, C

    1999-08-23

    A method developed to determine organic and inorganic selenium species in human urine samples is presented in detail. After a simple sample treatment based on elimination of non-charged organic compounds, selenium species were separated by high performance liquid chromatography (HPLC) on a Spherisorb 5 ODS/AMINO column using two different chromatographic conditions: phosphate buffers at pH 2.8 and 6.0. Detection was carried out using an on-line inductively coupled plasma mass spectrometer (ICP-MS). Trimethylselenonium ion and two unknown selenium species in urine samples were found. Selenium species were shown to have stability problems, with the maximum allowed storage time of 1 week.

  15. Determination of 24 trace elements in felsic rocks by inductively coupled plasma mass spectrometry after lithium metaborate fusion

    NASA Astrophysics Data System (ADS)

    Panteeva, S. V.; Gladkochoub, D. P.; Donskaya, T. V.; Markova, V. V.; Sandimirova, G. P.

    2003-02-01

    An improved lithium metaborate fusion technique for inductively coupled plasma mass spectrometric analysis of felsic rocks is proposed. The method involves the dissolution of fused sample material with HF followed by treatment with HNO 3. The decomposition method developed was used for the determination of trace elements in ancient felsic volcanic rocks and granites of Southern Siberia and further applied to petrologic modeling and the geodynamic setting of the rock origin. Data for geological reference materials STM-1, G-2, GSP-1, AGV-1 and BCR-1 were used for method validation and experimental results obtained agreed well with certified values. Detection limits determined ranged from 0.021 to 0.24 μg/g for Y, Pr, middle and heavy rare earth elements (REE), Ta, U and from 0.44 to 2.07 μg/g for Rb, Sr, Zr, Nb, Ba, light REE, Hf and Th.

  16. Aluminium content of some processed foods, raw materials and food additives in China by inductively coupled plasma-mass spectrometry.

    PubMed

    Deng, Gui-Fang; Li, Ke; Ma, Jing; Liu, Fen; Dai, Jing-Jing; Li, Hua-Bin

    2011-01-01

    The level of aluminium in 178 processed food samples from Shenzhen city in China was evaluated using inductively coupled plasma-mass spectrometry. Some processed foods contained a concentration of up to 1226 mg/kg, which is about 12 times the Chinese food standard. To establish the main source in these foods, Al levels in the raw materials were determined. However, aluminium concentrations in raw materials were low (0.10-451.5 mg/kg). Therefore, aluminium levels in food additives used in these foods was determined and it was found that some food additives contained a high concentration of aluminium (0.005-57.4 g/kg). The results suggested that, in the interest of public health, food additives containing high concentrations of aluminium should be replaced by those containing less. This study has provided new information on aluminium levels in Chinese processed foods, raw materials and a selection of food additives.

  17. Assessment of lead, cadmium and mercury in seafood marketed in Puglia and Basilicata (Italy) by inductively coupled plasma mass spectrometry.

    PubMed

    Miedico, Oto; Iammarino, Marco; Pompa, Ciro; Tarallo, Marina; Chiaravalle, Antonio Eugenio

    2015-01-01

    Lead, cadmium and mercury are non-essential heavy metals that may interfere with biological systems, exhibiting high toxicity to human and marine biota. Due to bioaccumulation of heavy metals in the food chain, seafood may concentrate high levels of these contaminants since they are often at the top of aquatic food chain. In this study, 342 seafood samples, subdivided into four categories (bivalve molluscs, cephalopod molluscs, blue-fish and other sea fish), were analysed by inductively coupled plasma mass spectrometry, in order to assess the levels of lead, cadmium and mercury. Contamination levels higher than allowable limits were verified. In particular, two bivalve mollusc samples were non-compliant for lead and cadmium, four cephalopod mollusc samples non-compliant for cadmium and 14 samples (4 blue-fish and 10 other sea fish) non-compliant for mercury. This survey confirmed the necessity to perform routinely controls related to this type of food inspection.

  18. Determination of organomercury in biological reference materials by inductively coupled plasma mass spectrometry using flow injection analysis

    SciTech Connect

    Beauchemin, D.; Siu, K.W.; Berman, S.S.

    1988-12-01

    Inductively coupled plasma mass spectrometry was used for the determination of organomercury in two marine biological standard reference materials for trace metals (dogfish muscle tissue DORM-1 and lobster hepatopancreas TORT-1). In most parts of this study, the organomercury was extracted as the chloride from the material with toluene and back extracted into an aqueous medium of cysteine acetate. Since the final extracts contained more than 4% sodium, isotope dilution and flow injection analysis were used to respectively counter the effect of concomitant elements and avoid clogging the interface. Comparison of results with gas chromatography shows that the only significant organomercury is methyl-mercury. At least 93% of mercury in DORM-1 and 39% of mercury in TORT-1 exist as methylmercury.

  19. Determination of selenium species in human urine by high performance liquid chromatography and inductively coupled plasma mass spectrometry.

    PubMed

    Quijano, M A; Gutiérrez, A M; Pérez-Conde, M C; Cámara, C

    1999-08-23

    A method developed to determine organic and inorganic selenium species in human urine samples is presented in detail. After a simple sample treatment based on elimination of non-charged organic compounds, selenium species were separated by high performance liquid chromatography (HPLC) on a Spherisorb 5 ODS/AMINO column using two different chromatographic conditions: phosphate buffers at pH 2.8 and 6.0. Detection was carried out using an on-line inductively coupled plasma mass spectrometer (ICP-MS). Trimethylselenonium ion and two unknown selenium species in urine samples were found. Selenium species were shown to have stability problems, with the maximum allowed storage time of 1 week. PMID:18967706

  20. Determination of rare-earth elements in uranium-bearing materials by inductively coupled plasma mass spectrometry.

    PubMed

    Varga, Zsolt; Katona, Róbert; Stefánka, Zsolt; Wallenius, Maria; Mayer, Klaus; Nicholl, Adrian

    2010-03-15

    A novel and simple analytical procedure has been developed for the trace-level determination of lanthanides (rare-earth elements) in uranium-bearing materials by inductively coupled plasma sector-field mass spectrometry (ICP-SFMS). The method involves a selective extraction chromatographic separation of lanthanides using TRU resin followed by ICP-SFMS analysis. The limits of detection of the method proposed is in the low pg g(-1) range, which are approximately two orders of magnitude better than that of without chemical separation. The method was validated by the measurement of reference material and applied for the analysis of uranium ore concentrates (yellow cakes) for nuclear forensic purposes, as a potential application of the methodology. PMID:20152406

  1. Inductively Coupled Plasma/Mass Spectrometric Isotopic Determination of Nuclear Wastes Sources Associated with Hanford Tank Leaks

    SciTech Connect

    Evans, John C.; Dresel, P. Evan; Farmer, Orville T.

    2007-11-01

    The subsurface distribution of a nuclear waste tank leak on the U.S. Department of Energy’s Hanford Site was sampled by slant drilling techniques in order to characterize the chemical and radiological characteristics of the leaked material and assess geochemical transport properties of hazardous constituents. Sediment core samples recovered from the borehole were subjected to distilled water and acid leaching procedures with the resulting leachates analyzed for isotopic and chemical signatures. High-sensitivity inductively coupled plasma/mass spectrometry (ICP/MS) techniques were used for determination of isotopic ratios for Cs, I, Mo. Analysis of the isotopic patterns of I and Mo combined with associated chemical data showed evidence for at least two separate intrusions of nuclear waste into the subsurface. Isotopic data for Cs was inconclusive with respect to a source attribution signature.

  2. Using laser ablation/inductively coupled plasma mass spectrometry to bioimage multiple elements in mouse tumors after hyperthermia.

    PubMed

    Hsieh, Yi-Kong; Jiang, Pei-Shin; Yang, Bing-Shen; Sun, Tian-Ye; Peng, Hsu-Hsia; Wang, Chu-Fang

    2011-08-01

    In this study, we employed laser ablation/inductively coupled plasma mass spectrometry (LA-ICP-MS) to map the spatial distribution of Gd-doped iron oxide nanoparticles (IONPs) in one tumor slice that had been subjected to magnetic fluid hyperthermia (MFH). The mapping results revealed the high resolution of the elemental analysis, with the distribution of Gd atoms highly correlated with that of the Fe atoms. The spatial distributions of C, P, S, and Zn atoms revealed that the effect of MFH treatment was significantly dependent on the diffusion of the magnetic fluid in the tissue. An observed enrichment of Cu atoms after MFH treatment was probably due to inflammation in the tumor. The abnormal distribution of Ni atoms suggests a probable biochemical reaction in the tumor. Therefore, this LA-ICP-MS mapping technique can provide novel information regarding the spatial distribution of elements in tumors after cancer therapy.

  3. Determination of trace mercury species by high performance liquid chromatography-inductively coupled plasma mass spectrometry after cloud point extraction.

    PubMed

    Chen, Haiting; Chen, Jianguo; Jin, Xianzhong; Wei, Danyi

    2009-12-30

    A sensitive method for speciation analysis of inorganic mercury (Hg(2+)) and methyl mercury (MeHg(+)) has been developed by using high performance liquid chromatography (HPLC) combined with inductively coupled plasma mass spectrometry (ICP-MS) after cloud point extraction. The analytes were complexed with sodium diethyldithiocarbamate (DDTC) and preconcentrated by a non-ionic surfactant Triton X-114. Mercury species were effectively separated by HPLC in less than 6 min. The enhancement factors for 25 mL sample solution were 42 and 21, and the limits of detection were 4 and 10 ng L(-1) for Hg(2+) and MeHg(+), respectively. The developed method was successfully applied to the determination of trace amount of mercury species in environmental and biological samples.

  4. A simple and demountable capillary microflow nebulizer with a tapered tip for inductively coupled plasma mass spectrometry.

    PubMed

    Cheng, Heyong; Yin, Xuefeng; Xu, Zigang; Wang, Xiuzhong; Shen, Hong

    2011-07-15

    A simple and demountable capillary microflow nebulizer (d-CMN) was developed for inductively coupled plasma mass spectrometry (ICP-MS). It consisted of a nebulizer body, a fused-silica capillary with a tapered tip and a polytetrafluoroethylene (PTFE) adapter. The gas orifice i.d., the solution capillary tip i.d. and its wall thickness were 200, 30, and 5 μm, respectively. The sensitivities, detection limits, precisions and the long-term stability with the d-CMN were evaluated. The experimental results indicated that its performances at low uptake rates were similar or better than those obtained with the conventional concentric nebulizer at 820 μL/min and the micromist nebulizer at 200 μL/min. The demountable construction of the d-CMN permitted that the blocked or broken solution capillary could be conveniently renewed. The low self-aspiration rate (4.77 μL/min) and the analytical characteristics comparable to commercial microflow nebulizers made the d-CMN a good choice for coupling capillary electrophoresis and microbore high-performance liquid chromatograph to ICP-MS. The proposed d-CMN was successfully applied in the iodine speciation by coupling microchip capillary electrophoresis (MCE) to ICP-MS. The absolute detection limits for iodide and iodate of 0.20 and 0.29 fg were achieved with satisfactory resolution.

  5. Laser ablation-inductively coupled plasma mass spectrometry: an emerging technology for detecting rare cells in tissue sections.

    PubMed

    Managh, Amy J; Hutchinson, Robert W; Riquelme, Paloma; Broichhausen, Christiane; Wege, Anja K; Ritter, Uwe; Ahrens, Norbert; Koehl, Gudrun E; Walter, Lisa; Florian, Christian; Schlitt, Hans J; Reid, Helen J; Geissler, Edward K; Sharp, Barry L; Hutchinson, James A

    2014-09-01

    Administering immunoregulatory cells to patients as medicinal agents is a potentially revolutionary approach to the treatment of immunologically mediated diseases. Presently, there are no satisfactory, clinically applicable methods of tracking human cells in patients with adequate spatial resolution and target cell specificity over a sufficient period of time. Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) represents a potential solution to the problem of detecting very rare cells in tissues. In this article, this exquisitely sensitive technique is applied to the tracking of gold-labeled human regulatory macrophages (Mregs) in immunodeficient mice. Optimal conditions for labeling Mregs with 50-nm gold particles were investigated by exposing Mregs in culture to variable concentrations of label: Mregs incubated with 3.5 × 10(9) particles/ml for 1 h incorporated an average of 3.39 × 10(8) Au atoms/cell without loss of cell viability. Analysis of single, gold-labeled Mregs by LA-ICP-MS registered an average of 1.9 × 10(5) counts/cell. Under these conditions, 100% labeling efficiency was achieved, and label was retained by Mregs for ≥36 h. Gold-labeled Mregs adhered to glass surfaces; after 24 h of culture, it was possible to colabel these cells with human-specific (154)Sm-tagged anti-HLA-DR or (174)Yb-tagged anti-CD45 mAbs. Following injection into immunodeficient mice, signals from gold-labeled human Mregs could be detected in mouse lung, liver, and spleen for at least 7 d by solution-based inductively coupled plasma mass spectrometry and LA-ICP-MS. These promising results indicate that LA-ICP-MS tissue imaging has great potential as an analytical technique in immunology.

  6. Electrospray-Differential Mobility Hyphenated with Single Particle Inductively Coupled Plasma Mass Spectrometry for Characterization of Nanoparticles and Their Aggregates.

    PubMed

    Tan, Jiaojie; Liu, Jingyu; Li, Mingdong; El Hadri, Hind; Hackley, Vincent A; Zachariah, Michael R

    2016-09-01

    The novel hyphenation of electrospray-differential mobility analysis with single particle inductively coupled plasma mass spectrometry (ES-DMA-spICPMS) was demonstrated with the capacity for real-time size, mass, and concentration measurement of nanoparticles (NPs) on a particle-to-particle basis. In this proof-of-concept study, the feasibility of this technique was validated through both concentration and mass calibration using NIST gold NP reference materials. A detection limit of 10(5) NPs mL(-1) was determined under current experimental conditions, which is about 4 orders of magnitude lower in comparison to that of a traditional ES-DMA setup using a condensation particle counter as detector. Furthermore, independent and simultaneous quantification of both size and mass of NPs provides information regarding NP aggregation states. Two demonstrative applications include gold NP mixtures with a broad size range (30-100 nm), and aggregated gold NPs with a primary size of 40 nm. Finally, this technique was shown to be potentially useful for real-world samples with high ionic background due to its ability to remove dissolved ions yielding a cleaner background. Overall, we demonstrate the capacity of this new hyphenated technique for (1) clearly resolving NP populations from a mixture containing a broad size range; (2) accurately measuring a linear relationship, which should inherently exist between mobility size and one-third power of ICPMS mass for spherical NPs; (3) quantifying the early stage propagation of NP aggregation with well-characterized oligomers; and (4) differentiating aggregated NPs and nonaggregated states based on the "apparent density" derived from both DMA size and spICPMS mass.

  7. Electrospray-Differential Mobility Hyphenated with Single Particle Inductively Coupled Plasma Mass Spectrometry for Characterization of Nanoparticles and Their Aggregates.

    PubMed

    Tan, Jiaojie; Liu, Jingyu; Li, Mingdong; El Hadri, Hind; Hackley, Vincent A; Zachariah, Michael R

    2016-09-01

    The novel hyphenation of electrospray-differential mobility analysis with single particle inductively coupled plasma mass spectrometry (ES-DMA-spICPMS) was demonstrated with the capacity for real-time size, mass, and concentration measurement of nanoparticles (NPs) on a particle-to-particle basis. In this proof-of-concept study, the feasibility of this technique was validated through both concentration and mass calibration using NIST gold NP reference materials. A detection limit of 10(5) NPs mL(-1) was determined under current experimental conditions, which is about 4 orders of magnitude lower in comparison to that of a traditional ES-DMA setup using a condensation particle counter as detector. Furthermore, independent and simultaneous quantification of both size and mass of NPs provides information regarding NP aggregation states. Two demonstrative applications include gold NP mixtures with a broad size range (30-100 nm), and aggregated gold NPs with a primary size of 40 nm. Finally, this technique was shown to be potentially useful for real-world samples with high ionic background due to its ability to remove dissolved ions yielding a cleaner background. Overall, we demonstrate the capacity of this new hyphenated technique for (1) clearly resolving NP populations from a mixture containing a broad size range; (2) accurately measuring a linear relationship, which should inherently exist between mobility size and one-third power of ICPMS mass for spherical NPs; (3) quantifying the early stage propagation of NP aggregation with well-characterized oligomers; and (4) differentiating aggregated NPs and nonaggregated states based on the "apparent density" derived from both DMA size and spICPMS mass. PMID:27479448

  8. Determination of trace rare earth elements in gadolinium aluminate by inductively coupled plasma time of flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Saha, Abhijit; Deb, S. B.; Nagar, B. K.; Saxena, M. K.

    An analytical methodology was developed for the precise quantification of ten trace rare earth elements (REEs), namely, La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Tm, in gadolinium aluminate (GdAlO3) employing an ultrasonic nebulizer (USN)-desolvating device based inductively coupled plasma mass spectrometry (ICP-MS). A microwave digestion procedure was optimized for digesting 100 mg of the refractory oxide using a mixture of sulphuric acid (H2SO4), phosphoric acid (H3PO4) and water (H2O) with 1400 W power, 10 min ramp and 60 min hold time. An USN-desolvating sample introduction system was employed to enhance analyte sensitivities by minimizing their oxide ion formation in the plasma. Studies on the effect of various matrix concentrations on the analyte intensities revealed that precise quantification of the analytes was possible with matrix level of 250 mg L- 1. The possibility of using indium as an internal standard was explored and applied to correct for matrix effect and variation in analyte sensitivity under plasma operating conditions. Individual oxide ion formation yields were determined in matrix matched solution and employed for correcting polyatomic interferences of light REE (LREE) oxide ions on the intensities of middle and heavy rare earth elements (MREEs and HREEs). Recoveries of ≥ 90% were achieved for the analytes employing standard addition technique. Three real samples were analyzed for traces of REEs by the proposed method and cross validated for Eu and Nd by isotope dilution mass spectrometry (IDMS). The results show no significant difference in the values at 95% confidence level. The expanded uncertainty (coverage factor 1σ) in the determination of trace REEs in the samples were found to be between 3 and 8%. The instrument detection limits (IDLs) and the method detection limits (MDLs) for the ten REEs lie in the ranges 1-5 ng L- 1 and 7-64 μg kg- 1 respectively.

  9. Analysis of phosphorus herbicides by ion-pairing reversed-phase liquid chromatography coupled to inductively coupled plasma mass spectrometry with octapole reaction cell.

    PubMed

    Sadi, Baki B M; Vonderheide, Anne P; Caruso, Joseph A

    2004-09-24

    A reversed phase ion-pairing high performance liquid chromatographic (RPIP-HPLC) method is developed for the separation of two phosphorus herbicides, Glufosinate and Glyphosate as well as Aminomethylphosphonic acid (AMPA), the major metabolite of Glyphosate. Tetrabutylammonium hydroxide is used as the ion-pairing reagent in conjunction with an ammonium acetate/acetic acid buffering system at pH 4.7. An inductively coupled plasma mass spectrometer (ICP-MS) is coupled to the chromatographic system to detect the herbicides at m/z = 31P. Historically, phosphorus has been recognized as one of the elements difficult to analyze in argon plasma. This is due to its relatively high ionization potential (10.5 eV) as well as the inherent presence of the polyatomic interferences 14N16O1H+ and 15N16O+ overlapping its only isotope at m/z = 31. An octapole reaction cell is utilized to minimize the isobaric polyatomic interferences and to obtain the highest signal-to-background ratio. Detection limits were found to be in the low ppt range (25-32 ng/l). The developed method is successfully applied to the analysis of water samples collected from the Ohio River and spiked with a standard compounds at a level of 20 microg/l.

  10. Determination of heavy metals by inductively coupled plasma mass spectrometry after on-line separation and preconcentration

    NASA Astrophysics Data System (ADS)

    Dressler, Valderi L.; Pozebon, Dirce; Curtius, Adilson J.

    1998-10-01

    A method for the determination of Cu, As, Se, Cd, In, Hg, Tl, Pb and Bi in waters and in biological materials by inductively coupled plasma mass spectrometry, after an on-line separation, is described. The matrix separation and analyte preconcentration is accomplished by retention of the analytes complexed with the ammonium salt of O,O-diethyl dithiophosphoric acid in a HNO 3 solution on C 18 immobilized on silica in a minicolumn. Methanol, as eluent, is introduced in the conventional pneumatic nebulizer of the instrument. In order to use the best compromise conditions, concerning the ligand and acid concentrations, the analytes were determined in two separate groups. The enrichment factors were in the range from 5 to 61, depending on the analyte. The limits of detection varied from 0.43 ng L -1 for Bi to 33 ng L -1 for Cu. The sample consumption is only 2.3 mL for each group and the sampling frequency is 21 h -1. The accuracy was tested by analysing five certified reference materials: water, riverine water, urine, bovine muscle and bovine liver. The agreement between obtained and certified concentrations was very good, except for As. The relatively small volume of methanol, used as eluent, minimizes the problems produced by the introduction of organic solvent into the plasma.

  11. Determination and pharmacokinetic study of hydrocodone in human plasma by liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Zhang, Rui; Wang, Benjie; Wei, Chunmin; Yuan, Guiyan; Guo, Ruichen

    2009-01-01

    A rapid, highly sensitive and specific high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS-MS) quantitation method was developed and validated for the determination of hydrocodone in human plasma. Sample was extracted from 0.5mL heparinized plasma by a simple liquid-liquid extraction method and analyzed on a C18 column with a mobile phase of acetonitrile-water (78:22,v/v,0.1% acetic acid). Detection was carried out by positive elevtrospray ionization (ESI) in multiple reactions monitoring (MRM) mode of 300.3-->199.2 (m/z) for hydrocodone and 341.2-->107.2 (m/z) for canrenone (I.S.), respectively. A good linearity was obtained from 0.5 to 60 ng x mL(-1) and the lower limit of quantification (LLOQ) was 0.1 ng x mL(-1). Compared to an existing method, the extraction method, internal standard and chromatographic conditions were modified and the cost of a large amount of samples determination was decreased obviously. The method was successfully applied to the pharmacokinetic and bioequivalence studies in healthy Chinese volunteers. PMID:19728188

  12. Determination of lanthanides in rock samples by inductively coupled plasma mass spectrometry using thorium as oxide and hydroxide correction standard

    NASA Astrophysics Data System (ADS)

    Raut, Narendra M.; Huang, Li-Shing; Aggarwal, Suresh K.; Lin, King-Chuen

    2003-05-01

    Determination of lanthanides by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) using modified mathematical correction method has been studied. Normally, the ICP-MS analysis of middle and heavier lanthanides becomes difficult by severe spectroscopic overlap of M +, MO + or MOH + ions from lighter lanthanides and Ba. A correction method based on a single element oxide yield measurement, is a simple approach to correct for the above spectroscopic overlaps. But the uncertainty in the oxide and hydroxide yields measurement of lanthanides and barium over a long period of time can lead to inaccurate results even under fixed plasma conditions. To correct this, thorium was adopted as an oxide and hydroxide correction standard. Using a ratio of lanthanide oxide yield to thorium oxide yield, the lanthanide correction factors (LCF) were established and incorporated in the mathematical correction scheme. The same factors were also established for hydroxide correction. The proposed modified correction scheme was applied to the determination of lanthanides by ICP-MS from the USGS Standard Rock samples AGV-1 and G-2. The results are in good agreement with the reported values. The method also proved to be useful in isotopic ratio measurement of lanthanides having severe isobaric overlaps.

  13. Determination of arsenic species in Solanum Lyratum Thunb using capillary electrophoresis with inductively coupled plasma mass spectrometry.

    PubMed

    Shuai, Pei-Yu; Yang, Xiao-Jun; Qiu, Zong-Qing; Wu, Xiao-Hui; Zhu, Xi; Pokhrel, Ganga Raj; Fu, Yu-Ying; Ye, Hui-Min; Lin, Wen-Xiong; Yang, Gui-Di

    2016-08-01

    A simple and highly efficient interface to couple capillary electrophoresis with inductively coupled plasma mass spectrometry by a microflow polyfluoroalkoxy nebulizer and a quadruple ion deflector was developed in this study. By using this interface, six arsenic species, including arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, were baseline-separated and determined in a single run within 11 min under the optimized separation conditions. The instrumental detection limit was in the range of 0.02-0.06 ng/mL for the six arsenic compounds. Repeatability expressed as the relative standard deviation (n = 5) of both migration time and peak area were better than 2.5 and 4.3% for six arsenic compounds. The proposed method, combined with a closed-vessel microwave-assisted extraction procedure, was successfully applied for the determination of arsenic species in the Solanum Lyratum Thunb samples from Anhui province in China with the relative standard deviations (n = 5) ≤4%, method detection limits of 0.2-0.6 ng As/g and a recovery of 98-104%. The experimental results showed that arsenobetaine was the main speciation of arsenic in the Solanum Lyratum Thunb samples from different provinces in China, with a concentration of 0.42-1.30 μg/g. PMID:27378629

  14. Determination of trace-level haloacetic acids in drinking water by ion chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Liu, Yongjian; Mou, Shifen; Chen, Dengyun

    2004-06-11

    A new method for the determination of nine haloacetic acids (HAAs) with ion chromatography (IC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) was developed. With the very hydrophilic anion-exchange column and steep gradient of sodium hydroxide, the nine HAAs could be well separated in 15 min. After suppression with an ASRS suppressor that was introduced in between IC and ICP-MS, the background was much decreased, the interference caused by sodium ion present in eluent was removed, and the sensitivities of HAAs were greatly improved. The chlorinated and brominated HAAs could be detected as 35ClO and 79Br without interference of the matrix due to the elemental selective ICP-MS. The detection limits for mono-, di-, trichloroacetic acids were between 15.6 and 23.6 microg/l. For the other six bromine-containing HAAs, the detection limits were between 0.34 and 0.99 microg/l. With the pretreatment of OnGuard Ag cartridge to remove high concentration of chloride in sample, the developed method could be applied to the determination of HAAs in many drinking water matrices.

  15. Role of laser ablation-inductively coupled plasma-mass spectrometry in cultural heritage research: a review.

    PubMed

    Giussani, Barbara; Monticelli, Damiano; Rampazzi, Laura

    2009-03-01

    Cultural heritage represents a bridge between the contemporary society and the past populations, and a strong collaboration between archaeologists, art historians and analysts may lead to the decryption of the information hidden in an ancient object. Quantitative elemental compositional data play a key role in solving questions concerning dating, provenance, technology, use and the relationship of ancient cultures with the environment. Nevertheless, the scientific investigation of an artifact should be carried out complying with some important constraints: above all the analyses should be as little destructive as possible and performed directly on the object to preserve its integrity. Laser ablation sampling coupled to inductively coupled plasma-mass spectrometry (LA-ICP-MS) fulfils these requirements exhibiting comparably strong analytical performance in trace element determination. This review intends to show through the applications found in the literature how valuable is the contribution of LA-ICP-MS in the investigation of ancient materials such as obsidian, glass, pottery, human remains, written heritage, metal objects and miscellaneous stone materials. The main issues related to cultural heritage investigation are introduced, followed by a brief description of the features of this technique. An overview of the exploitation of LA-ICP-MS is then presented. Finally, advantages and drawbacks of this technique are critically discussed: the fit for purpose and prospects of the use of LA-ICP-MS are presented. PMID:19200475

  16. Role of laser ablation-inductively coupled plasma-mass spectrometry in cultural heritage research: a review.

    PubMed

    Giussani, Barbara; Monticelli, Damiano; Rampazzi, Laura

    2009-03-01

    Cultural heritage represents a bridge between the contemporary society and the past populations, and a strong collaboration between archaeologists, art historians and analysts may lead to the decryption of the information hidden in an ancient object. Quantitative elemental compositional data play a key role in solving questions concerning dating, provenance, technology, use and the relationship of ancient cultures with the environment. Nevertheless, the scientific investigation of an artifact should be carried out complying with some important constraints: above all the analyses should be as little destructive as possible and performed directly on the object to preserve its integrity. Laser ablation sampling coupled to inductively coupled plasma-mass spectrometry (LA-ICP-MS) fulfils these requirements exhibiting comparably strong analytical performance in trace element determination. This review intends to show through the applications found in the literature how valuable is the contribution of LA-ICP-MS in the investigation of ancient materials such as obsidian, glass, pottery, human remains, written heritage, metal objects and miscellaneous stone materials. The main issues related to cultural heritage investigation are introduced, followed by a brief description of the features of this technique. An overview of the exploitation of LA-ICP-MS is then presented. Finally, advantages and drawbacks of this technique are critically discussed: the fit for purpose and prospects of the use of LA-ICP-MS are presented.

  17. Complexation studies with lanthanides and humic acid analyzed by ultrafiltration and capillary electrophoresis-inductively coupled plasma mass spectrometry.

    PubMed

    Kautenburger, Ralf; Beck, Horst Philipp

    2007-08-01

    For the long-term storage of radioactive waste, detailed information about geo-chemical behavior of radioactive and toxic metal ions under environmental conditions is necessary. Humic acid (HA) can play an important role in the immobilisation or mobilisation of metal ions due to complexation and colloid formation. Therefore, we investigate the complexation behavior of HA and its influence on the migration or retardation of selected lanthanides (europium and gadolinium as homologues of the actinides americium and curium). Two independent speciation techniques, ultrafiltration and capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICP-MS) have been compared for the study of Eu and Gd interaction with (purified Aldrich) HA. The degree of complexation of Eu and Gd in 25 mg l(-1) Aldrich HA solutions was determined with a broad range of metal loading (Eu and Gd total concentration between 10(-6) and 10(-4) mol l(-1)), ionic strength of 10 mM (NaClO4) and different pH-values. From the CE-ICP-MS electropherograms, additional information on the charge of the Eu species was obtained by the use of 1-bromopropane as neutral marker. To detect HA in the ICP-MS and separate between HA complexed and non complexed metal ions in the CE-ICP-MS, we have halogenated the HA with iodine as ICP-MS marker. PMID:17459403

  18. Use of a parallel path nebulizer for capillary-based microseparation techniques coupled with an inductively coupled plasma mass spectrometer for speciation measurements

    NASA Astrophysics Data System (ADS)

    Yanes, Enrique G.; Miller-Ihli, Nancy J.

    2004-06-01

    A low flow, parallel path Mira Mist CE nebulizer designed for capillary electrophoresis (CE) was evaluated as a function of make-up solution flow rate, composition, and concentration, as well as the nebulizer gas flow rate. This research was conducted in support of a project related to the separation and quantification of cobalamin (vitamin B-12) species using microseparation techniques combined with inductively coupled plasma mass spectrometry (ICP-MS) detection. As such, Co signals were monitored during the nebulizer characterization process. Transient effects in the ICP were studied to evaluate the suitability of using gradients for microseparations and the benefit of using methanol for the make-up solution was demonstrated. Co signal response changed significantly as a function of changing methanol concentrations of the make-up solution and maximum signal enhancement was seen at 20% methanol with a 15 μl/min flow rate. Evaluation of the effect of changing the nebulizer gas flow rates showed that argon flows from 0.8 to 1.2 l/min were equally effective. The Mira Mist CE parallel path nebulizer was then evaluated for interfacing capillary microseparation techniques including capillary electrophoresis (CE) and micro high performance liquid chromatography (μHPLC) to inductively coupled plasma mass spectrometry (ICP-MS). A mixture of four cobalamin species standards (cyanocobalamin, hydroxocobalamin, methylcobalamin, and 5' deoxyadenosylcobalamin) and the corrinoid analogue cobinamide dicyanide were successfully separated using both CE-ICP-MS and μHPLC-ICP-MS using the parallel path nebulizer with a make-up solution containing 20% methanol with a flow rate of 15 μl/min.

  19. Calibration strategy for semi-quantitative direct gas analysis using inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Gerdes, Kirk; Carter, Kimberly E.

    2011-09-01

    A process is described by which an ICP-MS equipped with an Octopole Reaction System (ORS) is calibrated using liquid phase standards to facilitate direct analysis of gas phase samples. The instrument response to liquid phase standards is analyzed to produce empirical factors relating ion generation and transmission efficiencies to standard operating parameters. Empirical factors generated for liquid phase samples are then used to produce semi-quantitative analysis of both mixed liquid/gas samples and pure gas samples. The method developed is similar to the semi-quantitative analysis algorithms in the commercial software, which have here been expanded to include gas phase elements such as Xe and Kr. Equations for prediction of relative ionization efficiencies and isotopic transmission are developed for several combinations of plasma operating conditions, which allows adjustment of limited parameters between liquid and gas injection modes. In particular, the plasma temperature and electron density are calculated from comparison of experimental results to the predictions of the Saha equation. Comparisons between operating configurations are made to determine the robustness of the analysis to plasma conditions and instrument operating parameters. Using the methods described in this research, the elemental concentrations in a liquid standard containing 45 analytes and treated as an unknown sample were quantified accurately to ± 50% for most elements using 133Cs as a single internal reference. The method is used to predict liquid phase mercury within 12% of the actual concentration and gas phase mercury within 28% of the actual concentration. The results verify that the calibration method facilitates accurate semi-quantitative, gas phase analysis of metal species with sufficient sensitivity to quantify metal concentrations lower than 1 ppb for many metallic analytes.

  20. Evaluation of number concentration quantification by single-particle inductively coupled plasma mass spectrometry: microsecond vs. millisecond dwell times.

    PubMed

    Abad-Álvaro, Isabel; Peña-Vázquez, Elena; Bolea, Eduardo; Bermejo-Barrera, Pilar; Castillo, Juan R; Laborda, Francisco

    2016-07-01

    The quality of the quantitative information in single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS) depends directly on the number concentration of the nanoparticles in the sample analyzed, which is proportional to the flux of nanoparticles through the plasma. Particle number concentrations must be selected in accordance with the data acquisition frequency, to control the precision from counting statistics and the bias, which is produced by the occurrence of multiple-particle events recorded as single-particle events. With quadrupole mass spectrometers, the frequency of data acquisition is directly controlled by the dwell time. The effect of dwell times from milli- to microseconds (10 ms, 5 ms, 100 μs, and 50 μs) on the quality of the quantitative data has been studied. Working with dwell times in the millisecond range, precision figures about 5 % were achieved, whereas using microsecond dwell times, the suitable fluxes of nanoparticles are higher and precision was reduced down to 1 %; this was independent of the dwell time selected. Moreover, due to the lower occurrence of multiple-nanoparticle events, linear ranges are wider when dwell times equal to or shorter than 100 μs are used. A calculation tool is provided to determine the optimal concentration for any instrument or experimental conditions selected. On the other hand, the use of dwell times in the microsecond range reduces significantly the contribution of the background and/or the presence of dissolved species, in comparison with the use of millisecond dwell times. Although the use of dwell times equal to or shorter than 100 μs offers improved performance working in single-particle mode, the use of conventional dwell times (3-10 ms) should not be discarded, once their limitations are known.

  1. DETERMINATION OF 237NP AND PU ISOTOPES IN LARGE SOIL SAMPLES BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

    SciTech Connect

    Maxwell, S.

    2010-07-26

    A new method for the determination of {sup 237}Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of {sup 237}Np and Pu isotopes by ICP-MS. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via {sup 238}U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1 x 10{sup 6}. Alpha spectrometry can also be applied so that the shorter-lived {sup 238}Pu isotope can be measured successfully. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu and {sup 238}Pu were measured by alpha spectrometry.

  2. On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials.

    PubMed

    Fernández, Beatriz; Rodríguez-González, Pablo; García Alonso, J Ignacio; Malherbe, Julien; García-Fonseca, Sergio; Pereiro, Rosario; Sanz-Medel, Alfredo

    2014-12-01

    We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6-21% for pressed pellets and 3-21% for fused solids were obtained from n=3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches.

  3. High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Morgan, J.L.L.; Gordon, G.W.; Arrua, R.C.; Skulan, J.L.; Anbar, A.D.; Bullen, T.D.

    2011-01-01

    We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios (44Ca/42Ca and 44Ca/43Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10000; Ca/Ti > 10000000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ44/42Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2‰ (2σ).

  4. Investigations on the direct introduction of cigarette smoke for trace elements analysis by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chang, Michael J.; Naworal, John D.; Walker, Kathleen; Connell, Chris T.

    2003-11-01

    Direct introduction of mainstream cigarette smoke into an inductively coupled plasma mass spectrometry (ICP-MS) has been investigated with respect to its feasibility for on-line analysis of trace elements. An automated apparatus was designed and built interfacing a smoking machine with an ICP-MS for smoke generation, collection, injection and analysis. Major and minor elements present in the particulate phase and the gas phase of mainstream cigarette smoke of 2R4F reference cigarettes have been qualitatively identified by examination of their full mass spectra. This method provides a rapid-screening analysis of the transfer of trace elements into mainstream smoke during cigarette combustion. A full suite of elements present in the whole cigarette smoke has been identified, including As, B, Ba, Br, Cd, Cl, Cs, Cu, Hg, I, K, Li, Mn, Na, Pb, Rb, Sb, Sn, Tl and Zn. Of these elements, the major portions of B, Ba, Cs, Cu, K, Li, Mn, Na, Pb, Rb, Sn, Tl and Zn are present in the particulate phase, whereas the major portion of Hg is present in the gas phase. As, Br, Cd, Cl, I and Sb exist in a distribution between the gas phase and the particulate phase. Depending on the element, the precision of measurement ranges from 5 to 25% in terms of relative standard deviation of peak height and peak area, based on the fourth puff of 2R4F mainstream cigarette smoke analyzed in five smoking replicates.

  5. Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer.

    PubMed

    Wolf, Jan-Christoph; Etter, Raphael; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2016-07-01

    An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0 μg/m(3) to 6.3 μg/m(3). Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80 W) and weight (<13 kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection. Graphical Abstract ᅟ.

  6. Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer.

    PubMed

    Wolf, Jan-Christoph; Etter, Raphael; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2016-07-01

    An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0 μg/m(3) to 6.3 μg/m(3). Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80 W) and weight (<13 kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection. Graphical Abstract ᅟ. PMID:27020924

  7. Bioimaging of metals in brain tissue by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and metallomics.

    PubMed

    Becker, J Sabine; Matusch, Andreas; Palm, Christoph; Salber, Dagmar; Morton, Kathryn A; Becker, J Susanne

    2010-02-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been developed and established as an emerging technique in the generation of quantitative images of metal distributions in thin tissue sections of brain samples (such as human, rat and mouse brain), with applications in research related to neurodegenerative disorders. A new analytical protocol is described which includes sample preparation by cryo-cutting of thin tissue sections and matrix-matched laboratory standards, mass spectrometric measurements, data acquisition, and quantitative analysis. Specific examples of the bioimaging of metal distributions in normal rodent brains are provided. Differences to the normal were assessed in a Parkinson's disease and a stroke brain model. Furthermore, changes during normal aging were studied. Powerful analytical techniques are also required for the determination and characterization of metal-containing proteins within a large pool of proteins, e.g., after denaturing or non-denaturing electrophoretic separation of proteins in one-dimensional and two-dimensional gels. LA-ICP-MS can be employed to detect metalloproteins in protein bands or spots separated after gel electrophoresis. MALDI-MS can then be used to identify specific metal-containing proteins in these bands or spots. The combination of these techniques is described in the second section.

  8. Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer

    NASA Astrophysics Data System (ADS)

    Wolf, Jan-Christoph; Etter, Raphael; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

    2016-07-01

    An active capillary plasma ionization (ACI) source was coupled to a handheld mass spectrometer (Mini 10.5; Aston Labs, West Lafayette, IN, USA) and applied to the direct gas-phase detection and quantification of chemical warfare agent (CWA) related chemicals. Complementing the discontinuous atmospheric pressure interface (DAPI) of the Mini 10.5 mass spectrometer with an additional membrane pump, a quasi-continuous sample introduction through the ACI source was achieved. Nerve agent simulants (three dialkyl alkylphosphonates, a dialkyl phosporamidate, and the pesticide dichlorvos) were detected at low gas-phase concentrations with limits of detection ranging from 1.0 μg/m3 to 6.3 μg/m3. Our results demonstrate a sensitivity enhancement for portable MS-instrumentation by using an ACI source, enabling direct, quantitative measurements of volatile organic compounds. Due to its high sensitivity, selectivity, low power consumption (<80 W) and weight (<13 kg), this instrumentation has the potential for direct on-site CWA detection as required by military or civil protection.

  9. RAPID DETERMINATION OF 237 NP AND PU ISOTOPES IN WATER BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY AND ALPHA SPECTROMETRY

    SciTech Connect

    Maxwell, S.; Jones, V.; Culligan, B.; Nichols, S.; Noyes, G.

    2010-06-23

    A new method that allows rapid preconcentration and separation of plutonium and neptunium in water samples was developed for the measurement of {sup 237}Np and Pu isotopes by inductively-coupled plasma mass spectrometry (ICP-MS) and alpha spectrometry; a hybrid approach. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via peak tailing. The method provide enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then moving Pu to DGA resin for additional removal of uranium. The decontamination factor for uranium from Pu is almost 100,000 and the decontamination factor for U from Np is greater than 10,000. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration is performed using a streamlined calcium phosphate precipitation method. Purified solutions are split between ICP-MS and alpha spectrometry so that long and short-lived Pu isotopes can be measured successfully. The method allows for simultaneous extraction of 20 samples (including QC samples) in 4 to 6 hours, and can also be used for emergency response. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu, {sup 238}Pu, and {sup 239}Pu were measured by alpha spectrometry.

  10. Determination of the total and extractable mass fractions of cadmium and lead in mineral feed by using isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Vassileva, Emilia; Hoenig, Michel

    2011-09-01

    This paper describes the determination of the total and extractable mass fractions of Cd and Pb in mineral feed test sample distributed by the Community Reference Laboratory for Heavy Metals in Feed and Food (CRL-HM), in the frame of the fifth interlaboratory comparison for the European Union National Reference Laboratories (NRL). The developed in this study protocol for the total and extractable mass fractions of Pb and Cd in mineral feed sample is based on isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS). The applied dual spiking approach reduced by 50% the number of analytical steps. The addition of hydrofluoric acid in the digestion step was found necessary to ensure a full decomposition and complete isotope equilibration. Quadrupole inductively coupled plasma mass spectrometer equipped with collision reaction interface (CRI) was employed for the measurements of Cd and Pb. Two methods for the determination of Cd were applied and compared. In the first one the high molybdenum content was reduced by introduction of matrix separation step followed by standard ICP-MS mode measurement, whereas in the second one CRI mode was used for the determination of Cd without preliminary matrix separation. The estimation of the combined uncertainty was performed according to the ISO guidelines. Uncertainty propagation was used as a tool for validation of proposed analytical procedure. Contributions from the correction for moisture content, sample homogeneity, procedural blank, instrumental background and dead time effects were evaluated in both cases. The largest uncertainty contributors for Cd and Pb is due to the within bottle homogeneity of the mineral feed sample - 50.3% and 90% respectively. The IUPAC data for isotope composition are the second major contributor to the combined uncertainty of the result for the total mass fraction of Cd in mineral feed - 43.3%. However, the ID ICP-MS results achieved from the two series of samples (partial and

  11. Applications of inductively coupled plasma-mass spectrometry in environmental radiochemistry

    USGS Publications Warehouse

    Grain, J.S.

    1996-01-01

    The state of the art in ICP-MS is now such that there are few discernible differences between radiochemical and mass spectrometric determinations of longlived radionuclides. Indeed, ICP-MS may provide better (more sensitive) data for many radionuclides, depending upon how one wishes to define "long-lived." In lowlevel determinations, sample preparation remains an important part of the analytical procedure, even with ICP-MS, but the speed and isotopic selectivity of the mass spectrometer appear to offer distinct procedural advantages over radiochemical techniques. Therefore, "radioanalytical" ICP-MS applications should continue to grow, especially in the area of radiation protection, but further research (on efficient sample introduction, for example) and method development may be required to get ICP-MS "off the ground" in the geochemical research areas that have traditionally been supported by radiochemistry.

  12. Determination of microamounts of hafnium in zirconium using inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry during their separation by ion exchange on Diphonix chelating resin.

    PubMed

    Smolik, Marek; Jakóbik-Kolon, Agata

    2009-04-01

    Inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICPMS) methods were applied to check the possibility of determination of hafnium in zirconium at a level lower than 100 ppm. A zirconium matrix of hafnium content lower than 10 ppm was obtained using a worked-out separation method exploiting ion exchange on Diphonix resin. Both methods give results in good agreement with each other as well as with those for certified reference material BCR-098 (Zircaloy-4). They were utilized in determination of Hf in the samples collected during separation of microamounts of hafnium from zirconium by the mentioned ion exchange. These results proved the earlier described method of separation on Diphonix resin to be effective even when the initial concentration of hafnium in zirconium decreases from 2.4% to 0.0082%.

  13. Determination of hafnium at the 10(-4)% level (relative to zirconium content) using neutron activation analysis, inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry.

    PubMed

    Smolik, Marek; Polkowska-Motrenko, Halina; Hubicki, Zbigniew; Jakóbik-Kolon, Agata; Danko, Bożena

    2014-01-01

    Hafnium at the very low level of 1-8 ppm (in relation to zirconium) was determined in zirconium sulfate solutions (originating from investigations of the separation of ca. 44 ppm Hf from zirconium by means of the ion exchange method) by using three independent methods: inductively coupled plasma mass spectrometry (ICP MS), neutron activation analysis (NAA) and inductively coupled plasma atomic emission spectrometry (ICP-AES). The results of NAA and ICP MS determinations were consistent with each other across the entire investigated range (the RSD of both methods did not exceed 38%). The results of ICP-AES determination were more diverse, particularly at less than 5 ppm Hf (RSD was significantly higher: 29-253%). The ion exchange method exploiting Diphonix(®) resin proved sufficient efficiency in Zr-Hf separation when the initial concentration ratio of the elements ([Zr]0/[Hf]0) ranged from 1200 to ca. 143,000.

  14. Cooking strongly coupled plasmas

    NASA Astrophysics Data System (ADS)

    Clérouin, Jean

    2015-09-01

    We present the orbital-free method for dense plasmas which allows for efficient variable ionisation molecular dynamics. This approach is a literal application of density functional theory where the use of orbitals is bypassed by a semi-classical estimation of the electron kinetic energy through the Thomas-Fermi theory. Thanks to a coherent definition of ionisation, we evidence a particular regime in which the static structure no longer depends on the temperature: the Γ-plateau. With the help of the well-known Thomas-Fermi scaling laws, we derive the conditions required to obtain a plasma at a given value of the coupling parameter and deduce useful fits. Static and dynamical properties are predicted as well as a a simple equation of state valid on the Γ-plateau. We show that the one component plasma model can be helpful to describe the correlations in real systems.

  15. THE DEVELOPMENT OF IODINE BASED IMPINGER SOLUTIONS FOR THE EFFICIENT CAPTURE OF HG USING DIRECT INJECTION NEBULIZATION - INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY ANALYSIS

    EPA Science Inventory

    Inductively coupled plasma mass spectrometry (ICP/MS) with direct injection nebulization (DIN) was used to evaluate novel impinger solution compositions capable of capturing elemental mercury (Hgo) in EPA Method 5 type sampling. An iodine based impinger solutoin proved to be ver...

  16. Potential for using isotopically altered metalloproteins in species-specific isotope dilution analysis of proteins by HPLC coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Harrington, Chris F; Vidler, Daniel S; Watts, Michael J; Hall, John F

    2005-07-01

    The production and evaluation of an isotopically enriched metalloprotein standard for use as a calibrant in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is described. Using a model system involving the copper-containing protein rusticyanin (Rc) from the bacterium Acido-thiobacillus ferrooxidans, it was possible to demonstrate the analytical conditions that could be used for the measurement of metalloproteins by on-line IDMS analysis. Rc was chosen because it is a well-characterized protein with an established amino acid sequence and can be produced in suitable quantities using a bacterial recombinant system. Three different forms of the protein were studied by organic and inorganic mass spectrometry: the native form of the protein containing a natural isotopic profile for copper, an isotopically enriched species containing virtually all of its copper as the 65Cu isotope, and the nonmetalated apo form. Incorporation of the copper isotopes into the apo form of the protein was determined using a UV-vis spectrophotometric assay and shown to be complete for each of the copper-containing species. The experimental conditions required to maintain the conformational form of the protein with a nonexchangeable copper center were established using +ve electrospray mass spectrometry. A pH 7.0 buffer was found to afford the most appropriate conditions, and this was then used with HPLC-ICP-MS to verify the stability of the copper center by analysis of mixtures of different isotopic solutions. No exchange of the enriched copper isotope from Rc with an added naturally abundant inorganic copper cation was observed under a neutral pH environment, indicating that species-specific ID-MS analysis of metalloproteins is possible.

  17. Determination of rare earth element in carbonate using laser-ablation inductively-coupled plasma mass spectrometry: an examination of the influence of the matrix on laser-ablation inductively-coupled plasma mass spectrometry analysis.

    PubMed

    Tanaka, Kazuya; Takahashi, Yoshio; Shimizu, Hiroshi

    2007-02-01

    In this study, we examined the influence of the matrix on rare earth element (REE) analyses of carbonate with laser-ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) using carbonate and NIST glass standards. A UV 213 nm Nd:YAG laser system was coupled to an ICP-MS. Laser-ablation was carried out in both He and Ar atmospheres to investigate the influence of ablation gas on the analytical results. A small amount of N2 gas was added to the carrier gas to enhance the signal intensities. Synthetic CaCO3 standards, doped with REEs, as well as NIST glasses (NIST SRM 610 and 612) were used as calibration standards. Carbonatite, which is composed of pure calcite, was analyzed as carbonate samples. The degree of the influence of the matrix on the results was evaluated by comparing the results, which were calibrated by the synthetic CaCO3 and NIST glass standards. With laser-ablation in a He atmosphere, the differences between the results calibrated by the synthetic CaCO3 and NIST glass standards were less than 10% across the REE series, except for those of La which were 25%. In contrast, for the measurements made in an Ar atmosphere, the results calibrated by the synthetic CaCO3 and NIST glass standards differed by 25-40%. It was demonstrated that the LA-ICP-MS system can provide quantitative analysis of REE concentrations in carbonate samples using non matrix-matched standards of NIST glasses. PMID:17386560

  18. Analysis of bioethanol samples through Inductively Coupled Plasma Mass Spectrometry with a total sample consumption system

    NASA Astrophysics Data System (ADS)

    Sánchez, Carlos; Lienemann, Charles-Philippe; Todolí, Jose-Luis

    2016-10-01

    Bioethanol real samples have been directly analyzed through ICP-MS by means of the so called High Temperature Torch Integrated Sample Introduction System (hTISIS). Because bioethanol samples may contain water, experiments have been carried out in order to determine the effect of ethanol concentration on the ICP-MS response. The ethanol content studied went from 0 to 50%, because higher alcohol concentrations led to carbon deposits on the ICP-MS interface. The spectrometer default spray chamber (double pass) equipped with a glass concentric pneumatic micronebulizer has been taken as the reference system. Two flow regimes have been evaluated: continuous sample aspiration at 25 μL min- 1 and 5 μL air-segmented sample injection. hTISIS temperature has been shown to be critical, in fact ICP-MS sensitivity increased with this variable up to 100-200 °C depending on the solution tested. Higher chamber temperatures led to either a drop in signal or a plateau. Compared with the reference system, the hTISIS improved the sensitivities by a factor included within the 4 to 8 range while average detection limits were 6 times lower for the latter device. Regarding the influence of the ethanol concentration on sensitivity, it has been observed that an increase in the temperature was not enough to eliminate the interferences. It was also necessary to modify the torch position with respect to the ICP-MS interface to overcome them. This fact was likely due to the different extent of ion plasma radial diffusion encountered as a function of the matrix when working at high chamber temperatures. When the torch was moved 1 mm plasma down axis, ethanolic and aqueous solutions provided statistically equal sensitivities. A preconcentration procedure has been applied in order to validate the methodology. It has been found that, under optimum conditions from the point of view of matrix effects, recoveries for spiked samples were close to 100%. Furthermore, analytical concentrations for real

  19. Inductively coupled plasma mass spectrometry with a twin quadrupole instrument using laser ablation sample introduction and monodisperse dried microparticulate injection

    SciTech Connect

    Allen, L.A.

    1997-02-01

    The focus of this dissertation is the use of a twin quadrupole inductively coupled plasma mass spectrometer (ICP-MS) for the simultaneous detection of two m/z values. The twin quadrupole ICP-MS is used with laser ablation sample introduction in both the steady state (10 Hz) and single pulse modes. Steady state signals are highly correlated and the majority of flicker noise cancels when the ratio is calculated. Using a copper sample, the isotope ratio {sup 63}Cu{sup +}/{sup 65}Cu{sup +} is measured with a relative standard deviation (RSD) of 0.26%. Transient signals for single laser pulses are also obtained. Copper isotope ratio measurements for several laser pulses are measured with an RSD of 0.85%. Laser ablation (LA) is used with steel samples to assess the ability of the twin quadrupole ICP-MS to eliminate flicker noise of minor components of steel samples. Isotopic and internal standard ratios are measured in the first part of this work. The isotope ratio {sup 52}Cr{sup +}/{sup 53}Cr{sup +} (Cr present at 1.31 %) can be measured with an RSD of 0.06 % to 0.1 %. For internal standard elements, RSDs improve from 1.9 % in the Cr{sup +} signal to 0.12% for the ratio of {sup 51}V{sup +} to {sup 52}Cr{sup +}. In the second part of this work, one mass spectrometer is scanned while the second channel measures an individual m/z value. When the ratio of these two signals is calculated, the peak shapes in the mass spectrum are improved significantly. Pulses of analyte and matrix ions from individual drops are measured simultaneously using the twin quadrupole ICP-MS with monodisperse dried microparticulate injection (MDMI). At modest Pb concentrations (500 ppm), a shoulder on the leading edge of the Li{sup +} signal becomes apparent. Space charge effects are consistent with the disturbances seen.

  20. Extraction and analysis of silver and gold nanoparticles from biological tissues using single particle inductively coupled plasma mass spectrometry.

    PubMed

    Gray, Evan P; Coleman, Jessica G; Bednar, Anthony J; Kennedy, Alan J; Ranville, James F; Higgins, Christopher P

    2013-12-17

    Expanded use of engineered nanoparticles (ENPs) in consumer products increases the potential for environmental release and unintended biological exposures. As a result, measurement techniques are needed to accurately quantify ENP size, mass, and particle number distributions in biological matrices. This work combines single particle inductively coupled plasma mass spectrometry (spICPMS) with tissue extraction to quantify and characterize metallic ENPs in environmentally relevant biological tissues for the first time. ENPs were extracted from tissues via alkaline digestion using tetramethylammonium hydroxide (TMAH). Method development was performed using ground beef and was verified in Daphnia magna and Lumbriculus variegatus . ENPs investigated include 100 and 60 nm Au and Ag stabilized by polyvynylpyrrolidone (PVP). Mass- and number-based recovery of spiked Au and Ag ENPs was high (83-121%) from all tissues tested. Additional experiments suggested ENP mixtures (60 and 100 nm Ag ENPs) could be extracted and quantitatively analyzed. Biological exposures were also conducted to verify the applicability of the method for aquatic organisms. Size distributions and particle number concentrations were determined for ENPs extracted from D. magna exposed to 98 μg/L 100 nm Au and 4.8 μg/L 100 nm Ag ENPs. The D. magna nanoparticulate body burden for Au ENP uptake was 613 ± 230 μg/kgww, while the measured nanoparticulate body burden for D. magna exposed to Ag ENPs was 59 ± 52 μg/kgww. Notably, the particle size distributions determined from D. magna tissues suggested minimal shifts in the size distributions of ENPs accumulated, as compared to the exposure media.

  1. Trace rare earth element detection in food and agricultural products based on flow injection walnut shell packed microcolumn preconcentration coupled with inductively coupled plasma mass spectrometry.

    PubMed

    Li, Yan; Yang, Jia-lin; Jiang, Yan

    2012-03-28

    With the extensive use of rare earth elements (REEs) in agriculture as fertilizer and feed additives, the concentration of REEs has increased in environmental and biological samples and finally impaired human health by food chain accumulation. The determination of trace REEs has gained considerable importance because of their toxicity and increasing occurrence. In this work, walnut shell has been used as the green adsorbent in online preconcentration and detection of REEs in food and agricultural products coupled with inductively coupled plasma mass spectrometry (ICP-MS). Because of the porous surface and abundant -COO(-) groups on the walnut shell surface, the walnut shell-packed microcolumn provides high adsorption efficiency and high tolerable capacity for coexisting ions. Under the optimized conditions, the adsorption efficiency of the walnut shell packed microcolumn was as high as 98.9% for 15 REEs, and the tolerable concentration ratios were between 2000 and 80,000,000 for 37 kinds of coexisting interfering ions. The enhancement factors achieved were 79-102 for 15 REEs with a sample loading volume of 4.7 mL. The detection limits were in the range of 2-34 pg g(-1). The relative standard deviation for 11 replicate preconcentrations of 2.5 ng L(-1) REEs solution ranged from 0.5 to 2.0%. The present method was successfully applied to selective determination of REEs in 4 environmental and biological certified reference materials and 18 locally collected food and agricultural products.

  2. Electrothermal vaporization coupled with inductively coupled plasma array-detector mass spectrometry for the multielement analysis of Al2O3 ceramic powders

    SciTech Connect

    Peschel, Birgit U.; Andrade, Francisco J.; Wetzel, William C.; Schilling, G D.; Hieftje, Gary M.; Broekaert, Jose AC; Sperline, Roger; Denton, M BONNER.; Barinaga, Charles J.; Koppenaal, David W.

    2006-01-01

    An electrothermal vaporization (ETV) system useful for the analysis of solutions and slurries has been coupled with a sector-field inductively coupled plasma mass spectrometer (ICP-MS) equipped with an array detector. The ability of this instrument to record the transient signals produced in ETV-ICP-MS is demonstrated. Detection limits for Mn, Fe, Co, Ni, Cu, Zn and Ga are in the range of 4-60 pg ?L-1 for aqueous solutions and in the low ?g g-1 range for the analysis of 10 mg mL-1 slurries of Al2O3 powders. The dynamic ranges measured for Fe, Cu and Ga spanned 3-5 orders of magnitude when the detector was operated in the low-gain mode and appear to be limited by the ETV system. Trace amounts of Fe, Cu and Ga could be directly determined in Al2O3 powders at the 2-270 ?g g-1 level without the use of thermochemical reagents. The results well agree with literature values for Fe, whereas deviations of 30-50% at the 2-90 ?g g-1 level for Cu and Ga were found.

  3. Determination of actinides in environmental and biological samples using high-performance chelation ion chromatography coupled to sector-field inductively coupled plasma mass spectrometry.

    PubMed

    Truscott, J B; Jones, P; Fairman, B E; Evans, E H

    2001-08-31

    High-performance chelation ion chromatography, using a neutral polystyrene substrate dynamically loaded with 0.1 mM dipicolinic acid, coupled with sector-field inductively coupled plasma mass spectrometry has been successfully used for the separation of the actinides thorium, uranium, americium, neptunium and plutonium. Using this column it was possible to separate the various actinides from each other and from a complex sample matrix. In particular, it was possible to separate plutonium and uranium to facilitate the detection of the former free of spectral interference. The column also exhibited some selectivity for different oxidation states of Np, Pu and U. Two oxidation states each for plutonium and neptunium were found, tentatively identified as Np(V) and Pu(III) eluting at the solvent front, and Np(IV) and Pu(IV) eluting much later. Detection limits were 12, 8, and 4 fg for 237Np, 239Pu, and 241Am, respectively, for a 0.5 ml injection. The system was successfully used for the determination of 239Pu in NIST 4251 Human Lung and 4353 Rocky Flats Soil, with results of 570+/-29 and 2939+/-226 fg g(-1), respectively, compared with a certified range of 227-951 fg g(-1) for the former and a value of 3307+/-248 fg g(-1) for the latter. PMID:11589474

  4. Evaluation of Hydrodynamic Chromatography Coupled with UV-Visible, Fluorescence and Inductively Coupled Plasma Mass Spectrometry Detectors for Sizing and Quantifying Colloids in Environmental Media

    PubMed Central

    Philippe, Allan; Schaumann, Gabriele E.

    2014-01-01

    In this study, we evaluated hydrodynamic chromatography (HDC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of nanoparticles in environmental samples. Using two commercially available columns (Polymer Labs-PDSA type 1 and 2), a set of well characterised calibrants and a new external time marking method, we showed that flow rate and eluent composition have few influence on the size resolution and, therefore, can be adapted to the sample particularity. Monitoring the agglomeration of polystyrene nanoparticles over time succeeded without observable disagglomeration suggesting that even weak agglomerates can be measured using HDC. Simultaneous determination of gold colloid concentration and size using ICP-MS detection was validated for elemental concentrations in the ppb range. HDC-ICP-MS was successfully applied to samples containing a high organic and ionic background. Indeed, online combination of UV-visible, fluorescence and ICP-MS detectors allowed distinguishing between organic molecules and inorganic colloids during the analysis of Ag nanoparticles in synthetic surface waters and TiO2 and ZnO nanoparticles in commercial sunscreens. Taken together, our results demonstrate that HDC-ICP-MS is a flexible, sensitive and reliable method to measure the size and the concentration of inorganic colloids in complex media and suggest that there may be a promising future for the application of HDC in environmental science. Nonetheless the rigorous measurements of agglomerates and of matrices containing natural colloids still need to be studied in detail. PMID:24587393

  5. Speciation of chromium and its distribution in tea leaves and tea infusion using titanium dioxide nanotubes packed microcolumn coupled with inductively coupled plasma mass spectrometry.

    PubMed

    Chen, Shizhong; Zhu, Shengping; He, Yuanyuan; Lu, Dengbo

    2014-05-01

    Titanium dioxide nanotubes (TDNTs) were used as a solid phase extraction adsorbent for chromium species by a packed microcolumn coupled with inductively coupled plasma mass spectrometry (ICP-MS), including total, suspended and soluble chromium as well as Cr(III) and Cr(VI) in tea leaves and tea infusion. The experimental results indicated that Cr(III) was quantitatively retained on TDNTs in the pH range of 5.0-8.0, while Cr(VI) remained in the solution. The total chromium was determined after reducing Cr(VI) to Cr(III). The concentration of Cr(VI) is calculated by the difference between total chromium and Cr(III). Under optimal conditions, the detection limits of this method were 0.0075ngmL(-1) for Cr(III). The relative standard deviation was 3.8% (n=9, c=1.0ngmL(-1)). This method was applied for the analysis of the speciation of chromium and its distribution and content in tea leaves, tea infusion and a certified reference material of tea leaves with satisfactory results.

  6. Evaluation of hydrodynamic chromatography coupled with UV-visible, fluorescence and inductively coupled plasma mass spectrometry detectors for sizing and quantifying colloids in environmental media.

    PubMed

    Philippe, Allan; Schaumann, Gabriele E

    2014-01-01

    In this study, we evaluated hydrodynamic chromatography (HDC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of nanoparticles in environmental samples. Using two commercially available columns (Polymer Labs-PDSA type 1 and 2), a set of well characterised calibrants and a new external time marking method, we showed that flow rate and eluent composition have few influence on the size resolution and, therefore, can be adapted to the sample particularity. Monitoring the agglomeration of polystyrene nanoparticles over time succeeded without observable disagglomeration suggesting that even weak agglomerates can be measured using HDC. Simultaneous determination of gold colloid concentration and size using ICP-MS detection was validated for elemental concentrations in the ppb range. HDC-ICP-MS was successfully applied to samples containing a high organic and ionic background. Indeed, online combination of UV-visible, fluorescence and ICP-MS detectors allowed distinguishing between organic molecules and inorganic colloids during the analysis of Ag nanoparticles in synthetic surface waters and TiO₂ and ZnO nanoparticles in commercial sunscreens. Taken together, our results demonstrate that HDC-ICP-MS is a flexible, sensitive and reliable method to measure the size and the concentration of inorganic colloids in complex media and suggest that there may be a promising future for the application of HDC in environmental science. Nonetheless the rigorous measurements of agglomerates and of matrices containing natural colloids still need to be studied in detail.

  7. Speciation of chromium and its distribution in tea leaves and tea infusion using titanium dioxide nanotubes packed microcolumn coupled with inductively coupled plasma mass spectrometry.

    PubMed

    Chen, Shizhong; Zhu, Shengping; He, Yuanyuan; Lu, Dengbo

    2014-05-01

    Titanium dioxide nanotubes (TDNTs) were used as a solid phase extraction adsorbent for chromium species by a packed microcolumn coupled with inductively coupled plasma mass spectrometry (ICP-MS), including total, suspended and soluble chromium as well as Cr(III) and Cr(VI) in tea leaves and tea infusion. The experimental results indicated that Cr(III) was quantitatively retained on TDNTs in the pH range of 5.0-8.0, while Cr(VI) remained in the solution. The total chromium was determined after reducing Cr(VI) to Cr(III). The concentration of Cr(VI) is calculated by the difference between total chromium and Cr(III). Under optimal conditions, the detection limits of this method were 0.0075ngmL(-1) for Cr(III). The relative standard deviation was 3.8% (n=9, c=1.0ngmL(-1)). This method was applied for the analysis of the speciation of chromium and its distribution and content in tea leaves, tea infusion and a certified reference material of tea leaves with satisfactory results. PMID:24360447

  8. Ion-pair chromatography coupled to inductively coupled plasma-mass spectrometry (IPC-ICP-MS) as a method for thiomolybdate speciation in natural waters.

    PubMed

    Lohmayer, Regina; Reithmaier, Gloria Maria Susanne; Bura-Nakić, Elvira; Planer-Friedrich, Britta

    2015-03-17

    Molybdenum precipitates preferentially under reducing conditions; therefore, its occurrence in sediment records is used as an indicator of paleoredox conditions. Although thiomolybdates (MoO4-xSx(2-) with x = 1-4) supposedly are necessary intermediates in the process of molybdenum precipitation under anoxic conditions, there is no information about their abundance in natural environments, because of a lack of element-specific methods with sufficiently low detection limits. Here, we optimized ion-pair chromatographic separation for coupling to an inductively coupled plasma-mass spectrometry detector (IPC-ICP-MS). 2-Propanol (10%-25% gradient) replaced the previously used acetonitrile (25%-75%) as the solvent, to reduce the carbon load into the plasma. In synthetic solutions, formation of thiomolybdates was found to occur spontaneously in the presence of excess sulfide and the degree of thiolation was highest at pH 7. Excess hydroxyl led to a transformation of thiomolybdates to molybdate. Under acidic to neutral conditions, precipitation of molybdenum and hydrolysis of tetrathiomolybdate were observed. Flash-freezing was found to be suitable to stabilize tetrathiomolybdate, with <4% transformation over more than two months. High ionic strengths matrices (>2 mM) negatively affected the detection of molybdate, which eluted mainly in the dead volume, but had no negative effect on higher thiolated molybdates. Detection limits were ∼10 nM. With the newly developed IPC-ICP-MS method, thiomolybdates were found to form spontaneously in euxinic marine waters after adding a molybdate spike and occur naturally in sulfidic geothermal waters.

  9. A high-efficiency cross-flow micronebulizer interface for capillary electrophoresis and inductively coupled plasma mass spectrometry.

    PubMed

    Li, J; Umemura, T; Odake, T; Tsunoda, K

    2001-12-15

    A pneumatic nebulizer interface for capillary electrophoresis (CE) and inductively coupled plasma mass spectrometry (ICPMS) is reported. The interface is constructed using a high-efficiency cross-flow micronebulizer (HECFMN) and has the following features. (1) Makeup solutions can be fed to the interface by nebulizer self-aspiration and liquid gravity pressurization. (2) The liquid dead volume of the interface is approximately 65 nL, much smaller than those (200-2500 nL) reported for other interfaces. (3) The interface can be stably operated at a liquid flow rate down to 5 microL/min with a high analyte transport efficiency up to 95% to the plasma and (4) does not induce noticeable laminar flow in the CE capillary at typical nebulizer gas flow rates of 0.8-1.2 L/min. Because of these features, baseline resolution of 10 lanthanides with a CE-ICPMS system using the HECFMN interface is achieved, and detection limits and peak asymmetry are 0.05-1 microg/L and 0.93-1.23, respectively, improved significantly over those reported previously for a CE-ICPMS system using a high-efficiency nebulizer interface. Peak precision for the 10 lanthanides is in the range of 6.2-12.3% RSD (N = 5). Peak widths are from 9.1 s for 139La to 17.9 s for 175Lu. The effects of nebulizer gas flow rate, makeup solution flow rate, and spray chamber volume on CE-ICPMS signal intensity and separation are also evaluated for the HECFMN interface by the separation of Cr3+ and Cr2O7(2-).

  10. Validation of the at-sea inductively-coupled plasma mass spectrometer (ICPMS)

    SciTech Connect

    Esser, B K; Volpe, A M.

    1998-09-28

    The ability of ICPMS to rapidly, precisely and accurately determine ultratrace metal concentrations and isotopic compositions in the marine environment will allow real-time water mass tracking using diagnostic trace metals and field determination of long-lived radionuclides. The LLNL system is designed to operate in three analytical modes: l A real-time analysis mode with rapid cycle times for mapping trace metal distributions in dynamic environments l An in-line pre-concentration/matrix elimination mode for mapping a broader range of trace metal distributions with greater sensitivity and precision in the coastal ocean l An off-line pre-concentration mode for achieving the sensitivity required to determine long-lived radionuclide concentrations and isotopic compositions. To validate these operational modes a representative set of real-world samples is required to demonstrate that the system works across the salinity and trace metal concentration range expected in the dynamically changing marine environment. Samples collected over a short period, along a transect that spans the salinity gradient from river to coastal ocean is preferable in terms of expected salinity and trace metal concentration range, and in assessing data quality by allowing interpretation of the data in the context of known oceanographic and physical processes. Laboratory validation of the ICPMS capability is twofold. The first part involves collection of a representative set of estuarine samples across a salinity gradient using trace metal sampling techniques. Then, trace metal concentrations and isotopic compositions of the collected samples were determined using the ICPMS instrument in the field van.

  11. Unambiguous characterization of gunshot residue particles using scanning laser ablation and inductively coupled plasma-mass spectrometry.

    PubMed

    Abrego, Zuriñe; Ugarte, Ana; Unceta, Nora; Fernández-Isla, Alberto; Goicolea, M Aranzazu; Barrio, Ramón J

    2012-03-01

    A new method based on scanning laser ablation and inductively coupled plasma-mass spectrometry (LA-ICPMS) for the detection and identification of gunshot residue (GSR) particles from firearms discharges has been developed. Tape lifts were used to collect inorganic residues from skin surfaces. The laser ablation pattern and ICPMS conditions were optimized for the detection of metals present in GSR, such as (121)Sb, (137)Ba, and (208)Pb. Other isotopes ((27)Al, (29)Si, (31)P, (33)S, (35)Cl, (39)K, (44)Ca, (57)Fe, (60)Ni, (63)Cu, (66)Zn, and (118)Sn) were monitored during the ICPMS analyses to obtain additional information to possibly classify the GSR particles as either characteristic of GSR or consistent with GSR. In experiments with real samples, different firearms, calibers, and ammunitions were used. The performed method evaluation confirms that the developed methodology can be used as an alternative to the standard scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) technique, with the significant advantage of drastically reducing the analysis time to less than 66 min. PMID:22304477

  12. Determining transport efficiency for the purpose of counting and sizing nanoparticles via single particle inductively coupled plasma mass spectrometry.

    PubMed

    Pace, Heather E; Rogers, Nicola J; Jarolimek, Chad; Coleman, Victoria A; Higgins, Christopher P; Ranville, James F

    2011-12-15

    Currently there are few ideal methods for the characterization of nanoparticles in complex, environmental samples, leading to significant gaps in toxicity and exposure assessments of nanomaterials. Single particle-inductively coupled plasma-mass spectrometry (spICPMS) is an emerging technique that can both size and count metal-containing nanoparticles. A major benefit of the spICPMS method is its ability to characterize nanoparticles at concentrations relevant to the environment. This paper presents a practical guide on how to count and size nanoparticles using spICPMS. Different methods are investigated for measuring transport efficiency (i.e., nebulization efficiency), an important term in the spICPMS calculations. In addition, an alternative protocol is provided for determining particle size that broadens the applicability of the technique to all types of inorganic nanoparticles. Initial comparison, using well-characterized, monodisperse silver nanoparticles, showed the importance of having an accurate transport efficiency value when determining particle number concentration and, if using the newly presented protocol, particle size. Ultimately, the goal of this paper is to provide improvements to nanometrology by further developing this technique for the characterization of metal-containing nanoparticles.

  13. Lead concentrations and isotope ratios in street dust determined by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

    PubMed

    Nageotte, S M; Day, J P

    1998-01-01

    A major source of environmental lead, particularly in urban areas, has been from the combustion of leaded petrol. Street dust has previously been used to assess urban lead contamination, and the dust itself can also be a potential source of lead ingestion, particularly to children. The progressive reduction of lead in petrol, in recent years, would be expected to have been reflected in a reduction of lead in urban dust. We have tested this hypothesis by repeating an earlier survey of Manchester street dust and carrying out a comparable survey in Paris. Samples were collected from streets and parks, lead was extracted by digestion with concentrated nitric acid and determined by electrothermal atomic absorption spectrometry. Lead isotope ratios were measured by inductively coupled plasma mass spectrometry. Results for Manchester show that lead concentrations have fallen by about 40% (street dust averages, 941 micrograms g-1 (ppm) in 1975 down to 569 ppm in 1997). In Paris, the lead levels in street dust are much higher and significant differences were observed between types of street (not seen in Manchester). Additionally, lead levels in parks were much lower than in Manchester. Samples collected under the Eiffel Tower had very high concentrations and lead isotope ratios showed that this was unlikely to be fallout from motor vehicles but could be due to the paint used on the tower. Isotope ratios measurements also revealed that lead additives used in France and the UK come from different sources.

  14. [Interest and limits of inductively coupled plasma mass spectrometry (ICP-MS) for urinary diagnosis of radionuclide internal contamination].

    PubMed

    Lecompte, Yannick; Bohand, Sandra; Laroche, Pierre; Cazoulat, Alain

    2013-01-01

    After a review of radiometric reference methods used in radiotoxicology, analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for the workplace urinary diagnosis of internal contamination by radionuclides are evaluated. A literature review (covering the period from 2000 to 2012) is performed to identify the different applications of ICP-MS in radiotoxicology for urine analysis. The limits of detection are compared to the recommendations of the International commission on radiological protection (ICRP 78: "Individual monitoring for internal exposure of workers"). Except one publication describing the determination of strontium-90 (β emitter), all methods using ICP-MS reported in the literature concern actinides (α emitters). For radionuclides with a radioactive period higher than 10(4) years, limits of detection are most often in compliance with ICRP publication 78 and frequently lower than radiometric methods. ICP-MS allows the specific determination of plutonium-239 + 240 isotopes which cannot be discriminated by α spectrometry. High resolution ICP-MS can also measure uranium isotopic ratios in urine for total uranium concentrations lower than 20 ng/L. The interest of ICP-MS in radiotoxicology concerns essentially the urinary measurement of long radioactive period actinides, particularly for uranium isotope ratio determination and 239 and 240 plutonium isotopes discrimination. Radiometric methods remain the most efficient for the majority of other radionuclides.

  15. Influence of sample matrix components on the selection of calibration strategies in electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Fonseca, R. W.; Miller-Ihli, N. J.

    1996-11-01

    Quantification of both digested and slurry samples were studied using ultrasonic slurry electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS). The results of external calibration using aqueous standards, method of additions, and In as an internal standard were compared. The elements studied include: Mn, Ni and Cu and the materials analyzed include: NIST SRM 1548 total diet and SRM 1549 milk powder. Palladium was used as a physical carrier and oxygen ashing was used to remove the organic part of the slurry matrix. Different degrees of matrix suppression effects were observed when different skimmer cones were employed. Aging of the skimmer cone and consequent loss of its original circular symmetry and decrease in orifice size resulted in differences in sampling of the ion beam and changes in the degree of matrix effects were observed as the skimmer cone was rotated. The presence of matrix suppression effects is evidenced by strong suppressions in the Ar 2, C and analyte signals. When matrix suppression effects were present, the method of external calibration provided low recoveries (average accuracy 73 ± 12%), therefore it was necessary to use the method of additions to compensate for these problems, providing an average accuracy of 108 ± 13%. When matrix effects were absent, the external calibration method resulted in an average accuracy of 101 ± 16%.

  16. Estimation of honey authenticity by multielements characteristics using inductively coupled plasma-mass spectrometry (ICP-MS) combined with chemometrics.

    PubMed

    Chudzinska, M; Baralkiewicz, D

    2010-01-01

    In our study the mineral content of 55 honey samples, which represented three different types of honey: honeydew, buckwheat and rape honey from different areas in Poland, was evaluated. Determination of 13 elements (Al, B, Ba, Ca, Cd, Cu, K, Mg, Mn, Na, Ni, Pb, Zn) was performed using inductively coupled plasma-mass spectrometry. We tried to prove that the analysis of quality and quantity of honey elements could be used to define honey origin by using ICP-MS as a technique for simultaneous determination of elements. Chemometric methods, such as CA and PCA, were applied to classify honey according to mineral content. CA showed three clusters corresponding to the three botanical origins of honey. PCA permitted the reduction of 13 variables to four principal components explaining 77.19% of the total variance. The first most important principal component was strongly associated with the value of K, Al, Ni and Cd. This study revealed that CA and PCA analysis appear useful tools for differentiation of honey samples authenticity using the profile of mineral content and they highlighted the relationship between the elements distribution and honey type.

  17. Characterization of the elemental composition of newborn blood spots using sector-field inductively coupled plasma-mass spectrometry

    PubMed Central

    Langer, Erica K.; Johnson, Kimberly J.; Shafer, Martin M.; Gorski, Patrick; Overdier, Joel; Musselman, Jessica; Ross, Julie A.

    2010-01-01

    We developed extraction and analysis protocols for element detection in neonatal blood spots (NBSs) using sector-field inductively coupled plasma-mass spectrometry (SF-ICP-MS). A 5% (v/v) nitric acid element extraction protocol was optimized and used to simultaneously measure 28 elements in NBS card filter paper and 150 NBSs. NBS element concentrations were corrected for filter paper background contributions estimated from measurements in samples obtained from either unspotted or spotted NBS cards. A lower 95% uncertainty limit (UL) that accounted for ICP-MS method, filter paper element concentration, and element recovery uncertainties was calculated by standard methods for each individual’s NBS element concentration. Filter paper median element levels were highly variable within and between lots for most elements. After accounting for measurement uncertainties, 11 elements (Ca, Cs, Cu, Fe, K, Mg, Na, P, Rb, S, Zn) had lower 95% ULs >0 ng/spot with estimated concentrations ranging from 0.05->50,000 ng/spot in ≥50% of NBS samples in both correction methods. In a NBS sample minority, Li, Cd, Cs, Cr, Ni, Mo, and Pb had estimated concentrations ≥20-fold higher than the respective median level. Taking measurement uncertainties into account, this assay could be used for semiquantitative newborn blood element measurement and for detection of individuals exposed to supraphysiologic levels of some trace elements. Adequate control of filter paper element contributions remains the primary obstacle to fully quantitative element measurement in newborn blood using NBSs. PMID:20588324

  18. The effect of ultrafast laser wavelength on ablation properties and implications on sample introduction in inductively coupled plasma mass spectrometry

    SciTech Connect

    LaHaye, N. L.; Harilal, S. S.; Diwakar, P. K.; Hassanein, A.; Kulkarni, P.

    2013-07-14

    We investigated the role of femtosecond (fs) laser wavelength on laser ablation (LA) and its relation to laser generated aerosol counts and particle distribution, inductively coupled plasma-mass spectrometry (ICP-MS) signal intensity, detection limits, and elemental fractionation. Four different NIST standard reference materials (610, 613, 615, and 616) were ablated using 400 nm and 800 nm fs laser pulses to study the effect of wavelength on laser ablation rate, accuracy, precision, and fractionation. Our results show that the detection limits are lower for 400 nm laser excitation than 800 nm laser excitation at lower laser energies but approximately equal at higher energies. Ablation threshold was also found to be lower for 400 nm than 800 nm laser excitation. Particle size distributions are very similar for 400 nm and 800 nm wavelengths; however, they differ significantly in counts at similar laser fluence levels. This study concludes that 400 nm LA is more beneficial for sample introduction in ICP-MS, particularly when lower laser energies are to be used for ablation.

  19. Inductively coupled plasma-mass spectrometric method for the determination of dissolved trace elements in natural water

    USGS Publications Warehouse

    Garbarino, J.R.; Taylor, Howard E.

    1996-01-01

    An inductively coupled plasma-mass spectrometry method was developed for the determination of dissolved Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sr, Tl, U, V, and Zn in natural waters. Detection limits are generally in the 50-100 picogram per milliliter (pg/mL) range, with the exception of As which is in the 1 microgram per liter (ug/L) range. Interferences associated with spectral overlap from concomitant isotopes or molecular ions and sample matrix composition have been identified. Procedures for interference correction and reduction related to isotope selection, instrumental operating conditions, and mathematical data processing techniques are described. Internal standards are used to minimize instrumental drift. The average analytical precision attainable for 5 times the detection limit is about 16 percent. The accuracy of the method was tested using a series of U.S. Geological Survey Standard Reference Water Standards (SWRS), National Research Council Canada Riverine Water Standard, and National Institute of Standards and Technology (NIST) Trace Elements in Water Standards. Average accuracies range from 90 to 110 percent of the published mean values.

  20. Visualizing fossilization using laser ablation-inductively coupled plasma-mass spectrometry maps of trace elements in Late Cretaceous bones

    USGS Publications Warehouse

    Koenig, A.E.; Rogers, R.R.; Trueman, C.N.

    2009-01-01

    Elemental maps generated by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) provide a previously unavailable high-resolution visualization of the complex physicochemical conditions operating within individual bones during the early stages of diagenesis and fossilization. A selection of LA-ICP-MS maps of bones collected from the Late Cretaceous of Montana (United States) and Madagascar graphically illustrate diverse paths to recrystallization, and reveal unique insights into geochemical aspects of taphonomic history. Some bones show distinct gradients in concentrations of rare earth elements and uranium, with highest concentrations at external bone margins. Others exhibit more intricate patterns of trace element uptake related to bone histology and its control on the flow paths of pore waters. Patterns of element uptake as revealed by LA-ICP-MS maps can be used to guide sampling strategies, and call into question previous studies that hinge upon localized bulk samples of fossilized bone tissue. LA-ICP-MS maps also allow for comparison of recrystallization rates among fossil bones, and afford a novel approach to identifying bones or regions of bones potentially suitable for extracting intact biogeochemical signals. ?? 2009 Geological Society of America.

  1. Characterization of silver nanoparticles using flow-field flow fractionation interfaced to inductively coupled plasma mass spectrometry.

    PubMed

    Poda, A R; Bednar, A J; Kennedy, A J; Harmon, A; Hull, M; Mitrano, D M; Ranville, J F; Steevens, J

    2011-07-01

    The ability to detect and identify the physiochemical form of contaminants in the environment is important for degradation, fate and transport, and toxicity studies. This is particularly true of nanomaterials that exist as discrete particles rather than dissolved or sorbed contaminant molecules in the environment. Nanoparticles will tend to agglomerate or dissolve, based on solution chemistry, which will drastically affect their environmental properties. The current study investigates the use of field flow fractionation (FFF) interfaced to inductively coupled plasma-mass spectrometry (ICP-MS) as a sensitive and selective method for detection and characterization of silver nanoparticles. Transmission electron microscopy (TEM) is used to verify the morphology and primary particle size and size distribution of precisely engineered silver nanoparticles. Subsequently, the hydrodynamic size measurements by FFF are compared to dynamic light scattering (DLS) to verify the accuracy of the size determination. Additionally, the sensitivity of the ICP-MS detector is demonstrated by fractionation of μg/L concentrations of mixed silver nanoparticle standards. The technique has been applied to nanoparticle suspensions prior to use in toxicity studies, and post-exposure biological tissue analysis. Silver nanoparticles extracted from tissues of the sediment-dwelling, freshwater oligochaete Lumbriculus variegatus increased in size from approximately 31-46nm, indicating a significant change in the nanoparticle characteristics during exposure.

  2. Inductively coupled plasma mass-spectrometric determination of platinum in excretion products of client-owned pet dogs.

    PubMed

    Janssens, T; Brouwers, E E M; de Vos, J P; de Vries, N; Schellens, J H M; Beijnen, J H

    2015-06-01

    Residues of antineoplastic drugs in canine excretion products may represent exposure risks to veterinary personnel, owners of pet dogs and other animal care-takers. The aim of this study was to measure the extent and duration of platinum (Pt) excretion in pet dogs treated with carboplatin. Samples were collected before and up to 21 days after administration of carboplatin. We used validated, ultra-sensitive, inductively coupled plasma-mass spectrometry assays to measure Pt in canine urine, faeces, saliva, sebum and cerumen. Results showed that urine is the major route of elimination of Pt in dogs. In addition, excretion occurs via faeces and saliva, with the highest amounts eliminated during the first 5 days. The amount of excreted Pt decreased over time but was still quantifiable at 21 days after administration of carboplatin. In conclusion, increased Pt levels were found in all measured excretion products up to 21 days after administration of carboplatin to pet dogs, with urine as the main route of excretion. These findings may be used to further adapt current veterinary guidelines on safe handling of antineoplastic drugs and treated animals. PMID:23714139

  3. [Determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry].

    PubMed

    Lin, Li; Chen, Guang; Chen, Yuhong

    2011-07-01

    A method was established for the determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP/ MS). Alkaline extraction and IC-ICP/MS were applied as the sample pre-treatment method and the detection technique respectively, for iodate and iodide determination. Moreover, high-temperature pyrolysis absorption was adopted as the pre-treatment method for total iodine analysis, which finally converted all the iodine species into iodide and measured the iodide by IC-ICP/MS. The recoveries of iodine for alkaline extraction and high-temperature pyrolysis absorption were 89.6%-97.5% and 95.2%-111.2%, respectively. The results were satisfactory. The detection limit of iodine was 0.010 mg/kg. The iodine and its speciation contents in several kinds of plant samples such as seaweeds, kelp, cabbage, tea leaf and spinach were investigated. It was shown that the iodine in seaweeds mainly existed as organic iodine; while the ones in kelp, cabbage, tea leaf and spinach mainly existed as inorganic iodine.

  4. Multielemental analysis in vegetable edible oils by inductively coupled plasma mass spectrometry after solubilisation with tetramethylammonium hydroxide.

    PubMed

    Savio, Marianela; Ortiz, María S; Almeida, César A; Olsina, Roberto A; Martinez, Luis D; Gil, Raúl A

    2014-09-15

    Trace metals have negative effects on the oxidative stability of edible oils and they are important because of possibility for oils characterisation. A single-step procedure for trace elemental analysis of edible oils is presented. To this aim, a solubilisation with tetramethylammonium hydroxide (TMAH) was assayed prior to inductively coupled plasma mass spectrometry detection. Small amounts of TMAH were used, resulting in high elemental concentrations. This method was applied to edible oils commercially available in Argentine. Elements present in small amounts (Cu, Ge, Mn, Mo, Ni, Sb, Sr, Ti, and V) were determined in olive, corn, almond and sunflower oils. The limits of detection were between 0.004 μg g(-1) for Mn and Sr, and 0.32 μg g(-1) for Sb. Principal components analysis was used to correlate the content of trace metals with the type of oils. The two first principal components retained 91.6% of the variability of the system. This is a relatively simple and safe procedure, and could be an attractive alternative for quality control, traceability and routine analysis of edible oils.

  5. A rugged and transferable method for determining blood cadmium, mercury, and lead with inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    McShane, William J.; Pappas, R. Steven; Wilson-McElprang, Veronica; Paschal, Dan

    2008-06-01

    A simple, high-throughput method for determining total cadmium, mercury, and lead in blood in cases of suspected exposure, using inductively coupled plasma-mass spectrometry (ICP-MS), has been developed and validated. One part matrix-matched standards, blanks, or aliquots of blood specimens were diluted with 49 parts of a solution containing 0.25% (w/w) tetramethylammonium hydroxide; 0.05% v/v Triton X-100 (blood cell membranes and protein solubilization); 0.01% (w/v) ammonium pyrolidinedithiocarbamate (mercury memory effect prevention and oxidation state stabilization, solubilization by complexation of all three metals); 1% v/v isopropanol (signal enhancement); and 10 μg/L iridium (internal standard). Thus the final dilution factor is 1 + 49. The method provides the basis for the determination of total cadmium, mercury, and lead for assessment of environmental, occupational, accidental ingestion or elevated exposures from other means. Approximately 80 specimens, including blanks, calibration standards, and quality control materials can be processed in an 8-h day. The method has been evaluated by examining reference materials from the National Institute of Standards and Technology, as well as by participation in six rounds of proficiency testing intercomparisons led by the Wadsworth Center of the New York State Department of Health. This method was developed for the purpose of increasing U.S. emergency response laboratory capacity. To this end, 33 U.S. state, and 1 district health department laboratories have validated this method in their own laboratories.

  6. Application of Inductively Coupled Plasma Mass Spectrometry to the determination of uranium isotope ratios in individual particles for nuclear safeguards

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao Zhi; Esaka, Fumitaka; Esaka, Konomi T.; Magara, Masaaki; Sakurai, Satoshi; Usuda, Shigekazu; Watanabe, Kazuo

    2007-10-01

    The capability of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of uranium isotope ratios in individual particles was determined. For this purpose, we developed an experimental procedure including single particle transfer with a manipulator, chemical dissolution and isotope ratio analysis, and applied to the analysis of individual uranium particles in certified reference materials (NBL CRM U050 and U350). As the result, the 235U/ 238U isotope ratio for the particle with the diameter between 0.5 and 3.9 μm was successfully determined with the deviation from the certified ratio within 1.8%. The relative standard deviation (R.S.D.) of the 235U/ 238U isotope ratio was within 4.2%. Although the analysis of 234U/ 238U and 236U/ 238U isotope ratios gave the results with inferior precision, the R.S.D. within 20% was possible for the measurement of the particle with the diameter more than 2.1 μm. The developed procedure was successfully applied to the analysis of a simulated environmental sample prepared from a mixture of indoor dust (NIST SRM 2583) and uranium particles (NBL CRM U050, U350 and U950a). From the results, the proposed procedure was found to be an alternative analytical tool for nuclear safeguards.

  7. Unambiguous characterization of gunshot residue particles using scanning laser ablation and inductively coupled plasma-mass spectrometry.

    PubMed

    Abrego, Zuriñe; Ugarte, Ana; Unceta, Nora; Fernández-Isla, Alberto; Goicolea, M Aranzazu; Barrio, Ramón J

    2012-03-01

    A new method based on scanning laser ablation and inductively coupled plasma-mass spectrometry (LA-ICPMS) for the detection and identification of gunshot residue (GSR) particles from firearms discharges has been developed. Tape lifts were used to collect inorganic residues from skin surfaces. The laser ablation pattern and ICPMS conditions were optimized for the detection of metals present in GSR, such as (121)Sb, (137)Ba, and (208)Pb. Other isotopes ((27)Al, (29)Si, (31)P, (33)S, (35)Cl, (39)K, (44)Ca, (57)Fe, (60)Ni, (63)Cu, (66)Zn, and (118)Sn) were monitored during the ICPMS analyses to obtain additional information to possibly classify the GSR particles as either characteristic of GSR or consistent with GSR. In experiments with real samples, different firearms, calibers, and ammunitions were used. The performed method evaluation confirms that the developed methodology can be used as an alternative to the standard scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) technique, with the significant advantage of drastically reducing the analysis time to less than 66 min.

  8. Determination of platinum surface contamination in veterinary and human oncology centres using inductively coupled plasma mass spectrometry.

    PubMed

    Janssens, T; Brouwers, E E M; de Vos, J P; de Vries, N; Schellens, J H M; Beijnen, J H

    2015-09-01

    The objective of this study was to determine the surface contamination with platinum-containing antineoplastic drugs in veterinary and human oncology centres. Inductively coupled plasma mass spectrometry was used to measure platinum levels in surface samples. In veterinary and human oncology centres, 46.3 and 68.9% of the sampled surfaces demonstrated platinum contamination, respectively. Highest platinum levels were found in the preparation rooms (44.6 pg cm(-2)) in veterinary centres, while maximal levels in human centres were found in oncology patient-only toilets (725 pg cm(-2)). Transference of platinum by workers outside areas where antineoplastic drugs were handled was observed in veterinary and human oncology centres. In conclusion, only low levels of platinum contamination attributable to carboplatin were found in the sampled veterinary oncology centres. However, dispersion of platinum outside areas where antineoplastic drugs were handled was detected in veterinary and human oncology centres. Consequently, not only personnel, but also others may be exposed to platinum.

  9. Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

    2006-03-01

    Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1.

  10. Characterization of a Sealed Americium-Beryllium (AmBe) Source by Inductively Coupled Plasma Mass Spectrometry

    SciTech Connect

    James Sommers; Marcos Jimenez; Mary Adamic; Jeffrey Giglio; Kevin Carney

    2009-12-01

    Two Americium-Beryllium neutron sources were dismantled, sampled (sub-sampled) and analyzed via inductively coupled plasma mass spectrometry (ICP-MS). Characteristics such as “age” since purification, actinide content, trace metal content and inter and intra source composition were determined. The “age” since purification of the two sources was determined to be 25.0 and 25.4 years, respectively. The systematic errors in the “age” determination were ± 4 % 2s. The amount and isotopic composition of U and Pu varied substantially between the sub-samples of Source 2 (n=8). This may be due to the physical means of sub-sampling or the way the source was manufactured. Source 1 was much more consistent in terms of content and isotopic composition (n=3 sub-samples). The Be-Am ratio varied greatly between the two sources. Source 1 had an Am-Be ratio of 6.3 ± 52 % (1s). Source 2 had an Am-Be ratio of 9.81 ± 3.5 % (1s). In addition, the trace element content between the samples varied greatly. Significant differences were determined between Source 1 and 2 for Sc, Sr, Y, Zr, Mo, Ba and W.

  11. Measurement of airborne gunshot particles in a ballistics laboratory by sector field inductively coupled plasma mass spectrometry.

    PubMed

    Diaz, Ernesto; Sarkis, Jorge E Souza; Viebig, Sônia; Saldiva, Paulo

    2012-01-10

    The present study aimed determines lead (Pb), antimony (Sb) and barium (Ba) as the major elements present in GSR in the environmental air of the Ballistics Laboratory of the São Paulo Criminalistics Institute (I.C.-S.P.), São Paulo, SP, Brazil. Micro environmental monitors (mini samplers) were located at selected places. The PM(2.5) fraction of this airborne was collected in, previously weighted filters, and analyzed by sector field inductively coupled plasma mass spectrometer (SF-HR-ICP-MS). The higher values of the airborne lead, antimony and barium, were found at the firing range (lead (Pb): 58.9 μg/m(3); barium (Ba): 6.9 μg/m(3); antimony (Sb): 7.3 μg/m(3)). The mean value of the airborne in this room during 6 monitored days was Pb: 23.1 μg/m(3); Ba: 2.2 μg/m(3); Sb: 1.5 μg/m(3). In the water tank room, the air did not show levels above the limits of concern. In general the airborne lead changed from day to day, but the barium and antimony remained constant. Despite of that, the obtained values suggest that the workers may be exposed to airborne lead concentration that can result in an unhealthy environment and could increase the risk of chronic intoxication.

  12. Determination of total chlorine and bromine in solid wastes by sintering and inductively coupled plasma-sector field mass spectrometry

    SciTech Connect

    Osterlund, Helene Rodushkin, Ilia; Ylinenjaervi, Karin; Baxter, Douglas C.

    2009-04-15

    A sample preparation method based on sintering, followed by analysis by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) for the simultaneous determination of chloride and bromide in diverse and mixed solid wastes, has been evaluated. Samples and reference materials of known composition were mixed with a sintering agent containing Na{sub 2}CO{sub 3} and ZnO and placed in an oven at 560 deg. C for 1 h. After cooling, the residues were leached with water prior to a cation-exchange assisted clean-up. Alternatively, a simple microwave-assisted digestion using only nitric acid was applied for comparison. Thereafter the samples were prepared for quantitative analysis by ICP-SFMS. The sintering method was evaluated by analysis of certified reference materials (CRMs) and by comparison with US EPA Method 5050 and ion chromatography with good agreement. Median RSDs for the sintering method were determined to 10% for both chlorine and bromine, and median recovery to 96% and 97%, respectively. Limits of detection (LODs) were 200 mg/kg for chlorine and 20 mg/kg for bromine. It was concluded that the sintering method is suitable for chlorine and bromine determination in several matrices like sewage sludge, plastics, and edible waste, as well as for waste mixtures. The sintering method was also applied for determination of other elements present in anionic forms, such as sulfur, arsenic, selenium and iodine.

  13. Rapid determination of (237)Np and plutonium isotopes in urine by inductively-coupled plasma mass spectrometry and alpha spectrometry.

    PubMed

    Maxwell, Sherrod L; Culligan, Brian K; Jones, Vernon D; Nichols, Sheldon T; Noyes, Gary W; Bernard, Maureen A

    2011-08-01

    A new rapid separation method was developed for the measurement of plutonium and neptunium in urine samples by inductively-coupled plasma mass spectrometry (ICP-MS) and/or alpha spectrometry with enhanced uranium removal. This method allows separation and preconcentration of plutonium and neptunium in urine samples using stacked extraction chromatography cartridges and vacuum box flow rates to facilitate rapid separations. There is an increasing need to develop faster analytical methods for emergency response samples. There is also enormous benefit to having rapid bioassay methods in the event that a nuclear worker has an uptake (puncture wound, etc.) to assess the magnitude of the uptake and guide efforts to mitigate dose (e.g., tissue excision and chelation therapy). This new method focuses only on the rapid separation of plutonium and neptunium with enhanced removal of uranium. For ICP-MS, purified solutions must have low salt content and low concentration of uranium due to spectral interference of (238)U(1)H(+) on m/z 239. Uranium removal using this method is enhanced by loading plutonium and neptunium initially onto TEVA resin, then moving plutonium to DGA resin where additional purification from uranium is performed with a decontamination factor of almost 1×10(5). If UTEVA resin is added to the separation scheme, a decontamination factor of ~3 × 10(6) can be achieved. PMID:21709507

  14. [Interest and limits of inductively coupled plasma mass spectrometry (ICP-MS) for urinary diagnosis of radionuclide internal contamination].

    PubMed

    Lecompte, Yannick; Bohand, Sandra; Laroche, Pierre; Cazoulat, Alain

    2013-01-01

    After a review of radiometric reference methods used in radiotoxicology, analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for the workplace urinary diagnosis of internal contamination by radionuclides are evaluated. A literature review (covering the period from 2000 to 2012) is performed to identify the different applications of ICP-MS in radiotoxicology for urine analysis. The limits of detection are compared to the recommendations of the International commission on radiological protection (ICRP 78: "Individual monitoring for internal exposure of workers"). Except one publication describing the determination of strontium-90 (β emitter), all methods using ICP-MS reported in the literature concern actinides (α emitters). For radionuclides with a radioactive period higher than 10(4) years, limits of detection are most often in compliance with ICRP publication 78 and frequently lower than radiometric methods. ICP-MS allows the specific determination of plutonium-239 + 240 isotopes which cannot be discriminated by α spectrometry. High resolution ICP-MS can also measure uranium isotopic ratios in urine for total uranium concentrations lower than 20 ng/L. The interest of ICP-MS in radiotoxicology concerns essentially the urinary measurement of long radioactive period actinides, particularly for uranium isotope ratio determination and 239 and 240 plutonium isotopes discrimination. Radiometric methods remain the most efficient for the majority of other radionuclides. PMID:23747664

  15. Complexation of europium and uranium by humic acids analyzed by capillary electrophoresis-inductively coupled plasma mass spectrometry.

    PubMed

    Möser, Christina; Kautenburger, Ralf; Philipp Beck, Horst

    2012-05-01

    Investigations of the mobility of radioactive and nonradioactive substances in the environment are important tasks for the development of a future disposal in deep geological formations. Dissolved organic matter (DOM) can play an important role in the mobilization of metal ions due to complexation. In this study, we investigate the complexation behavior of humic acid (HA) as a model substance for DOM and its influence on the migration of europium as homologue for the actinide americium and uranium as the principal component of nuclear fuel. As speciation technique, capillary electrophoresis (CE) was hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). For the study, 0.5 mg·L⁻¹ of the metals and 25 mg·L⁻¹ of (purified Aldrich) HA and an aqueous solution sodium-perchlorate with an ionic strength of 10 mM at pH 5 were used. CE-ICP-MS clearly shows the different speciation of the triple positively charged europium and the double positively charged uranyl cation with HA. PMID:22648819

  16. Analysis of Mineral and Heavy Metal Content of Some Commercial Fruit Juices by Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Dehelean, Adriana; Magdas, Dana Alina

    2013-01-01

    The presence of potentially toxic elements and compounds in foodstuffs is of intense public interest and thus requires rapid and accurate methods to determine the levels of these contaminants. Inductively coupled plasma mass spectrometry is a powerful tool for the determination of metals and nonmetals in fruit juices. In this study, 21 commercial fruit juices (apple, peach, apricot, orange, kiwi, pear, pineapple, and multifruit) present on Romanian market were investigated from the heavy metals and mineral content point of view by ICP-MS. Our obtained results were compared with those reported in literature and also with the maximum admissible limit in drinking water by USEPA and WHO. For Mn the obtained values exceeded the limits imposed by these international organizations. Co, Cu, Zn, As, and Cd concentrations were below the acceptable limit for drinking water for all samples while the concentrations of Ni and Pb exceeded the limits imposed by USEPA and WHO for some fruit juices. The results obtained in this study are comparable to those found in the literature. PMID:24453811

  17. Determination of noble metals in biological samples by electrothermal vaporization inductively coupled plasma mass spectrometry, following cloud point extraction

    NASA Astrophysics Data System (ADS)

    Andreia Mesquita da Silva, Márcia; Lúcia Azzolin Frescura, Vera; José Curtius, Adilson

    2001-10-01

    A simple separation procedure for noble metals based on cloud point extraction is proposed. The analyte ions in aqueous acidic solution, obtained by the acid digestion of the samples, were complexed with O, O-diethyl-dithiophosphate and Triton X-114 was added as a non-ionic surfactant. By increasing the temperature up to the cloud point, a phase separation occurs, resulting in an aqueous phase and a surfactant-rich phase containing most of the analytes that were complexed. The metals in the surfactant-rich phase were determined by electrothermal vaporization inductively coupled plasma mass spectrometry. The extraction conditions as well as the instrumental parameters were optimized. Enrichment factors ranging from 7 (Rh) to 60 (Pt) and limits of detection from 0.6 (Pt) to 3.0 ng l -1 (Rh) were obtained in the digested samples. The extraction was not efficient for Ir. Among the reference materials analyzed in this work, only one (SRM 2670, urine) presented recommended values for Au and Pt. Due to the non-availability of adequate CRMs, accuracy was assessed by spiking known analyte amounts to the acid digests. Recoveries close to 100% were observed for all the studied elements but Ru. Poor agreement between found and recommended values was observed for non-digested urine sample, probably due to the carrier effect of co-extracted residual matrix components. However, good agreement was reached after urine acid mineralization.

  18. Provenance determination of oriental porcelain using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS).

    PubMed

    Bartle, Emma K; Watling, R John

    2007-03-01

    The sale of fraudulent oriental ceramics constitutes a large proportion of the illegal artifact and antique trade and threatens to undermine the legitimate international market. The sophistication and skill of forgers has reached a level where, using traditional appraisal by eye and hand, even the most experienced specialist is often unable to distinguish between a genuine and fraudulent piece. In addition, current provenancing techniques such as energy-dispersive X-ray fluorescence (EDXRF) spectrometry and thermoluminescence (TL) dating can result in significant damage to the artifact itself. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), a relatively nondestructive analytical technique, has been used for the provenance determination of materials based on geographical origin. The technique requires the production of a laser crater, c. 100 microm in diameter, which is essentially invisible to the naked eye. Debris from this crater is analyzed using ICP-MS, with the results forming the basis of the provenance establishment protocol. Chinese, Japanese, and English porcelain shards have been analyzed using this protocol and generic isotopic distribution patterns have been produced that enable the provenance establishment of porcelain artifacts to their country of production. Minor variations between elemental fingerprints of artifacts produced in the same country also indicate that it may be possible to further provenance oriental ceramics to a specific production region or kiln site.

  19. Trace elemental analysis of automotive paints by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS).

    PubMed

    Hobbs, Andria L; Almirall, José R

    2003-08-01

    Paints and coatings are frequently encountered as types of materials that are submitted to forensic science laboratories as a result of trace evidence transfers. The aim of this study was to develop a method to complement the commonly used techniques in a forensic laboratory in order to better characterize these samples for forensic purposes. A laser ablation method has been used to simultaneously sample several layers directly prior to introduction into an inductively coupled plasma-mass spectrometer for the detection and quantification of the trace metals present in the layer(s). Time-resolved analysis plots displaying the elemental response and quantification of selected metals are compared to associate/discriminate paint samples. Matrix-matched standards were successfully incorporated into the analysis scheme for quantification of lead in the solid paint samples. Preparation of new matrix-matched standards for quantification of additional elements developed for this study are also presented. A sample set of eighteen (18) survey automotive paint samples have been analyzed with the developed method in order to determine the utility of LA-ICP-MS for trace element analysis of paints.

  20. High performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry for V and Ni quantification as tetrapyrroles

    NASA Astrophysics Data System (ADS)

    Duyck, Christiane Béatrice; Saint'Pierre, Tatiana Dillenburg; Miekeley, Norbert; da Fonseca, Teresa Cristina Oliveira; Szatmari, Peter

    2011-05-01

    A method was developed for the determination of V and Ni as tetrapyrroles by High Performance Liquid Chromatography hyphenated to Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) using reversed phase and elution gradient. Chlorinated solvents and tetrahydrofuran were investigated as regard to separation time and ICP-MS detection efficiencies. The final elution gradient program started from pure methanol to a mixture of 20:80 (v/v) chloroform:methanol. External quantification of V and Ni with inorganic standards by flow injection ICP-MS, used online with HPLC, resulted in 95% of recoveries. The Limits of Detection for V during methanol elution and for Ni during the 20% chloroform gradient elution were evaluated by their minimum detectable concentrations, which were, respectively, 5 μg L - 1 and 8 μg L - 1 . The methodology was applied to polar and resin fractions separated from a Brazilian crude oil and a sediment extract from an oil-polluted area in the Guanabara Bay, Rio de Janeiro, Brazil. Vanadium as tetrapyrroles represented the totality of V content in the polar fraction, whereas Ni was in different polar forms in the resin and sediment extract.

  1. Rapid determination of (237)Np and plutonium isotopes in urine by inductively-coupled plasma mass spectrometry and alpha spectrometry.

    PubMed

    Maxwell, Sherrod L; Culligan, Brian K; Jones, Vernon D; Nichols, Sheldon T; Noyes, Gary W; Bernard, Maureen A

    2011-08-01

    A new rapid separation method was developed for the measurement of plutonium and neptunium in urine samples by inductively-coupled plasma mass spectrometry (ICP-MS) and/or alpha spectrometry with enhanced uranium removal. This method allows separation and preconcentration of plutonium and neptunium in urine samples using stacked extraction chromatography cartridges and vacuum box flow rates to facilitate rapid separations. There is an increasing need to develop faster analytical methods for emergency response samples. There is also enormous benefit to having rapid bioassay methods in the event that a nuclear worker has an uptake (puncture wound, etc.) to assess the magnitude of the uptake and guide efforts to mitigate dose (e.g., tissue excision and chelation therapy). This new method focuses only on the rapid separation of plutonium and neptunium with enhanced removal of uranium. For ICP-MS, purified solutions must have low salt content and low concentration of uranium due to spectral interference of (238)U(1)H(+) on m/z 239. Uranium removal using this method is enhanced by loading plutonium and neptunium initially onto TEVA resin, then moving plutonium to DGA resin where additional purification from uranium is performed with a decontamination factor of almost 1×10(5). If UTEVA resin is added to the separation scheme, a decontamination factor of ~3 × 10(6) can be achieved.

  2. Speciation analysis of mercury in natural water and fish samples by using capillary electrophoresis-inductively coupled plasma mass spectrometry.

    PubMed

    Zhao, YunQiang; Zheng, JinPing; Fang, Ling; Lin, Qin; Wu, YongNing; Xue, ZhiMin; Fu, FengFu

    2012-01-30

    A environment-friendly microwave-assisted extraction used to extract trace mercury compounds from fish samples, and a ultra-sensitive method for the analysis of Hg(II), methylmercury (MeHg) and ethylmercury (EtHg) by using capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) were described in this study. The extraction method is environment-friendly, simple, effective, and can be used to extract trace mercury compounds in fish samples with a satisfied recovery within several minutes. The CE-ICP-MS analytical method has a detection limit as lower as 0.021-0.032 ng Hg/mL for MeHg, EtHg and Hg(II), and can be used to determined ultratrace MeHg, EtHg and Hg(II) in natural water and fish samples directly without any preconcentration. With the help of the above methods, we have successfully determined MeHg, EtHg and Hg(II) in dried fish (Tapertail anchovy) muscle and natural water within 25 min with a RSD (relative standard deviation, n=6) <5% and a recovery of 94-103%. Our results showed that dried muscle of T. anchovy contained only one species of mercury, MeHg, indicating that MeHg is easier to be accumulated by aquatic organisms. PMID:22284493

  3. Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

    2006-03-01

    Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1. PMID:16496054

  4. Determination of total chlorine and bromine in solid wastes by sintering and inductively coupled plasma-sector field mass spectrometry.

    PubMed

    Osterlund, Heléne; Rodushkin, Ilia; Ylinenjärvi, Karin; Baxter, Douglas C

    2009-04-01

    A sample preparation method based on sintering, followed by analysis by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) for the simultaneous determination of chloride and bromide in diverse and mixed solid wastes, has been evaluated. Samples and reference materials of known composition were mixed with a sintering agent containing Na(2)CO(3) and ZnO and placed in an oven at 560 degrees C for 1h. After cooling, the residues were leached with water prior to a cation-exchange assisted clean-up. Alternatively, a simple microwave-assisted digestion using only nitric acid was applied for comparison. Thereafter the samples were prepared for quantitative analysis by ICP-SFMS. The sintering method was evaluated by analysis of certified reference materials (CRMs) and by comparison with US EPA Method 5050 and ion chromatography with good agreement. Median RSDs for the sintering method were determined to 10% for both chlorine and bromine, and median recovery to 96% and 97%, respectively. Limits of detection (LODs) were 200mg/kg for chlorine and 20mg/kg for bromine. It was concluded that the sintering method is suitable for chlorine and bromine determination in several matrices like sewage sludge, plastics, and edible waste, as well as for waste mixtures. The sintering method was also applied for determination of other elements present in anionic forms, such as sulfur, arsenic, selenium and iodine. PMID:19091539

  5. Direct determination of dissolved phosphate and silicate in seawater by ion exclusion chromatography sector field inductively coupled plasma mass spectrometry.

    PubMed

    Yang, Lu; Pagliano, Enea; Mester, Zoltán

    2014-03-18

    A method is described for the direct determination of dissolved phosphate and silicate in seawater using ion exclusion chromatography (IEC) coupled with sector field inductively coupled plasma mass spectrometry (SF-ICPMS). Dissolved silicate was determined by double isotope dilution using a (29)Si spike, whereas one point gravimetric standard addition with internal standard of the same (29)Si spike was employed to quantitate dissolved phosphate. Medium resolution was used for all measurements in order to resolve polyatomic interferences on Si and P isotopes. Concentrations of 1.670 ± 0.008 and 30.20 ± 0.09 μM (SD, n = 6) with precisions of 0.47 and 0.31% for the dissolved phosphate and silicate, respectively, were obtained in National Research Council Canada certified reference material MOOS-3 seawater, in good agreement with certified values of 1.60 ± 0.15 and 30.5 ± 0.8 μM (U, k = 2), respectively. The reported method is a rapid (10 min per run), simple, and accurate online technique that requires no sample pretreatment. Moreover, this procedure achieves <0.5% precision (at above analyte concentrations) and method detection limits of 0.006 and 0.004 μM (0.18 as P and 0.11 ng g(-1) as Si), respectively, using a of 100 μL injection of seawater. The proposed technique is robust and well-suited for the determination of dissolved phosphate and silicate in seawater.

  6. Speciation of gadolinium in surface water samples and plants by hydrophilic interaction chromatography hyphenated with inductively coupled plasma mass spectrometry.

    PubMed

    Lindner, Uwe; Lingott, Jana; Richter, Silke; Jakubowski, Norbert; Panne, Ulrich

    2013-02-01

    Hydrophilic interaction chromatography (HILIC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was optimized for speciation analysis of gadolinium-based contrast agents in environmental samples, in particular surface river waters and plants. Surface water samples from the Teltow channel, near Berlin, were investigated over a distance of 5 km downstream from the influx of a wastewater treatment plant. The total concentration of gadolinium increased significantly from 50 to 990 ng L(-1) due to the influx of the contrast agents. After complete mixing with the river water, the concentration remained constant over a distance of at least 4 km. Two main substances [Dotarem(®) (Gd-DOTA) and Gadovist(®) (Gd-BT-DO3A)] have been identified in the river water using standards. A gadolinium-based contrast agent, possibly Gd-DOTA (Dotarem(®)), was also detected in water plant samples taken from the Teltow channel. Therefore, uptake of contrast agents [Gadovist(®) (Gd-BTDO3A), Magnevist(®) (Gd-DTPA), Omniscan(®) (Gd-DTPA-BMA), Dotarem(®) (Gd-DOTA), and Multihance(®) (Gd-BOPTA)] by plants was investigated in a model experiment using Lepidium sativum (cress plants). HILIC-ICP-MS was used for identification of different contrast agents, and a first approach for quantification using aqueous standard solutions was tested. For speciation analysis, all investigated contrast agents could be extracted from the plant tissues with a recovery of about 54 % for Multihance(®) (Gd-BOPTA) up to 106 % for Gadovist(®) (Gd-BT-DO3A). These experiments demonstrate that all contrast agents investigated are transported from the roots to the leaves where the highest content was measured.

  7. Evaluation of liquid chromatography inductively coupled plasma mass spectrometry for arsenic speciation in water from industrial treatment of shale

    NASA Astrophysics Data System (ADS)

    Duarte, Fábio Andrei; Pereira, Juliana Severo Fagundes; Mesko, Márcia Foster; Goldschmidt, Fabiane; Flores, Érico Marlon de Moraes; Dressler, Valderi Luiz

    2007-09-01

    This work describes an arsenic speciation analysis in aqueous effluent from a shale industrial plant using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC-ICP-MS). Arsenic species have been separated through an anion-exchange column and several parameters investigated, such as retention time, pH, flow rate and concentration of the mobile phase (ammonium carbonate), chloride interference and column conditioning time. The best conditions have been found by fixing the pH of the mobile phase at 8.7. Keeping the mobile phase flow rate at 1.5 ml min - 1 , arsenic species were separated by varying the concentration of the mobile phase and the time of elution, as follow: 1.5 mmol l - 1 for 10 min, 12 mmol l - 1 for 10 min and 20 mmol l - 1 for 10 min, respectively. Up to 13 As species present in the samples were separated under these conditions and the following species could be identified and quantified: arsenite [As(III)], dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate [As(V)]. The limits of detection of the LC-ICP-MS method were 0.02, 0.06, 0.04 and 0.10 μg l - 1 of As(III), DMA, MMA, and As(V), respectively. The concentration of these species in the samples were from 3.7 to 6.4 μg l - 1 , 6.9 to 13.2 μg l - 1 , 100 to 142 μg l - 1 and 808 to 1363 μg l - 1 for As(III), DMA, MMA and As(V), respectively. The accuracy, evaluated by recovery tests, varied from 94 to 105% and the precision, evaluated by the relative standard deviation was typically lower than 10%.

  8. Quasi ?non-destructive? laser ablation-inductively coupled plasma-mass spectrometry fingerprinting of sapphires

    NASA Astrophysics Data System (ADS)

    Guillong, M.; Günther, D.

    2001-07-01

    A homogenized 193 nm excimer laser with a flat-top beam profile was used to study the capabilities of LA-ICP-MS for 'quasi' non-destructive fingerprinting and sourcing of sapphires from different locations. Sapphires contain 97-99% of Al 2O 3 (corundum), with the remainder composed of several trace elements, which can be used to distinguish the origin of these gemstones. The ablation behavior of sapphires, as well as the minimum quantity of sample removal that is required to determine these trace elements, was investigated. The optimum ablation conditions were a fluency of 6 J cm -2, a crater diameter of 120 μm, and a laser repetition rate of 10 Hz. The optimum time for the ablation was determined to be 2 s, equivalent to 20 laser pulses. The mean sample removal was 60 nm per pulse (approx. 3 ng per pulse). This allowed satisfactory trace element determination, and was found to cause the minimum amount of damage, while allowing for the fingerprinting of sapphires. More than 40 isotopes were measured using different spatial resolutions (20-120 μm) and eight elements were reproducibly detected in 25 sapphire samples from five different locations. The reproducibility of the trace element distribution is limited by the heterogeneity of the sample. The mean of five or more replicate analyses per sample was used. Calibration was carried out using NIST 612 glass reference material as external standard. The linear dynamic range of the ICP-MS (nine orders of magnitude) allowed the use of Al, the major element in sapphire, as an internal standard. The limits of detection for most of the light elements were in the μg g -1 range and were better for heavier elements (mass >85), being in the 0.1 μg g -1 range. The accuracy of the determinations was demonstrated by comparison with XRF analyses of the same set of samples. Using the quantitative analyses obtained using LA-ICP-MS, natural sapphires from five different origins were statistically classified using ternary plots and

  9. Development and Validation of an Inductively Coupled Plasma Mass Spectrometry (ICP-MS) Method for Quantitative Analysis of Platinum in Plasma, Urine, and Tissues.

    PubMed

    Zhang, Ti; Cai, Shuang; Forrest, Wai Chee; Mohr, Eva; Yang, Qiuhong; Forrest, M Laird

    2016-09-01

    Cisplatin, a platinum chemotherapeutic, is one of the most commonly used chemotherapeutic agents for many solid tumors. In this work, we developed and validated an inductively coupled plasma mass spectrometry (ICP-MS) method for quantitative determination of platinum levels in rat urine, plasma, and tissue matrices including liver, brain, lungs, kidney, muscle, heart, spleen, bladder, and lymph nodes. The tissues were processed using a microwave accelerated reaction system (MARS) system prior to analysis on an Agilent 7500 ICP-MS. According to the Food and Drug Administration guidance for industry, bioanalytical validation parameters of the method, such as selectivity, accuracy, precision, recovery, and stability were evaluated in rat biological samples. Our data suggested that the method was selective for platinum without interferences caused by other presenting elements, and the lower limit of quantification was 0.5 ppb. The accuracy and precision of the method were within 15% variation and the recoveries of platinum for all tissue matrices examined were determined to be 85-115% of the theoretical values. The stability of the platinum-containing solutions, including calibration standards, stock solutions, and processed samples in rat biological matrices was investigated. Results indicated that the samples were stable after three cycles of freeze-thaw and for up to three months. PMID:27527103

  10. Iodine determination in food by inductively coupled plasma mass spectrometry after digestion by microwave-induced combustion.

    PubMed

    Mesko, Márcia F; Mello, Paola A; Bizzi, Cezar A; Dressler, Valderi L; Knapp, Guenter; Flores, Erico M M

    2010-09-01

    Iodine determination in food samples was performed by inductively coupled plasma mass spectrometry (ICP-MS) after digestion by microwave-induced combustion (MIC). Sample masses up to 500 mg of bovine liver, corn starch, milk powder, or wheat flour were completely combusted using the MIC system. Ammonium nitrate (6 mol l(-1) solution, 50 μl) was used as an aid for ignition and vessels were charged with 15 bar of O(2). The use of H(2)O, 0.9 mmol l(-1) H(2)O(2), 10 to 50 mmol l(-1) (NH(4))(2)CO(3) and 56 mmol l(-1) tetramethylammonium hydroxide was investigated as absorbing solutions, as well as the suitability of performing a reflux step after the combustion process. Digestion of food samples by pressurized microwave-assisted acid digestion, microwave-assisted extraction and conventional extraction of iodine in alkaline solution were also evaluated. Iodine recoveries higher than 99% were obtained using MIC and 50 mmol l(-1) (NH(4))(2)CO(3) or 56 mmol l(-1) tetramethylammonium hydroxide as absorbing solution and with 5 min for the reflux step. Accuracy was evaluated using certified reference materials (bovine muscle, corn bran, and milk powder) and agreement better than 97% was obtained. The limit of quantification by MIC and further ICP-MS determination was 0.002 µg g(-1). Blanks were always low and no memory effects were observed. Digestion by MIC allowed the processing of up to eight samples by each run in 25 min with high efficiency of digestion (residual carbon content lower than 1%) providing a suitable medium for further iodine determination by ICP-MS. PMID:20464381

  11. Iodine determination in food by inductively coupled plasma mass spectrometry after digestion by microwave-induced combustion.

    PubMed

    Mesko, Márcia F; Mello, Paola A; Bizzi, Cezar A; Dressler, Valderi L; Knapp, Guenter; Flores, Erico M M

    2010-09-01

    Iodine determination in food samples was performed by inductively coupled plasma mass spectrometry (ICP-MS) after digestion by microwave-induced combustion (MIC). Sample masses up to 500 mg of bovine liver, corn starch, milk powder, or wheat flour were completely combusted using the MIC system. Ammonium nitrate (6 mol l(-1) solution, 50 μl) was used as an aid for ignition and vessels were charged with 15 bar of O(2). The use of H(2)O, 0.9 mmol l(-1) H(2)O(2), 10 to 50 mmol l(-1) (NH(4))(2)CO(3) and 56 mmol l(-1) tetramethylammonium hydroxide was investigated as absorbing solutions, as well as the suitability of performing a reflux step after the combustion process. Digestion of food samples by pressurized microwave-assisted acid digestion, microwave-assisted extraction and conventional extraction of iodine in alkaline solution were also evaluated. Iodine recoveries higher than 99% were obtained using MIC and 50 mmol l(-1) (NH(4))(2)CO(3) or 56 mmol l(-1) tetramethylammonium hydroxide as absorbing solution and with 5 min for the reflux step. Accuracy was evaluated using certified reference materials (bovine muscle, corn bran, and milk powder) and agreement better than 97% was obtained. The limit of quantification by MIC and further ICP-MS determination was 0.002 µg g(-1). Blanks were always low and no memory effects were observed. Digestion by MIC allowed the processing of up to eight samples by each run in 25 min with high efficiency of digestion (residual carbon content lower than 1%) providing a suitable medium for further iodine determination by ICP-MS.

  12. High temperature liquid chromatography-inductively coupled plasma mass spectrometry for the determination of arsenosugars in biological samples.

    PubMed

    Terol, Amanda; Ardini, Francisco; Grotti, Marco; Todolí, José Luis

    2012-11-01

    The potential of high temperature liquid chromatography (HTLC) with detection by inductively coupled plasma mass spectrometry (ICP-MS) for the determination of arsenosugars in marine organisms was examined for the first time. The retention behavior of four naturally occurring dimethylarsinoylribosides was studied on a graphite column using plain water as mobile phase. An aqueous solution of pH 8, ionic strength 13.8mM and containing 2% (v/v) of methanol, along with a column temperature of 120°C and a liquid flow rate of 1.0 mL/min, were selected as the optimal conditions, as they allowed the separation of the four arsenosugars in less than 18 min, without any interferences due to other common arsenic species (arsenite, arsenate, dimethylarsinate, methylarsonate and arsenobetaine). The run time could be further decreased to 12 min by working at 1.5 mL/min, although with a 3-4 times loss of sensitivity. The procedural limits of detection were 0.03-0.04 μg As/g dry mass, and the precision of the procedure ranged from 4% for arsenosugar glycerol to 18% for arsenosugar sulfate (RSD%, n=5). The developed method was applied to a number of representative biological samples, such as algae and crustaceans, providing results consistent with previous studies. In the red algae samples, the most of extracted arsenic was as arsenosugars (81-97%), mainly arsenosugar phosphate (56-94%). On the other hand, lower concentrations of these compounds were found in the crustacean, accounting for about 15% of the extracted arsenic.

  13. Non-spectral interferences due to the presence of sulfuric acid in inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    García-Poyo, M. Carmen; Grindlay, Guillermo; Gras, Luis; de Loos-Vollebregt, Margaretha T. C.; Mora, Juan

    2015-03-01

    Results of a systematic study concerning non-spectral interferences from sulfuric acid containing matrices on a large number of elements in inductively coupled plasma-mass spectrometry (ICP-MS) are presented in this work. The signals obtained with sulfuric acid solutions of different concentrations (up to 5% w w- 1) have been compared with the corresponding signals for a 1% w w- 1- nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for 128Te+, 78Se+ and 75As+ were significantly higher when using sulfuric acid matrices (up to 2.2-fold for 128Te+ and 78Se+ and 1.8-fold for 75As+ in the presence of 5 w w-1 sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for 31P+ is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for 128Te+, 78Se+, 75As+ and 31P+ are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S+ species in the plasma. Theoretical data suggest that Os, Sb, Pt, Ir, Zn and Hg could also be involved in sulfur-based charge transfer reactions, but no experimental evidence has been found. The presence of sulfuric acid gives rise to lower ion signals (about 10-20% lower) for the other nuclides tested, thus indicating the negative matrix effect caused by changes in the amount of analyte loading of the plasma. The elemental composition of a certified low-density polyethylene sample (ERM-EC681K) was determined by ICP-MS after two different sample digestion procedures, one of them including sulfuric acid. Element concentrations were in agreement with the certified values, irrespective of the acids used for the digestion. These results demonstrate that the use of matrix-matched standards allows the accurate determination of the tested elements in a sulfuric acid matrix.

  14. Determination of peanut allergens in cereal-chocolate-based snacks: metal-tag inductively coupled plasma mass spectrometry immunoassay versus liquid chromatography/electrospray ionization tandem mass spectrometry.

    PubMed

    Careri, Maria; Elviri, Lisa; Maffini, Monica; Mangia, Alessandro; Mucchino, Claudio; Terenghi, Mattia

    2008-01-01

    A comparison of two methods for the identification and determination of peanut allergens based on europium (Eu)-tagged inductively coupled plasma mass spectrometry (ICP-MS) immunoassay and on liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) with a triple quadrupole mass analyzer was carried out on a complex food matrix like a chocolate rice crispy-based snack. The LC/MS/MS method was based on the determination of four different peptide biomarkers selective for the Ara h2 and Ara h3/4 peanut proteins. The performance of this method was compared with that of a non-competitive sandwich enzyme-linked immunosorbent assay (ELISA) method with ICP-MS detection of the metal used to tag the antibody for the quantitative peanut protein analysis in food. The limit of detection (LOD) and quantitation of the ICP-MS immunoassay were 2.2 and 5 microg peanuts g(-1) matrix, respectively, the recovery ranged from 86 +/- 18% to 110 +/- 4% and linearity was proved in the 5-50 microg g(-1) range. The LC/MS/MS method allowed us to obtain LODs of 1 and 5 microg protein g(-1) matrix for Ara h3/4 and Ara h2, respectively, thus obtaining significantly higher values with respect to the ELISA ICP-MS method, taking into account the different expression for concentrations. Linearity was established in the 10-200 microg g(-1) range of peanut proteins in the food matrix investigated and good precision (RSD <10%) was demonstrated. Both the two approaches, used for screening or confirmative purposes, showed the power of mass spectrometry when used as a very selective detector in difficult matrices even if some limitations still exist, i.e. matrix suppression in the LC/ESI-MS/MS procedure and the change of the Ag/Ab binding with matrix in the ICP-MS method.

  15. Speciation analysis of inorganic tin by on-column complexation ion chromatography with inductively coupled plasma mass spectrometry and electrospray mass spectrometry.

    PubMed

    Huang, Li; Yang, Die; Guo, Xiangquan; Chen, Zuliang

    2014-11-14

    Inductively coupled plasma-mass spectrometry (ICP-MS) and electrospray mass spectrometry (ESI-MS) were used as complementary methods to identify Sn-pentaacetic acid (DTPA) complex formation. ESI-MS was used to initially confirm the formation of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) and their MS spectra suggest these tin complexes were stable in solution. On-column complexation of tin with DTPA and the separation of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) was performed on anion-exchange chromatography with an mobile phase containing 20mM NH4NO3 and 3mM DTPA at pH 6.0, and the subsequent detection of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) was achieved by ICP-MS. Linear plots were obtained in a concentration range of 1.0-1000 μg L(-1) with detection limits ranging from 0.1 to 0.3 μg L(-1). The developed procedure allows the simultaneous determination of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) in less than 5 min with a RSD between 2.1 and 2.7%. The recoveries of [Sn(DTPA)](3-) and [Sn(DTPA)](1-) were found to be 96.8 and 99.4%, respectively, when the sample was spiked with 20 μg L(-1) standard. Finally, the proposed procedure was used for the determination of tin species in contaminated water.

  16. Linearization of calibration curves by aerosol carrier effect of CCl 4 vapor in electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kántor, Tibor; de Loos-Vollebregt, Margaretha T. C.

    2005-03-01

    Carbon tetrachloride vapor as gaseous phase modifier in a graphite furnace electrothermal vaporizer (GFETV) converts heavy volatile analyte forms to volatile and medium volatile chlorides and produces aerosol carrier effect, the latter being a less generally recognized benefit. However, the possible increase of polyatomic interferences in inductively coupled plasma mass spectrometry (GFETV-ICP-MS) by chlorine and carbon containing species due to CCl 4 vapor introduction has been discouraging with the use of low resolution, quadrupole type MS equipment. Being aware of this possible handicap, it was aimed at to investigate the feasibility of the use of this halogenating agent in ICP-MS with regard of possible hazards to the instrument, and also to explore the advantages under these specific conditions. With sample gas flow (inner gas flow) rate not higher than 900 ml min -1 Ar in the torch and 3 ml min -1 CCl 4 vapor flow rate in the furnace, the long-term stability of the instrument was ensured and the following benefits by the halocarbon were observed. The non-linearity error (defined in the text) of the calibration curves (signal versus mass functions) with matrix-free solution standards was 30-70% without, and 1-5% with CCl 4 vapor introduction, respectively, at 1 ng mass of Cu, Fe, Mn and Pb analytes. The sensitivity for these elements increased by 2-4-fold with chlorination, while the relative standard deviation (RSD) was essentially the same (2-5%) for the two cases in comparison. A vaporization temperature of 2650 °C was required for Cr in Ar atmosphere, while 2200 °C was sufficient in Ar + CCl 4 atmosphere to attain complete vaporization. Improvements in linear response and sensitivity were the highest for this least volatile element. The pyrolytic graphite layer inside the graphite tube was protected by the halocarbon, and tube life time was further increased by using traces of hydrocarbon vapor in the external sheath gas of the graphite furnace. Details

  17. A lectin-coupled, targeted proteomic mass spectrometry (MRM MS) platform for identification of multiple liver cancer biomarkers in human plasma.

    PubMed

    Ahn, Yeong Hee; Shin, Park Min; Oh, Na Ree; Park, Gun Wook; Kim, Hoguen; Yoo, Jong Shin

    2012-09-18

    Aberrantly glycosylated proteins related to liver cancer progression were captured with specific lectin and identified from human plasma by multiple reaction monitoring (MRM) mass spectrometry as multiple biomarkers for hepatocellular carcinoma (HCC). The lectin fractionation for fucosylated protein glycoforms in human plasma was conducted with a fucose-specific aleuria aurantia lectin (AAL). Following tryptic digestion of the lectin-captured fraction, plasma samples from 30 control cases (including 10 healthy, 10 hepatitis B virus [HBV], and 10 cirrhosis cases) and 10 HCC cases were quantitatively analyzed by MRM to identify which glycoproteins are viable HCC biomarkers. A1AG1, AACT, A1AT, and CERU were found to be potent biomarkers to differentiate HCC plasma from control plasmas. The AUROC generated independently from these four biomarker candidates ranged from 0.73 to 0.92. However, the lectin-coupled MRM assay with multiple combinations of biomarker candidates is superior statistically to those generated from the individual candidates with AUROC more than 0.95, which can be an alternative to the immunoassay inevitably requiring tedious development of multiple antibodies against biomarker candidates to be verified. Eventually the lectin-coupled, targeted proteomic mass spectrometry (MRM MS) platform was found to be efficient to identify multiple biomarkers from human plasma according to cancer progression.

  18. Asymmetric flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry for the quantification of quantum dots bioconjugation efficiency.

    PubMed

    Menéndez-Miranda, Mario; Encinar, Jorge Ruiz; Costa-Fernández, José M; Sanz-Medel, Alfredo

    2015-11-27

    Hyphenation of asymmetric flow field-flow fractionation (AF4) to an on-line elemental detection (inductively coupled plasma-mass spectrometry, ICP-MS) is proposed as a powerful diagnostic tool for quantum dots bioconjugation studies. In particular, conjugation effectiveness between a "model" monoclonal IgG antibody (Ab) and CdSe/ZnS core-shell Quantum Dots (QDs), surface-coated with an amphiphilic polymer, has been monitored here by such hybrid AF4-ICP-MS technique. Experimental conditions have been optimized searching for a proper separation between the sought bioconjugates from the eventual free reagents excesses employed during the bioconjugation (QDs and antibodies). Composition and pH of the carrier have been found to be critical parameters to ensure an efficient separation while ensuring high species recovery from the AF4 channel. An ICP-MS equipped with a triple quadropole was selected as elemental detector to enable sensitive and reliable simultaneous quantification of the elemental constituents, including sulfur, of the nanoparticulated species and the antibody. The hyphenated technique used provided nanoparticle size-based separation, elemental detection, and composition analysis capabilities that turned out to be instrumental in order to investigate in depth the Ab-QDs bioconjugation process. Moreover, the analytical strategy here proposed allowed us not only to clearly identify the bioconjugation reaction products but also to quantify nanoparticle:antibodies bioconjugation efficiency. This is a key issue in future development of analytical and bioanalytical photoluminescent QDs applications. PMID:26493473

  19. Magnetic immunoassay coupled with inductively coupled plasma mass spectrometry for simultaneous quantification of alpha-fetoprotein and carcinoembryonic antigen in human serum

    NASA Astrophysics Data System (ADS)

    Zhang, Xing; Chen, Beibei; He, Man; Zhang, Yiwen; Xiao, Guangyang; Hu, Bin

    2015-04-01

    The absolute quantification of glycoproteins in complex biological samples is a challenge and of great significance. Herein, 4-mercaptophenylboronic acid functionalized magnetic beads were prepared to selectively capture glycoproteins, while antibody conjugated gold and silver nanoparticles were synthesized as element tags to label two different glycoproteins. Based on that, a new approach of magnetic immunoassay-inductively coupled plasma mass spectrometry (ICP-MS) was established for simultaneous quantitative analysis of glycoproteins. Taking biomarkers of alpha-fetoprotein (AFP) and carcinoembryonic antigen (CEA) as two model glycoproteins, experimental parameters involved in the immunoassay procedure were carefully optimized and analytical performance of the proposed method was evaluated. The limits of detection (LODs) for AFP and CEA were 0.086 μg L- 1 and 0.054 μg L- 1 with the relative standard deviations (RSDs, n = 7, c = 5 μg L- 1) of 6.5% and 6.2% for AFP and CEA, respectively. Linear range for both AFP and CEA was 0.2-50 μg L- 1. To validate the applicability of the proposed method, human serum samples were analyzed, and the obtained results were in good agreement with that obtained by the clinical chemiluminescence immunoassay. The developed method exhibited good selectivity and sensitivity for the simultaneous determination of AFP and CEA, and extended the applicability of metal nanoparticle tags based on ICP-MS methodology in multiple glycoprotein quantifications.

  20. Direct analysis of ultra-trace semiconductor gas by inductively coupled plasma mass spectrometry coupled with gas to particle conversion-gas exchange technique.

    PubMed

    Ohata, Masaki; Sakurai, Hiromu; Nishiguchi, Kohei; Utani, Keisuke; Günther, Detlef

    2015-09-01

    An inductively coupled plasma mass spectrometry (ICPMS) coupled with gas to particle conversion-gas exchange technique was applied to the direct analysis of ultra-trace semiconductor gas in ambient air. The ultra-trace semiconductor gases such as arsine (AsH3) and phosphine (PH3) were converted to particles by reaction with ozone (O3) and ammonia (NH3) gases within a gas to particle conversion device (GPD). The converted particles were directly introduced and measured by ICPMS through a gas exchange device (GED), which could penetrate the particles as well as exchange to Ar from either non-reacted gases such as an air or remaining gases of O3 and NH3. The particle size distribution of converted particles was measured by scanning mobility particle sizer (SMPS) and the results supported the elucidation of particle agglomeration between the particle converted from semiconductor gas and the particle of ammonium nitrate (NH4NO3) which was produced as major particle in GPD. Stable time-resolved signals from AsH3 and PH3 in air were obtained by GPD-GED-ICPMS with continuous gas introduction; however, the slightly larger fluctuation, which could be due to the ionization fluctuation of particles in ICP, was observed compared to that of metal carbonyl gas in Ar introduced directly into ICPMS. The linear regression lines were obtained and the limits of detection (LODs) of 1.5 pL L(-1) and 2.4 nL L(-1) for AsH3 and PH3, respectively, were estimated. Since these LODs revealed sufficiently lower values than the measurement concentrations required from semiconductor industry such as 0.5 nL L(-1) and 30 nL L(-1) for AsH3 and PH3, respectively, the GPD-GED-ICPMS could be useful for direct and high sensitive analysis of ultra-trace semiconductor gas in air.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  2. Towards silicon speciation in light petroleum products using gas chromatography coupled to inductively coupled plasma mass spectrometry equipped with a dynamic reaction cell

    NASA Astrophysics Data System (ADS)

    Chainet, Fabien; Lienemann, Charles-Philippe; Ponthus, Jeremie; Pécheyran, Christophe; Castro, Joaudimir; Tessier, Emmanuel; Donard, Olivier François Xavier

    2014-07-01

    Silicon speciation has recently gained interest in the oil and gas industry due to the significant poisoning problems caused by silicon on hydrotreatment catalysts. The poisoning effect clearly depends on the structure of the silicon species which must be determined and quantified. The hyphenation of gas chromatography (GC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) allows a specific detection to determine the retention times of all silicon species. The aim of this work is to determine the retention indices of unknown silicon species to allow their characterization by a multi-technical approach in order to access to their chemical structure. The optimization of the dynamic reaction cell (DRC) of the ICP-MS using hydrogen as reactant gas successfully demonstrated the resolution of the interferences (14N14N+ and 12C16O+) initially present on 28Si. The linearity was excellent for silicon compounds and instrumental detection limits ranged from 20 to 140 μg of Si/kg depending on the response of the silicon compounds. A continuous release of silicon in the torch was observed most likely due to the use of a torch and an injector which was made of quartz. A non-universal response for silicon was observed and it was clearly necessary to use response coefficients to quantify silicon compounds. Known silicon compounds such as cyclic siloxanes (D3-D16) coming from PDMS degradation were confirmed. Furthermore, more than 10 new silicon species never characterized before in petroleum products were highlighted in polydimethylsiloxane (PDMS) degradation samples produced under thermal cracking of hydrocarbons. These silicon species mainly consisted of linear and cyclic structures containing reactive functions such as ethoxy, peroxide and hydroxy groups which can be able to react with the alumina surface and hence, poison the catalyst. This characterization will further allow the development of innovative solutions such as trapping silicon compounds or

  3. Inductively coupled helium plasma torch

    DOEpatents

    Montaser, Akbar; Chan, Shi-Kit; Van Hoven, Raymond L.

    1989-01-01

    An inductively coupled plasma torch including a base member, a plasma tube and a threaded insert member within the plasma tube for directing the plasma gas in a tangential flow pattern. The design of the torch eliminates the need for a separate coolant gas tube. The torch can be readily assembled and disassembled with a high degree of alignment accuracy.

  4. Determination of Mercury Content in a Shallow Firn Core from Summit, Greenland by Isotope Dilution Inductively Coupled Plasma Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mann, Jacqueline L.; Long, Stephen E.; Shuman, Christopher A.; Kelly, W. Robert

    2003-01-01

    The total mercury Hg content was determined in 6 cm sections of a near-surface 7 m firn core and in surrounding surface snow from Summit, Greenland (elevation: 3238 m, 72.58 N, 38.53 W) in May 2001 by isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICP-MS). The focus of this research was to evaluate the capability of the ID-CV-ICPMS technique for measuring trace levels of Hg typical of polar snow and firn. Highly enriched Hg-201 isotopic spike is added to approximately 10 ml melted core and thoroughly mixed. The Hg(+2) in the sample is reduced on line with tin (II) chloride (SnCl2) and the elemental Hg (Hg(0)) vapor pre-concentrated on to gold gauze using a commercial amalgam system. The Hg is then thermally desorbed and introduced into a quadrupole ICP-MS. The blank corrected Hg concentrations determined for all samples ranged from 0.25 ng/L to 1.74 ng/L (ppt) (average 0.59 ng/L plus or minus 0.28 ng/L) and fall within the range of those previously determined by Boutron et al., 1998 (less than or equal to 0.05 ng/L to 2.0 ng/L) for the Summit site. The average blank value was 0.19 ng/L plus or minus 0.045 ng/L (n=6). The Hg values specifically for the firn core range from 0.25 ng/L to 0.87 ng/L (average 0.51 ng/L plus or minus 0.13 ng/L) and show both values declining with time and larger variability in concentration in the top 1.8 m.

  5. Microwave assisted extraction of iodine and bromine from edible seaweed for inductively coupled plasma-mass spectrometry determination.

    PubMed

    Romarís-Hortas, Vanessa; Moreda-Piñeiro, Antonio; Bermejo-Barrera, Pilar

    2009-08-15

    The feasibility of microwave energy to assist the solubilisation of edible seaweed samples by tetramethylammonium hydroxide (TMAH) has been investigated to extract iodine and bromine. Inductively coupled plasma-mass spectrometry (ICP-MS) has been used as a multi-element detector. Variables affecting the microwave assisted extraction/solubilisation (temperature, TMAH volume, ramp time and hold time) were firstly screened by applying a fractional factorial design (2(5-1)+2), resolution V and 2 centre points. When extracting both halogens, results showed statistical significance (confidence interval of 95%) for TMAH volume and temperature, and also for the two order interaction between both variables. Therefore, these two variables were finally optimized by a 2(2)+star orthogonal central composite design with 5 centre points and 2 replicates, and optimum values of 200 degrees C and 10 mL for temperature and TMAH volume, respectively, were found. The extraction time (ramp and hold times) was found statistically non-significant, and values of 10 and 5 min were chosen for the ramp time and the hold time, respectively. This means a fast microwave heating cycle. Repeatability of the over-all procedure has been found to be 6% for both elements, while iodine and bromine concentrations of 24.6 and 19.9 ng g(-1), respectively, were established for the limit of detection. Accuracy of the method was assessed by analyzing the NIES-09 (Sargasso, Sargassum fulvellum) certified reference material (CRM) and the iodine and bromine concentrations found have been in good agreement with the indicative values for this CRM. Finally, the method was applied to several edible dried and canned seaweed samples.

  6. Use of inductively coupled plasma-mass spectrometry in boron-10 stable isotope experiments with plants, rats, and humans.

    PubMed Central

    Vanderpool, R A; Hoff, D; Johnson, P E

    1994-01-01

    The commercial availability of inductively coupled plasma-mass spectrometry technology (ICP-MS) has presented the opportunity to measure the boron concentrations and isotope ratios in a large number of samples with minimal sample preparation. A typical analytical sequence for fecal samples consists of 25 acid blanks, 1 digestion blank, 5 calibration solutions, 4 standard reference material solutions, 10 samples, and 4 natural abundance bias standards. Boron detection limits (3 x 1 sigma) for acid blanks are 0.11 ppb for 10B, and 0.40 ppb for 11B. Isotope ratios were measured in fecal samples with 20 to 50 ppb boron with < 2% relative standard deviation. Rapid washout and minimal memory effects were observed for a 50 ppb beryllium internal standard, but a 200 ppb boron biological sample had a 1.0 ppb boron memory after a 6-min washout. Boron isotope ratios in geological materials are highly variable; apparently this variability is reflected in plants of a fixed natural abundance value for boron requires that a natural abundance ratio be determined for each sample or related data set. The natural abundance variability also prevents quantitation and calculation of isotope dilution by instrument-supplied software. To measure boron transport in animal systems, 20 micrograms of 10B were fed to a fasted rat. During the 3 days after a 10B oral dose, 95% of the 10B was recovered from the urine and 4% from the feces. Urinary isotope ratios, 11B/10B, changed from a natural abundance of 4.1140 to an enriched value of 0.95077, a 77% change.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7889873

  7. Determination of trace impurities in high purity gold by inductively coupled plasma mass spectrometry with prior matrix removal by electrodeposition

    NASA Astrophysics Data System (ADS)

    Sun, Y. C.; Hsieh, C. H.; Lin, T. S.; Wen, J. C.

    2000-09-01

    A novel method for the determination of 11 trace impurities (Be, Mg, Cr, Mn, Ni, Cu, Zn, Ag, Pd, Sn and Pb) in high purity gold with a combination of electrochemical deposition separation and inductively coupled plasma mass spectrometric measurement was investigated. In the present study, an efficient separation procedure was developed to remove the gold matrix by the electrodepositon method on the basis of the difference in reduction potential of gold and the other trace impurities. The effects of deposition potential, deposition time and composition of the electrolyte on the separation efficiency were studied. According to our experimental results, most impurities, except for silver, can remain in the electrolyte and the interference from gold can be completely removed through the application of electrodeposition at suitable potential. To achieve simultaneous separation of silver from the gold matrix, a unique complexation reaction between silver ions and ammonia ions was successfully employed to alter the reduction potential of silver ion. By way of a suitable adjustment of the deposition potential and the composition of electrolytes, the spike recoveries of 11 interesting impurities were found to be in the range of 85-105%. The limit of detection (based on the 3-σ criterion) of these elements was 10 -1-10 -2 μg g -1. The applicability of the proposed method has also been validated by the analysis of high purity gold reference materials (FAU9 and FAU11, Royal Canadian Mint). Comparing with the certified values, the recoveries of interesting elements were found to be in the range of 82-118% through the use of proposed method.

  8. [Determination of five arsenic species in rice by liquid chromatography-inductively coupled plasma-mass spectrometry].

    PubMed

    Gong, Jiadi; Cao, Xiaolin; Cao, Zhaoyun; Bian, Yingfang; Yu, Shasha; Chen, Mingxue

    2014-07-01

    A method was developed for the simultaneous determination of arsenic acid [As (V)], arsenious acid [As (III)], arsenobetaine (AsB), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in rice by liquid chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS). The extraction reagent was 0.3 mol/L nitric acid with heat-assistant condition for 1.5 h at 95 degrees C. Then, the five arsenic species were separated by an anion exchange column (Dionex IonPac AS19, 250 mm x 4 mm) and detected by ICP-MS. Four kinds of extracted solutions were compared through the extraction efficiency. The concentration of nitric acid, the temperature and the extraction time were optimized. The recoveries of the five arsenic species spiked in rice at two levels ranged from 89.6% to 99.5% with the relative standard deviations (RSDs, n = 5) of 0.6% - 3.6%. The measured values of the arsenic species in standard rice materials were consistent with their standard values. The linear ranges were 0.05 - 200 microg/L for AsB and DMA, 0.10-400 microg/L for As (III) and MMA, 0.15-600 microg/L for As (V). The limits of detection for the five arsenic species were 0.15-0.45 microg/kg. The results showed that the method is much more precise for the risk assessment of the rice. This method is simple, accurate and durable for the determination of arsenic species in rice.

  9. Determination of trace elements in water samples by ultrasonic nebulization inductively coupled plasma mass spectrometry after cloud point extraction

    NASA Astrophysics Data System (ADS)

    Mesquita da Silva, Márcia Andreia; Azzolin Frescura, Vera Lúcia; Curtius, Adilson José

    2000-07-01

    A preconcentration method for low concentrations of Ag, As, Au, Cd, Cu, Pb and Se in water, using cloud point extraction is proposed. The analytes in the initial aqueous solution, acidified with hydrochloric acid, are complexed with ammonium O, O-diethyl-dithiophosphate, and 0.05% m/v Triton X-114 is added as surfactant. The complexation allows the separation of the analytes from alkali, alkaline earth and other elements, which are not complexed. After phase separation, by increasing the temperature above 20°C, depending on the cloud point of the mixture, and dilution of the surfactant-rich phase with a mixture of 60% v/v methanol and 40% v/v of 1% v/v aqueous nitric acid solution, the enriched analytes are determined by inductively coupled plasma mass spectrometry, using ultrasonic nebulization, injecting 100 μl of the enriched phase with a flow injection (FI) system. Since the initial volume is 40 ml and the final volume is 1 ml, good enrichment factors are obtained. After optimization of the complexation (pH and DDTP concentration), of extraction conditions, sample introduction (FI and ultrasonic nebulizer parameters) and spectrometer conditions, the method was applied to the analysis of riverine water, sea water and enriched water reference materials, and good agreement with the certified values was obtained. By introducing the organic extract with the FI system and using ultrasonic nebulization, no carbon deposits on the interface cones and lens were observed, allowing extensive use of the spectrometer without cleaning and re-optimization.

  10. Speciation analysis of mercury in cereals by liquid chromatography chemical vapor generation inductively coupled plasma-mass spectrometry.

    PubMed

    Lin, Liang-Yen; Chang, Lan-Fang; Jiang, Shiuh-Jen

    2008-08-27

    A simple and rapid procedure for the separation and determination of inorganic, methyl, and ethyl mercury compounds was described using liquid chromatography (LC) followed by vapor generation inductively coupled plasma-mass spectrometry (VG-ICP-MS). Well resolved chromatograms were obtained within 5 min by reversed-phase liquid chromatography with a C8 column as the stationary phase and a pH 4.7 solution containing 0.5% v/v 2-mercaptoethanol and 5% v/v methanol as the mobile phase. The separated mercury compounds were converted to mercury vapors by an in situ nebulizer/vapor generation system for their introduction into ICP. The concentrations of NaBH4 and HNO3 required for vapor generation were also optimized. The method was applied for the speciation of mercury in reference materials NIST SRM 1568a Rice Flour and NIST SRM 1567a Wheat Flour and also rice flour and wheat flour samples purchased locally. The accuracy of the procedure was verified by analyzing the certified reference material NRCC DOLT-3 Dogfish Liver for methyl mercury. Precision between sample replicates was better than 13% for all the determinations. The detection limits of the mercury compounds studied were in the range 0.003-0.006 ng Hg mL(-1) in the injected solutions, which correspond to 0.02-0.06 ng g(-1) in original flour samples. A microwave-assisted extraction procedure was adopted for the extraction of mercury compounds from rice flour, wheat flour, and fish samples using a mobile phase solution.

  11. Comparison of inductively coupled plasma mass spectrometry and colorimetric determination of total and extractable phosphorus in soils

    NASA Astrophysics Data System (ADS)

    Ivanov, Krasimir; Zaprjanova, Penka; Petkova, Milena; Stefanova, Violeta; Kmetov, Veselin; Georgieva, Deyana; Angelova, Violina

    2012-05-01

    The most widely used method for determination of total phosphorus in soils is perchloric acid digestion, followed by a colorimetric assay to measure the concentration of P in solution. The first part of this study compares an alternative digestion method, using aqua regia (ISO 11466 and EPA Method 3052), with perchloric acid digestion procedure, and also compares inductively coupled plasma mass spectroscopy (ICP-MS) with colorimetry for the measurement of P on the basis of five internationally certified standard soils and 20 real-life soils with widely different extractability of phosphorus. The phosphorus concentration was determined by means of the reduced phosphomolybdenum blue and ICP-MS. The relationship between methods has been examined statistically. Good agreement of the results from colorimetry and ICP-MS was established for all certified soils. The microwave-assisted digestion with aqua regia was comparable, both in precision and accuracy, with the hot plate aqua regia method. The phosphorus concentration found with the HF + HClO4 digestion method was in good agreement with the certified mean values, while the superiority in extracting phosphorus, when compared to other methods, was obvious. Soil testing for plant-available phosphorus in Bulgaria and many European countries is most commonly conducted using acid Ca-lactate extraction (Egner-Riehm test) and alkaline sodium bicarbonate extraction (BDS ISO 11263:2002), based on Olsen test, followed by a colorimetric assay to measure the concentration of P in solution. The second part of this study reports the differences between Egner-Riehm test and BDS ISO 11263:2002 measured colorimetrically and by ICP-MS. Fifty soils were selected from South Bulgaria to represent a wide range of soil properties. It was established that ICP-MS consistently yielded significantly higher P concentrations than the colorimetric method in both extraction tests, and the relative differences were greatest in soils with lower P

  12. Visualizing trace element distribution in quartz using cathodoluminescence, electron microprobe, and laser ablation-inductively coupled plasma-mass spectrometry

    USGS Publications Warehouse

    Rusk, Brian; Koenig, Alan; Lowers, Heather

    2011-01-01

    Cathodoluminescent (CL) textures in quartz reveal successive histories of the physical and chemical fluctuations that accompany crystal growth. Such CL textures reflect trace element concentration variations that can be mapped by electron microprobe or laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Trace element maps in hydrothermal quartz from four different ore deposit types (Carlin-type Au, epithermal Ag, porphyry-Cu, and MVT Pb-Zn) reveal correlations among trace elements and between trace element concentrations and CL textures. The distributions of trace elements reflect variations in the physical and chemical conditions of quartz precipitation. These maps show that Al is the most abundant trace element in hydrothermal quartz. In crystals grown at temperatures below 300 °C, Al concentrations may vary by up to two orders of magnitude between adjacent growth zones, with no evidence for diffusion. The monovalent cations Li, Na, and K, where detectable, always correlate with Al, with Li being the most abundant of the three. In most samples, Al is more abundant than the combined total of the monovalent cations; however, in the MVT sample, molar Al/Li ratios are ~0.8. Antimony is present in concentrations up to ~120 ppm in epithermal quartz (~200–300 °C), but is not detectable in MVT, Carlin, or porphyry-Cu quartz. Concentrations of Sb do not correlate consistently with those of other trace elements or with CL textures. Titanium is only abundant enough to be mapped in quartz from porphyry-type ore deposits that precipitate at temperatures above ~400 °C. In such quartz, Ti concentration correlates positively with CL intensity, suggesting a causative relationship. In contrast, in quartz from other deposit types, there is no consistent correlation between concentrations of any trace element and CL intensity fluctuations.

  13. Total arsenic determination and speciation in infant food products by ion chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Vela, Nohora P; Heitkemper, Douglas T

    2004-01-01

    Health risk associated with dietary arsenic intake may be different for infants and adults. Seafood is the main contributor to arsenic intake for adults while terrestrial-based food is the primary source for infants. Processed infant food products such as rice-based cereals, mixed rice/formula cereals, milk-based infant formula, applesauce and puree of peaches, pears, carrots, sweet potatoes, green beans, and squash were evaluated for total and speciated arsenic content. Arsenic concentrations found in rice-based cereals (63-320 ng/g dry weight) were similar to those reported for raw rice. Results for the analysis of powdered infant formula by inductively coupled plasma-mass spectrometry (ICP-MS) indicated a narrow and low arsenic concentration range (12 to 17 ng/g). Arsenic content in puree infant food products, including rice cereals, fruits, and vegetables, varies from <1 to 24 ng/g wet weight. Sample treatment with trifluoroacetic acid at 100 degrees C were an efficient and mild method for extraction of arsenic species present in different food matrixes as compared to alternative methods that included sonication and accelerated solvent extraction. Extraction recoveries from 94 to 128% were obtained when the summation of species was compared to total arsenic. The ion chromatography (IC)-ICP-MS method selected for arsenic speciation allowed for the quantitative determination of inorganic arsenic [As(III) + As(V)], dimethylarsinic acid (DMA), and methylarsonic acid (MMA). Inorganic arsenic and DMA are the main species found in rice-based and mixed rice/formula cereals, although traces of MMA were also detected. Inorganic arsenic was present in freeze-dried sweet potatoes, carrots, green beans, and peaches. MMA and DMA were not detected in these samples. Arsenic species in squash, pears, and applesauce were not detected above the method detection limit [5 ng/g dry weight for As(III), MMA, and DMA and 10 ng/g dry weight for As(V)].

  14. Manganese species from human serum, cerebrospinal fluid analyzed by size exclusion chromatography-, capillary electrophoresis coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Michalke, Bernhard; Berthele, Achim; Mistriotis, Panos; Ochsenkühn-Petropoulou, Maria; Halbach, Stefan

    2007-01-01

    Manganese (Mn) at high concentrations can have adverse effects on health, mainly because of its toxicity to the central nervous system. Health impacts of Mn are known mostly from occupational health studies, but the exact mechanisms how Mn, being bound to transferrin (TF) in the blood, enters the brain--are unknown. Mn speciation at the neural barriers can help to obtain more information about the pathways and carriers. This paper summarizes investigations on the size distribution of Mn carriers (e.g. proteins, peptides, carbonic acids) in serum before the neural barriers and in cerebrospinal fluid (CSF) behind them as a first characterization step of the Mn carriers being involved in moving Mn across the neural barriers. Further identification of Mn-species in CSF was successfully achieved by CZE-inductively coupled plasma (ICP)-dynamic reaction cell (DRC)-mass spectrometry (MS). Serum samples showed Mn mean concentrations of 1.7+/-0.8 microg L(-1). The size distribution of Mn-carriers showed a main peak in the TF/albumin size fitting to the known physiological ligands. However, also an increasing Mn peak at 700 Da with increasing total Mn concentration was seen. Samples of CSF showed Mn mean concentrations of 2.6 microg L(-1)=48 nM. In CSF Mn was found to be mostly bound to low-molecular-mass (LMM)-Mn carriers in the range of 640-680 Da. This is similar to the LMM compound in serum and to Mn-citrate complexes suggested to be present in body fluids. Citrate concentration was 573 microM, thus being in huge excess compared to Mn. CSF was further analyzed by CZE-ICP-DRC-MS. Several Mn-species were monitored and mostly identified. The most abundant Mn-species was Mn-citrate at a concentration of around 0.7 microg Mn L(-1). PMID:18039486

  15. Sensitive redox speciation of iron, neptunium, and plutonium by capillary electrophoresis hyphenated to inductively coupled plasma sector field mass spectrometry.

    PubMed

    Graser, Carl-Heinrich; Banik, Nidhu Lal; Bender, Kerstin Anne; Lagos, Markus; Marquardt, Christian Michael; Marsac, Rémi; Montoya, Vanessa; Geckeis, Horst

    2015-10-01

    The long-term safety assessment for nuclear waste repositories requires a detailed understanding of actinide (geo)chemistry. Advanced analytical tools are required to gain insight into actinide speciation in a given system. The geochemical conditions in the vicinity of a nuclear repository control the redox state of radionuclides, which in turn has a strong impact on their mobility. Besides the long-lived radionuclides plutonium (Pu) and neptunium (Np), which are key elements in high level nuclear waste, iron (Fe) represents a main component in natural systems controlling redox-related geochemical processes. Measuring the oxidation state distribution for redox sensitive radionuclides and other metal ions is challenging at trace concentrations below the detection limit of most available spectroscopic methods (≥10(-6) M). Consequently, ultrasensitive new analytical techniques are required. Capillary electrophoresis (CE) is a suitable separation method for metal cations. CE hyphenated to inductively coupled plasma sector field mass spectrometry (CE-ICP-SF-MS) was used to measure the redox speciation of Pu (III, IV, V, VI), Np (IV, V, VI), and Fe (II, III) at concentrations lower than 10(-7) M. CE coupling and separation parameters such as sample gas pressure, make up flow rate, capillary position, auxiliary gas flow, as well as the electrolyte system were optimized to obtain the maximum sensitivity. We obtain detection limits of 10(-12) M for Np and Pu. The various oxidation state species of Pu and Np in different samples were separated by application of an acetate-based electrolyte system. The separation of Fe (II) and Fe (III) was investigated using different organic complexing ligands, EDTA, and o-phenanthroline. For the Fe redox system, a limit of detection of 10(-8) M was calculated. By applying this analytical system to sorption studies, we were able to underline previously published results for the sorption behavior of Np in highly diluted concentrations, and

  16. High-Speed, Integrated Ablation Cell and Dual Concentric Injector Plasma Torch for Laser Ablation-Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Douglas, David N; Managh, Amy J; Reid, Helen J; Sharp, Barry L

    2015-11-17

    In recent years, laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) has gained increasing importance for biological analysis, where ultratrace imaging at micrometer resolution is required. However, while undoubtedly a valuable research tool, the washout times and sensitivity of current technology have restricted its routine and clinical application. Long periods between sampling points are required to maintain adequate spatial resolution. Additionally, temporal signal dispersion reduces the signal-to-noise ratio, which is a particular concern when analyzing discrete samples, such as individual particles or cells. This paper describes a novel, two-volume laser ablation cell and integrated ICP torch designed to minimize aerosol dispersion for fast, efficient sample transport. The holistic design utilizes a short, continuous diameter fused silica conduit, which extends from the point of ablation, through the ICP torch, and into the base of the plasma. This arrangement removes the requirement for a dispersive component for argon addition, and helps to keep the sample on axis with the ICP cone orifice. Hence, deposition of sample on the cones is theoretically reduced with a resulting improvement in the absolute sensitivity (counts per unit mole). The system described here achieved washouts of 1.5, 3.2, and 4.9 ms for NIST 612 glass, at full width half, 10%, and 1% maximum, respectively, with an 8-14-fold improvement in absolute sensitivity, compared to a single volume ablation cell. To illustrate the benefits of this performance, the system was applied to a contemporary bioanalytical challenge, specifically the analysis of individual biological cells, demonstrating similar improvements in performance.

  17. High-Speed, Integrated Ablation Cell and Dual Concentric Injector Plasma Torch for Laser Ablation-Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Douglas, David N; Managh, Amy J; Reid, Helen J; Sharp, Barry L

    2015-11-17

    In recent years, laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) has gained increasing importance for biological analysis, where ultratrace imaging at micrometer resolution is required. However, while undoubtedly a valuable research tool, the washout times and sensitivity of current technology have restricted its routine and clinical application. Long periods between sampling points are required to maintain adequate spatial resolution. Additionally, temporal signal dispersion reduces the signal-to-noise ratio, which is a particular concern when analyzing discrete samples, such as individual particles or cells. This paper describes a novel, two-volume laser ablation cell and integrated ICP torch designed to minimize aerosol dispersion for fast, efficient sample transport. The holistic design utilizes a short, continuous diameter fused silica conduit, which extends from the point of ablation, through the ICP torch, and into the base of the plasma. This arrangement removes the requirement for a dispersive component for argon addition, and helps to keep the sample on axis with the ICP cone orifice. Hence, deposition of sample on the cones is theoretically reduced with a resulting improvement in the absolute sensitivity (counts per unit mole). The system described here achieved washouts of 1.5, 3.2, and 4.9 ms for NIST 612 glass, at full width half, 10%, and 1% maximum, respectively, with an 8-14-fold improvement in absolute sensitivity, compared to a single volume ablation cell. To illustrate the benefits of this performance, the system was applied to a contemporary bioanalytical challenge, specifically the analysis of individual biological cells, demonstrating similar improvements in performance. PMID:26460246

  18. Some Rare Earth Elements Analysis by Microwave Plasma Torch Coupled with the Linear Ion Trap Mass Spectrometry

    PubMed Central

    Xiong, Xiaohong; Jiang, Tao; Qi, Wenhao; Zuo, Jun; Yang, Meiling; Fei, Qiang; Xiao, Saijin; Yu, Aimin; Zhu, Zhiqiang; Chen, Huanwen

    2015-01-01

    A sensitive mass spectrometric analysis method based on the microwave plasma technique is developed for the fast detection of trace rare earth elements (REEs) in aqueous solution. The plasma was produced from a microwave plasma torch (MPT) under atmospheric pressure and was used as ambient ion source of a linear ion trap mass spectrometer (LTQ). Water samples were directly pneumatically nebulized to flow into the plasma through the central tube of MPT. For some REEs, the generated composite ions were detected in both positive and negative ion modes and further characterized in tandem mass spectrometry. Under the optimized conditions, the limit of detection (LOD) was at the level 0.1 ng/mL using MS2 procedure in negative mode. A single REE analysis can be completed within 2~3 minutes with the relative standard deviation ranging between 2.4% and 21.2% (six repeated measurements) for the 5 experimental runs. Moreover, the recovery rates of these REEs are between the range of 97.6%–122.1%. Two real samples have also been analyzed, including well and orange juice. These experimental data demonstrated that this method is a useful tool for the field analysis of REEs in water and can be used as an alternative supplement of ICP-MS. PMID:26421013

  19. Some Rare Earth Elements Analysis by Microwave Plasma Torch Coupled with the Linear Ion Trap Mass Spectrometry.

    PubMed

    Xiong, Xiaohong; Jiang, Tao; Qi, Wenhao; Zuo, Jun; Yang, Meiling; Fei, Qiang; Xiao, Saijin; Yu, Aimin; Zhu, Zhiqiang; Chen, Huanwen

    2015-01-01

    A sensitive mass spectrometric analysis method based on the microwave plasma technique is developed for the fast detection of trace rare earth elements (REEs) in aqueous solution. The plasma was produced from a microwave plasma torch (MPT) under atmospheric pressure and was used as ambient ion source of a linear ion trap mass spectrometer (LTQ). Water samples were directly pneumatically nebulized to flow into the plasma through the central tube of MPT. For some REEs, the generated composite ions were detected in both positive and negative ion modes and further characterized in tandem mass spectrometry. Under the optimized conditions, the limit of detection (LOD) was at the level 0.1 ng/mL using MS(2) procedure in negative mode. A single REE analysis can be completed within 2~3 minutes with the relative standard deviation ranging between 2.4% and 21.2% (six repeated measurements) for the 5 experimental runs. Moreover, the recovery rates of these REEs are between the range of 97.6%-122.1%. Two real samples have also been analyzed, including well and orange juice. These experimental data demonstrated that this method is a useful tool for the field analysis of REEs in water and can be used as an alternative supplement of ICP-MS. PMID:26421013

  20. On-line electrochemically controlled solid-phase extraction interfaced to electrospray and inductively coupled plasma mass spectrometry.

    PubMed

    Liljegren, Gustav; Forsgard, Niklas; Zettersten, Camilla; Pettersson, Jean; Svedberg, Malin; Herranen, Merja; Nyholm, Leif

    2005-10-01

    Electrochemically controlled solid-phase extractions of anions were interfaced on-line to electrospray mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS), using polypyrrole coated electrodes and a thin-layer electrochemical (EC) flow cell. The results indicate that electrochemically controlled solid-phase extraction (EC-SPE) can be used as a versatile potential controlled sample preparation technique for a range of anions and that the properties of the polypyrrole coatings can be modified by altering the electrodeposition conditions. In the present study, the influence of interfering anions (i.e., fluoride and sulfate), and the anion used during the electropolymerisation, on the bromide extraction recovery was investigated for EC-SPE interfaced to ICP-MS. The results of these experiments show that the interference due to the presence of similar concentrations of sulfate can be reduced when using a polypyrrole coating electropolymerised in the presence of bromide ions. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements were also used to study the morphology of the coatings, as well as the variations in the film thickness within the coatings. The effect of different desorption techniques on the bromide preconcentration factor in the ICP-MS on-line flow system was also examined. Stopped-flow desorption was found to give rise to significantly increased preconcentration factors in comparison with desorptions in flowing solutions. While the desorption efficiency depends on the type of desorption electrolyte (the electrolyte in which the desorption takes place), due to the competing influx of cations, the influence of the pH on the switching charge of the polypyrrole coating was found to be small, at constant ionic strength. To study the applicability of the EC-SPE technique with respect to real samples, investigations were also made with tap water samples spiked with different bromide concentrations. The

  1. [The determination of the natural content of chemical elements in human biological objects (liver, kidney, stomach) by mass spectrometry with inductively coupled plasma].

    PubMed

    Luzanova, I S; Svetlolobov, D Iu; Zorin, Iu V

    2014-01-01

    The objective of the present work was to continue the studies of the sites of concentration of the chemical elements corresponding to normal homeostasis in human biological objects by mass spectrometry with inductively coupled plasma. The study yielded the data on the natural content of 27 elements in the cadaveric liver, kidney, and stomach. It is recommended to use these findings as the reference parameters corresponding to normal homeostasis.

  2. 2D elemental mapping of sections of human kidney stones using laser ablation inductively-coupled plasma-mass spectrometry: Possibilities and limitations

    NASA Astrophysics Data System (ADS)

    Vašinová Galiová, Michaela; Čopjaková, Renata; Škoda, Radek; Štěpánková, Kateřina; Vaňková, Michaela; Kuta, Jan; Prokeš, Lubomír; Kynický, Jindřich; Kanický, Viktor

    2014-10-01

    A 213 nm Nd:YAG-based laser ablation (LA) system coupled to quadrupole-based inductively coupled plasma-mass spectrometer and an ArF* excimer-based LA-system coupled to a double-focusing sector field inductively coupled plasma-mass spectrometer were employed to study the spatial distribution of various elements in kidney stones (uroliths). Sections of the surfaces of uroliths were ablated according to line patterns to investigate the elemental profiles for the different urolith growth zones. This exploratory study was mainly focused on the distinguishing of the main constituents of urinary calculus fragments by means of LA-ICP-mass spectrometry. Changes in the ablation rate for oxalate and phosphate phases related to matrix density and hardness are discussed. Elemental association was investigated on the basis of 2D mapping. The possibility of using NIST SRM 1486 Bone Meal as an external standard for calibration was tested. It is shown that LA-ICP-MS is helpful for determination of the mineralogical composition and size of all phases within the analyzed surface area, for tracing down elemental associations and for documenting the elemental content of urinary stones. LA-ICP-MS results (elemental contents and maps) are compared to those obtained with electron microprobe analysis and solution analysis ICP-MS.

  3. Magnetic solid phase extraction coupled with inductively coupled plasma mass spectrometry for the speciation of mercury in environmental water and human hair samples.

    PubMed

    Ma, Shishuai; He, Man; Chen, Beibei; Deng, Wenchao; Zheng, Qi; Hu, Bin

    2016-01-01

    In this work, γ-mercaptopropyltrimethoxysilane (γ-MPTS) modified Fe3O4@SiO2 magnetic nanoparticles (MNPs) was successfully prepared, and characterized by Fourier transform infrared spectrometer (FT-IR), Transmission electron microscope (TEM) and Vibrating sample magnetometer (VSM). The sorption performance of the prepared Fe3O4@SiO2@γ-MPTS MNPs towards methylmercury (CH3Hg(+)) and inorganic mercury (Hg(2+)) was investigated. It was found that CH3Hg(+) and Hg(2+) could be simultaneously retained on the prepared Fe3O4@SiO2@γ-MPTS MNPs, and the quantitative elution of CH3Hg(+) and total mercury (THg) was achieved by using 1.5 mol L(-1) HCl containing 0.01% and 3% thiourea (m/v), respectively. And the levels of Hg(2+) were obtained by subtracting CH3Hg(+) from THg. Based on the above facts, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the speciation of CH3Hg(+) and Hg(2+). Various experimental parameters affecting MSPE of CH3Hg(+) and Hg(2+) such as pH, eluent, sample volume, and co-existing ions have been studied. Under the optimized conditions, the limits of detection (LODs) for CH3Hg(+) and THg were 1.6 and 1.9 ng L(-1), respectively. The accuracy of the proposed method was validated by analysis of a Certified Reference Material NRCC DORM-2 dogfish muscle, and the determined values are in good agreement with the certified values. The proposed method has also been successfully applied for the speciation of CH3Hg(+) and Hg(2+) in environmental water and human hair samples.

  4. Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory - Determination of Elements in Whole-Water Digests Using Inductively Coupled Plasma-Optical Emission Spectrometry and Inductively Coupled Plasma-Mass Spectrometry

    USGS Publications Warehouse

    Garbarino, John R.; Struzeski, Tedmund M.

    1998-01-01

    Inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) can be used to determine 26 elements in whole-water digests. Both methods have distinct advantages and disadvantages--ICP-OES is capable of analyzing samples with higher elemental concentrations without dilution, however, ICP-MS is more sensitive and capable of determining much lower elemental concentrations. Both techniques gave accurate results for spike recoveries, digested standard reference-water samples, and whole-water digests. Average spike recoveries in whole-water digests were 100 plus/minus 10 percent, although recoveries for digests with high dissolved-solid concentrations were lower for selected elements by ICP-MS. Results for standard reference-water samples were generally within 1 standard deviation of hte most probable values. Statistical analysis of the results from 43 whole-water digest indicated that there was no significant difference among ICP-OES, ICP-MS, and former official methods of analysis for 24 of the 26 elements evaluated.

  5. Determination of mercury in fish otoliths by cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS)†

    PubMed Central

    Kenduzler, Erdal; Ates, Mehmet; Arslan, Zikri; McHenry, Melanie; Tchounwou, Paul B.

    2012-01-01

    A method based on cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS) has been developed for determination of inorganic mercury, Hg(II), and total mercury in fish otoliths. Sodium borohydride (NaBH4) was used as the only reducing agent and its concentration was optimized across an acidity gradient to selectively reduce Hg(II) without affecting methylmercury, CH3Hg(I). Inorganic Hg was quantitatively reduced to elemental mercury (Hg0) with 1×10−4% (m/v) NaBH4. CH3Hg(I) required a minimum of 0.5% (m/v) NaBH4 for complete reduction. Increasing the HCl concentration of solution to 5% (v/v) improved the selectivity toward Hg(II) as it decreased the signals from CH3Hg(I) to baseline levels. Potassium ferricyanide solution was the most effective in eliminating the memory effects of Hg compared with a number of chelating and oxidizing agents, including EDTA, gold chloride, thiourea, cerium ammonium nitrate and 2-mercaptoethylamine chloride. The relative standard deviation (RSD) was less than 5% for 1.0 μg L−1 Hg(II) solution. The detection limits were 4.2 and 6.4 ng L−1 (ppt) for Hg(II) and total Hg, respectively. Sample dissolution conditions and recoveries were examined with ultra-pure CaCO3 (99.99%) spiked with Hg(II) and CH3HgCl. Methylmercury was stable when dissolution was performed with up to 20% (v/v) HCl at 100 oC. Recoveries from spiked solutions were higher than 95% for both Hg(II) and CH3Hg(I). The method was applied to the determination of Hg(II) and total Hg concentrations in the otoliths of red emperor (CRM 22) and Pacific halibut. Total Hg concentration in the otoliths was 0.038 ± 0.004 μg g−1 for the red emperor and 0.021 ± 0.003 μg g−1 for the Pacific halibut. Inorganic Hg accounted for about 25% of total Hg indicating that Hg in the otoliths was predominantly organic mercury (e.g., methylmercury). However, as opposed to the bioaccumulation in tissues, methylmercury levels in otoliths was very low suggesting a

  6. Laser ablation inductively coupled plasma dynamic reaction cell mass spectrometry for the multi-element analysis of polymers

    NASA Astrophysics Data System (ADS)

    Resano, M.; García-Ruiz, E.; Vanhaecke, F.

    2005-11-01

    In this work, the potential of laser ablation-inductively coupled plasma-mass spectrometry for the fast analysis of polymers has been explored. Different real-life samples (polyethylene shopping bags, an acrylonitrile butadiene styrene material and various plastic bricks) as well as several reference materials (VDA 001 to 004, Cd in polyethylene) have been selected for the study. Two polyethylene reference materials (ERM-EC 680 and 681), for which a reference or indicative value for the most relevant metals is available, have proved their suitability as standards for calibration. Special attention has been paid to the difficulties expected for the determination of Cr at the μg g - 1 level in this kind of materials, due to the interference of ArC + ions on the most abundant isotopes of Cr. The use of ammonia as a reaction gas in a dynamic reaction cell is shown to alleviate this problem, resulting in a limit of detection of 0.15 μg g - 1 for this element, while limiting only modestly the possibilities of the technique for simultaneous multi-element analysis. In this regard, As is the analyte most seriously affected by the use of ammonia, and its determination has to be carried out in vented mode, at the expense of measuring time. In all cases studied, accurate results could be obtained for elements ranging in content from the sub-μg g - 1 level to tens of thousands of μg g - 1 . However, the use of an element of known concentration as internal standard may be needed for materials with a matrix significantly different from that of the standard (polyethylene in this work). Precision ranged between 5% and 10% RSD for elements found at the 10 μg g - 1 level or higher, while this value could deteriorate to 20% for analytes found at the sub-μg g - 1 level. Overall, the technique evaluated presents many advantages for the fast and accurate multi-element analysis of these materials, avoiding laborious digestion procedures and minimizing the risk of analyte losses due

  7. RAPID DETERMINATION OF ACTINIDES IN URINE BY INDUCTIVELY-COUPLED PLASMA MASS SPECTROMETRY AND ALPHA SPECTROMETRY: A HYBRID APPROACH

    SciTech Connect

    Maxwell, S.; Jones, V.

    2009-05-27

    A new rapid separation method that allows separation and preconcentration of actinides in urine samples was developed for the measurement of longer lived actinides by inductively coupled plasma mass spectrometry (ICP-MS) and short-lived actinides by alpha spectrometry; a hybrid approach. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration, if required, is performed using a streamlined calcium phosphate precipitation. Similar technology has been applied to separate actinides prior to measurement by alpha spectrometry, but this new method has been developed with elution reagents now compatible with ICP-MS as well. Purified solutions are split between ICP-MS and alpha spectrometry so that long- and short-lived actinide isotopes can be measured successfully. The method allows for simultaneous extraction of 24 samples (including QC samples) in less than 3 h. Simultaneous sample preparation can offer significant time savings over sequential sample preparation. For example, sequential sample preparation of 24 samples taking just 15 min each requires 6 h to complete. The simplicity and speed of this new method makes it attractive for radiological emergency response. If preconcentration is applied, the method is applicable to larger sample aliquots for occupational exposures as well. The chemical recoveries are typically greater than 90%, in contrast to other reported methods using flow injection separation techniques for urine samples where plutonium yields were 70-80%. This method allows measurement of both long-lived and short-lived actinide isotopes. 239Pu, 242Pu, 237Np, 243Am, 234U, 235U and 238U were measured by ICP-MS, while 236Pu, 238Pu, 239Pu, 241Am, 243Am and 244Cm were measured by alpha spectrometry. The method can also be adapted so that the separation of uranium isotopes for assay is not required, if uranium assay by direct dilution of the urine sample is preferred instead

  8. Gadolinium-uptake by aquatic and terrestrial organisms-distribution determined by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Lingott, Jana; Lindner, Uwe; Telgmann, Lena; Esteban-Fernández, Diego; Jakubowski, Norbert; Panne, Ulrich

    2016-02-01

    Gadolinium (Gd) based contrast agents (CA) are used to enhance magnetic resonance imaging. As a consequence of excretion by patients and insufficient elimination in wastewater treatment plants they are detected in high concentrations in surface water. At present, little is known about the uptake of these species by living organisms in aquatic systems. Therefore the uptake of gadolinium containing chelates by plants and animals grown in exposed water or on soil irrigated with exposed water was investigated. For this purpose two types of plants were treated with two different contrast agents. The uptake of the Gd contrast agents was studied by monitoring the elemental distribution with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). This technique allows the multi-elemental analysis of solid samples with high resolution and little sample preparation. The analysis of L. minor showed that the uptake of Gd correlated with the concentration of gadodiamide in the water. The higher the concentration in the exposed water, the larger the Gd signal in the LA-ICP-MS acquired image. Exposure time experiments showed saturation within one day. The L. minor had contact with the CAs through roots and fronds, whereas the L. sativum only showed uptake through the roots. These results show that an external absorption of the CA through the leaves of L. sativum was impossible. All the analyzed parts of the plant showed Gd signal from the CA; the highest being at the main vein of the leaf. It is shown that the CAs can be taken up from plants. Furthermore, the uptake and distribution of Gd in Daphnia magna were shown. The exposure via cultivation medium is followed by Gd signals on the skin and in the area of the intestine, while the uptake via exposed nutrition algae causes the significantly highest Gd intensities in the area of the intestine. Because there are hints of negative effects for human organism these findings are important as they show that Gd based

  9. Speciation of arsenic in different types of nuts by ion chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Kannamkumarath, Sasi S; Wróbel, Kazimierz; Wróbel, Katarzyna; Caruso, Joseph A

    2004-03-24

    In this work the quantitative determination and analytical speciation of arsenic were undertaken in different types of nuts, randomly purchased from local markets. The hardness of the whole nuts and high lipid content made the preparation of this material difficult for analysis. The lack of sample homogeneity caused irreproducible results. To improve the precision of analysis, arsenic was determined separately in nut oil and in the defatted sample. The lipids were extracted from the ground sample with the two portions of a mixture of chloroform and methanol (2:1). The defatted material was dried and ground again, yielding a fine powder. The nut oil was obtained by combining the two organic extracts and by evaporating the solvents. The two nut fractions were microwave digested, and total arsenic was determined by inductively coupled plasma mass spectrometry (ICP-MS). The results obtained for oils from different types of nuts showed element concentration in the range 2.9-16.9 ng g(-)(1). Lower levels of arsenic were found in defatted material (<0.1 ng g(-)(1) with the exception of Brazil nuts purchased with and without shells, 3.0 and 2.8 ng g(-)(1) respectively). For speciation analysis of arsenic in nut oils, elemental species were extracted from 2 g of oil with 12 mL of chloroform/methanol (2:1) and 8 mL of deionized water. The aqueous layer, containing polar arsenic species, was evaporated and the residue dissolved and analyzed by ion chromatography-ICP-MS. The anion exchange chromatography enabled separation of As(III), dimethylarsinic acid (DMAs(V)), monomethylarsonic acid (MMAs(V)), and As(V) within 8 min. Several types of nuts were analyzed, including walnuts, Brazil nuts, almonds, cashews, pine nuts, peanuts, pistachio nuts, and sunflower seeds. The recovery for the speciation procedure was in the range 72.7-90.6%. The primary species found in the oil extracts were As(III) and As(V). The arsenic concentration levels in these two species were 0.7-12.7 and 0

  10. Gadolinium-uptake by aquatic and terrestrial organisms-distribution determined by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Lingott, Jana; Lindner, Uwe; Telgmann, Lena; Esteban-Fernández, Diego; Jakubowski, Norbert; Panne, Ulrich

    2016-02-01

    Gadolinium (Gd) based contrast agents (CA) are used to enhance magnetic resonance imaging. As a consequence of excretion by patients and insufficient elimination in wastewater treatment plants they are detected in high concentrations in surface water. At present, little is known about the uptake of these species by living organisms in aquatic systems. Therefore the uptake of gadolinium containing chelates by plants and animals grown in exposed water or on soil irrigated with exposed water was investigated. For this purpose two types of plants were treated with two different contrast agents. The uptake of the Gd contrast agents was studied by monitoring the elemental distribution with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). This technique allows the multi-elemental analysis of solid samples with high resolution and little sample preparation. The analysis of L. minor showed that the uptake of Gd correlated with the concentration of gadodiamide in the water. The higher the concentration in the exposed water, the larger the Gd signal in the LA-ICP-MS acquired image. Exposure time experiments showed saturation within one day. The L. minor had contact with the CAs through roots and fronds, whereas the L. sativum only showed uptake through the roots. These results show that an external absorption of the CA through the leaves of L. sativum was impossible. All the analyzed parts of the plant showed Gd signal from the CA; the highest being at the main vein of the leaf. It is shown that the CAs can be taken up from plants. Furthermore, the uptake and distribution of Gd in Daphnia magna were shown. The exposure via cultivation medium is followed by Gd signals on the skin and in the area of the intestine, while the uptake via exposed nutrition algae causes the significantly highest Gd intensities in the area of the intestine. Because there are hints of negative effects for human organism these findings are important as they show that Gd based

  11. Cathodoluminescence, laser ablasion inductively coupled plasma mass spectrometry, electron probe microanalysis and electron paramagnetic resonance analyses of natural sphalerite

    USGS Publications Warehouse

    Karakus, M.; Hagni, R.D.; Koenig, A.; Ciftc, E.

    2008-01-01

    Natural sphalerite associated with copper, silver, lead-zinc, tin and tungsten deposits from various world-famous mineral deposits have been studied by cathodoluminescence (CL), laser ablasion inductively coupled plasma mass spectrometry (LA-ICP-MS), electron probe microanalysis (EPMA) and electron paramagnetic resonance (EPR) to determine the relationship between trace element type and content and the CL properties of sphalerite. In general, sphalerite produces a spectrum of CL colour under electron bombardment that includes deep blue, turquoise, lime green, yellow-orange, orange-red and dull dark red depending on the type and concentration of trace quantities of activator ions. Sphalerite from most deposits shows a bright yellow-orange CL colour with ??max centred at 585 nm due to Mn2+ ion, and the intensity of CL is strongly dependent primarily on Fe2+ concentration. The blue emission band with ??max centred at 470-490 nm correlates with Ga and Ag at the Tsumeb, Horn Silver, Balmat and Kankoy mines. Colloform sphalerite from older well-known European lead-zinc deposits and late Cretaceous Kuroko-type VMS deposits of Turkey shows intense yellowish CL colour and their CL spectra are characterised by extremely broad emission bands ranging from 450 to 750 nm. These samples are characterised by low Mn (<10 ppm) and Ag (<1 ppm), and they are enriched in Tl (1-30 ppm) and Pb (80-1500 ppm). Strong green CL is produced by sphalerite from the Balmat-Edwards district. Amber, lime-green and red-orange sphalerite produced weak orange-red CL at room temperatures, with several emission bands centred at 490, 580, 630, 680, 745, with ??max at 630 nm being the strongest. These emission bands are well correlated with trace quantities of Sn, In, Cu and Mn activators. Sphalerite from the famous Ogdensburg and Franklin mines exhibited brilliant deep blue and orange CL colours and the blue CL may be related to Se. Cathodoluminescence behaviour of sphalerite serves to characterise ore

  12. Development of an analytical method for the determination of polybrominated diphenyl ethers in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Novak, Petra; Zuliani, Tea; Milačič, Radmila; Ščančar, Janez

    2016-04-01

    Polybrominated diphenyl ethers (PBDEs) are flame retardants. As a consequence of their widespread use, they have been released into the environment. PBDEs are lipophilic organic contaminants that enter wastewater treatment plants (WWTPs) from urban, agricultural and industrial discharges. Because of their low aqueous solubility and resistance to biodegradation, up to 90% of the PBDEs are accumulated in the sewage sludge during the wastewater treatment. To assess the possibilities for sludge re-use, a reliable determination of the concentrations of these PBDEs is of crucial importance. Six PBDE congeners (BDE 28, BDE 47, BDE 99, BDE 100, BDE 153 and BDE 154) are listed as priority substances under the EU Water Framework Directive. In the present work a simple analytical method with minimal sample-preparation steps was developed for a sensitive and reliable determination of the six PBDEs in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). For this purpose an extraction procedure was optimised. Different extracting agents (methanol (MeOH), acetic acid (AcOH)/MeOH mixture (3:1) and 0.1 mol L(-1) hydrochloric acid (HCl) in MeOH) followed by the addition of a Tris-citrate buffer (co-extracting agent) and iso-octane were applied under different modes of extraction (mechanical shaking, microwave- and ultrasound-assisted extraction). Mechanical shaking or the microwave-assisted extraction of sewage sludge with 0.1 mol L(-1) HCl in MeOH and the subsequent addition of the Tris-citrate buffer and the iso-octane extracted the PBDEs from the complex sludge matrix most effectively. However, due to easier sample manipulation during the extraction step, mechanical shaking was used. The PBDEs in the organic phase were quantified with GC-ICP-MS by applying a standard addition calibration method. The spike recovery test (recoveries between 95 and 104%) and comparative analyses with the species-specific isotope

  13. Evaluation of space charge effects in the second vacuum stage of a commercial inductively coupled plasma mass spectrometer by planar laser-induced fluorescence imaging

    NASA Astrophysics Data System (ADS)

    Edmund, Alisa J.; Bergeson, Scott D.; Lyon, Mary; Taylor, Nicholas; Kalinitchenko, Iouri; Farnsworth, Paul B.

    2012-10-01

    The effect of matrix on the formation and focusing of a Ca ion beam in the second vacuum stage of an inductively coupled plasma mass spectrometer has been evaluated with the use of planar laser induced fluorescence. A cross section of the beam was imaged near the entrance to the mass analyzer of a commercial instrument. Characteristics of the beam from a solution containing only the Ca analyte closely matched those predicted by simulation software. The individual addition of three matrix species, Mg, Cs, and Pb, had minor effect on beam shape. Cs and Pb both affected the beam trajectory. The most pronounced effect was with the Pb matrix, which caused an order-of-magnitude drop in the Ca signal intensity at the electron multiplier of the mass spectrometer. The loss in signal was due primarily to a shift in the direction and location of the Ca ion beam that caused it to miss the entrance into the mass analyzer.

  14. Speciation of Selenium in Selenium-Enriched Sunflower Oil by High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry/Electrospray-Orbitrap Tandem Mass Spectrometry.

    PubMed

    Bierla, Katarzyna; Flis-Borsuk, Anna; Suchocki, Piotr; Szpunar, Joanna; Lobinski, Ryszard

    2016-06-22

    The reaction of sunflower oil with selenite produces a complex mixture of selenitriglycerides with antioxidant and anticancer properties. To obtain insight into the identity and characteristics of the species formed, an analytical approach based on the combination of high-performance liquid chromatography (HPLC) with (78)Se-specific selenium detection by inductively coupled plasma mass spectrometry (ICP MS) and high-resolution (100 000), high mass accuracy (<1 ppm) molecule-specific detection by electrospray-Orbitrap MS(3) was developed. For the first time, a non-aqueous mobile phase gradient was used in reversed-phase HPLC-ICP MS for the separation of a complex mixture of selenospecies and a mathematical correction of the background signal was developed. The identical chromatographic conditions served for the sample introduction into electrospray MS. Two types of samples were analyzed: sunflower oil dissolved in isopropanol and methanol extract of the oil containing 65% selenium. HPLC-ICP MS showed 14 peaks, 11 of which could also be detected in the methanol extract. Isotopic patterns corresponding to molecules with one or two selenium atoms could be attributed by Orbitrap MS at the retention times corresponding to the HPLC-ICP MS peak apexes. Structural data for these species were acquired by MS(2) and MS(3) fragmentation of protonated or sodiated ions using high-energy collisional dissociation (HCD). A total of 11 selenium-containing triglycerol derivatives resulting from the oxidation of one or two double bonds of linoleic acid and analogous derivatives of glycerol-mixed linoleate(s)/oleinate(s) have been identified for the first time. The presence of these species was confirmed by the targeted analysis in the total oil isopropanol solution. Their identification corroborated the predicted elution order in reversed-phase chromatography: LLL (glycerol trilinoleate), LLO (glycerol dilinoleate-oleinate), LOO (glycerol linoleate-dioleinate), OOO (glycerol

  15. Speciation of Selenium in Selenium-Enriched Sunflower Oil by High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry/Electrospray-Orbitrap Tandem Mass Spectrometry.

    PubMed

    Bierla, Katarzyna; Flis-Borsuk, Anna; Suchocki, Piotr; Szpunar, Joanna; Lobinski, Ryszard

    2016-06-22

    The reaction of sunflower oil with selenite produces a complex mixture of selenitriglycerides with antioxidant and anticancer properties. To obtain insight into the identity and characteristics of the species formed, an analytical approach based on the combination of high-performance liquid chromatography (HPLC) with (78)Se-specific selenium detection by inductively coupled plasma mass spectrometry (ICP MS) and high-resolution (100 000), high mass accuracy (<1 ppm) molecule-specific detection by electrospray-Orbitrap MS(3) was developed. For the first time, a non-aqueous mobile phase gradient was used in reversed-phase HPLC-ICP MS for the separation of a complex mixture of selenospecies and a mathematical correction of the background signal was developed. The identical chromatographic conditions served for the sample introduction into electrospray MS. Two types of samples were analyzed: sunflower oil dissolved in isopropanol and methanol extract of the oil containing 65% selenium. HPLC-ICP MS showed 14 peaks, 11 of which could also be detected in the methanol extract. Isotopic patterns corresponding to molecules with one or two selenium atoms could be attributed by Orbitrap MS at the retention times corresponding to the HPLC-ICP MS peak apexes. Structural data for these species were acquired by MS(2) and MS(3) fragmentation of protonated or sodiated ions using high-energy collisional dissociation (HCD). A total of 11 selenium-containing triglycerol derivatives resulting from the oxidation of one or two double bonds of linoleic acid and analogous derivatives of glycerol-mixed linoleate(s)/oleinate(s) have been identified for the first time. The presence of these species was confirmed by the targeted analysis in the total oil isopropanol solution. Their identification corroborated the predicted elution order in reversed-phase chromatography: LLL (glycerol trilinoleate), LLO (glycerol dilinoleate-oleinate), LOO (glycerol linoleate-dioleinate), OOO (glycerol

  16. [Determination of Total Sulfur Dioxide in Chinese Herbal Medicines via Triple Quadrupole Inductively Coupled Plasma Mass Spectrometry].

    PubMed

    Wang, Xiao-wei; Liu, Jing-fu; Guan, Hong; Wang, Xiao-yan; Shag, Bing; Zhang, Jing; Liu, Li-ping; Zhang, Ni-na

    2016-02-01

    As an important treatment method, sulfur fumigation plays an essential role in the production and preservation of traditional Chinese herbal medicines. Although there is strict regulation on the use of sulfur dioxide, the abuse of sulfur dioxide still occurred from time to time. And the public faces a high risk of exposure. Because of the poor precision and tedious preparation procedures of traditional recommended titration, the accurate and convenient determination of sulfur dioxide in Chinese herbal medicines is still a critical analytical task for medicines safety and the public health. In this study, an accurate, high-throughput, and convenient method for the absolute determination of SO₂ in Chinese herbal medicines based on triple quadrupole inductively coupled plasma mass spectrometry (ICP-MS/MS) technique is developed. The study compared the quantitative ability for sulfur when the ICP-MS operated under traditional single quadrupole (QMS) mode and novel triple quadrupole (MS/MS) mode with three Reaction/Collision cell condition (no gas, helium, and oxygen). The result indicated that when the concentration of sulfate ranging from 0.5 to 100 mg · L⁻¹, isotopic ³⁴S can be selected as quantitative ion either the ICP-MS operated under the QMS mode or MS/MS mode. The use of helium in the Reaction/Collision cell decreased the single intensity of background ions. Better than QMS mode, the MS/MS mode can effectively reduced background interference. But there are no significant differences about the linear range and limit of detection. However, when the ICP-MS operated under MS/MS mode and oxygen was used as reaction gas in the Reaction/Collision cell, the ICP-MS/MS provided an interference-free performance, the linear range and limit of detection improved significantly. Either ³²S or ³⁴S exhibits an excellent linearity (r > 0.999) over the concentration range of 0.02-100 mg · L⁻¹, with a limit of detection of 5.48 and 9.76 µg · L⁻¹ for

  17. Closed inductively coupled plasma cell

    DOEpatents

    Manning, Thomas J.; Palmer, Byron A.; Hof, Douglas E.

    1990-01-01

    A closed inductively coupled plasma cell generates a relatively high power, low noise plasma for use in spectroscopic studies. A variety of gases can be selected to form the plasma to minimize spectroscopic interference and to provide a electron density and temperature range for the sample to be analyzed. Grounded conductors are placed at the tube ends and axially displaced from the inductive coil, whereby the resulting electromagnetic field acts to elongate the plasma in the tube. Sample materials can be injected in the plasma to be excited for spectroscopy.

  18. Closed inductively coupled plasma cell

    DOEpatents

    Manning, T.J.; Palmer, B.A.; Hof, D.E.

    1990-11-06

    A closed inductively coupled plasma cell generates a relatively high power, low noise plasma for use in spectroscopic studies is disclosed. A variety of gases can be selected to form the plasma to minimize spectroscopic interference and to provide a electron density and temperature range for the sample to be analyzed. Grounded conductors are placed at the tube ends and axially displaced from the inductive coil, whereby the resulting electromagnetic field acts to elongate the plasma in the tube. Sample materials can be injected in the plasma to be excited for spectroscopy. 1 fig.

  19. Simultaneous extraction of arsenic and selenium species from rice products by microwave-assisted enzymatic extraction and analysis by ion chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Mar, Jorge L Guzmán; Reyes, Laura Hinojosa; Rahman, G M Mizanur; Kingston, H M Skip

    2009-04-22

    A microwave-assisted enzymatic extraction (MAEE) method was developed for the simultaneous extraction of arsenic (As) and selenium (Se) species in rice products. The total arsenic and selenium content in the enzymatic extracts were determined by inductively coupled plasma mass spectrometry (ICP-MS), while the speciation analysis was performed by ion chromatography coupled to inductively coupled plasma-mass spectrometry (IC-ICP-MS). The main factors affecting the enzymatic extraction process were evaluated in NIST SRM-1568a rice flour. The optimum extraction conditions were 500 mg of sample, 50 mg of protease XIV, and 25 mg of alpha-amylase in aqueous medium during 40 min at 37 degrees C. The extraction recoveries of total As and Se reached 100 +/- 3 and 80 +/- 4%, respectively. The species stability study during the MAEE process did not show transformation of the target species in rice products. The results of As speciation obtained for SRM-1568a were in agreement with previous studies of As speciation performed on the same reference material. The proposed method was applied to the determination of As and Se species in rice and rice-based cereals. Arsenite [As(III)], arsenate [As(V)], dimethylarsinic acid (DMA), and selenomethionine (SeMet) were the predominant species identified in rice products.

  20. Determination of lead, cadmium and mercury in blood for assessment of environmental exposure: A comparison between inductively coupled plasma mass spectrometry and atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Palmer, Christopher D.; Lewis, Miles E.; Geraghty, Ciaran M.; Barbosa, Fernando; Parsons, Patrick J.

    2006-08-01

    A biomonitoring method for the determination of Pb, Cd, and Hg at background levels in whole blood by inductively coupled plasma-mass spectrometry is described. While this method was optimized for assessing Pb, Cd and Hg at environmental levels, it also proved suitable for assessing concentrations associated with occupational exposure. The method requires as little as 200 μl of blood that is diluted 1 + 49 for direct analysis in the inductively coupled plasma-mass spectrometer. Method performance is compared to well-established AAS methods. Initial method validation was accomplished using National Institute of Standards and Technology (NIST) Standard Reference Material 966, Toxic Metals in Bovine Blood. Method detection limits (3s) are 0.05 μg dl - 1 for Pb, 0.09 μg l - 1 for Cd; and 0.17 μg l - 1 for Hg. Repeatability ranged from 1.4% to 2.8% for Pb; 3% to 10% for Cd; and 2.6% to 8.8% for Hg. In contrast, AAS method detection limits were 1 μg dl - 1 , 0.54 μg l - 1 , and 0.6 μg l - 1 , for Pb, Cd, and Hg, respectively. Further performance assessments were conducted over a 2-year period via participation in four international External Quality Assessment Schemes (EQAS) operated specifically for toxic metals in blood. This includes schemes operated by (a) the New York State Department of Health's Wadsworth Center, Albany, NY, USA (b) L'Institut National de Santé Publique du Québec, Centre de Toxicologie du Québec, Canada, (c) Friedrich-Alexander University, Erlangen, Germany, and (d) the University of Surrey, Guildford, UK Trace Elements scheme. The EQAS data reflect analytical performance for blind samples analyzed independently by both inductively coupled plasma-mass spectrometry and AAS methods.

  1. Barium determination in gastric contents, blood and urine by inductively coupled plasma mass spectrometry in the case of oral barium chloride poisoning.

    PubMed

    Łukasik-Głębocka, Magdalena; Sommerfeld, Karina; Hanć, Anetta; Grzegorowski, Adam; Barałkiewicz, Danuta; Gaca, Michał; Zielińska-Psuja, Barbara

    2014-01-01

    A serious case of barium intoxication from suicidal ingestion is reported. Oral barium chloride poisoning with hypokalemia, neuromuscular and cardiac toxicity, treated with intravenous potassium supplementation and hemodialysis, was confirmed by the determination of barium concentrations in gastric contents, blood, serum and urine using the inductively coupled plasma mass spectrometry method. Barium concentrations in the analyzed specimens were 20.45 µg/L in serum, 150 µg/L in blood, 10,500 µg/L in urine and 63,500 µg/L in gastric contents. Results were compared with barium levels obtained from a non-intoxicated person.

  2. Mapping of lead, magnesium and copper accumulation in plant tissues by laser-induced breakdown spectroscopy and laser-ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kaiser, J.; Galiová, M.; Novotný, K.; Červenka, R.; Reale, L.; Novotný, J.; Liška, M.; Samek, O.; Kanický, V.; Hrdlička, A.; Stejskal, K.; Adam, V.; Kizek, R.

    2009-01-01

    Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) were utilized for mapping the accumulation of Pb, Mg and Cu with a resolution up to 200 μm in a up to cm × cm area of sunflower ( Helianthus annuus L.) leaves. The results obtained by LIBS and LA-ICP-MS are compared with the outcomes from Atomic Absorption Spectrometry (AAS) and Thin-Layer Chromatography (TLC). It is shown that laser-ablation based analytical methods can substitute or supplement these techniques mainly in the cases when a fast multi-elemental mapping of a large sample area is needed.

  3. Determination of abacavir, tenofovir, darunavir, and raltegravir in human plasma and saliva using liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Yamada, Eiko; Takagi, Ritsuo; Sudo, Koji; Kato, Shingo

    2015-10-10

    A liquid chromatography-tandem mass spectrometry assay for the determination of abacavir (ABC), tenofovir (TFV), darunavir (DRV), and raltegravir (RAL) in human plasma and saliva was developed and validated to investigate the applicability of saliva as an appropriate specimen for therapeutic drug monitoring. As internal standards, TFV was chosen for ABC, ABC was chosen for TFV, RAL for DRV, and DRV for RAL. Sample preparation involved protein precipitation with acetonitrile, evaporation of solvent using a centrifugal evaporator, and reconstitution by dissolving the residue in mobile phase. Liquid chromatography was performed on a C18 reverse phase column (1.5 × 50 mm, 5 μm) isocratically at a flow rate of 0.2 mL/min using 5mM formic acid-3% (v/v) acetonitrile as the mobile phase for ABC and TFV and 5mM formic acid-35% (v/v) acetonitrile as the mobile phase for DRV and RAL. The run time was 6 min, and the retention time was approximately 2.0 min for TFV, 2.5 min for RAL, and 4-4.5 min for ABC and DRV. Analytes were detected using tandem mass spectrometry in positive electrospray ionization mode. The precursor/product ion transitions (m/z) were 287.3/191.2 for ABC, 288.5/176.2 for TFV, 548.3/392.3 for DRV, and 445.3/109.5 for RAL, and were monitored on a triple-quadrupole mass spectrometer operated in the multiple reaction monitoring mode. The linearity of the assay was assessed in the range 1-10,000 ng/mL for all four drugs. Within-run and between-run mean accuracy, precision, and the extraction recovery for all drugs were -14.5-18.1%, 1.2-13.1%, and 86.0-111.1%, respectively. The proposed assay is sufficiently sensitive and accurate to quantify these drugs in plasma and saliva, and is suitable for investigating the relationship between drug concentrations in plasma and saliva.

  4. High-Resolution Inductively Coupled Plasma Optical Emission Spectrometry for (234)U/(238)Pu Age Dating of Plutonium Materials and Comparison to Sector Field Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Krachler, Michael; Alvarez-Sarandes, Rafael; Rasmussen, Gert

    2016-09-01

    Employing a commercial high-resolution inductively coupled plasma optical emission spectrometry (HR-ICP-OES) instrument, an innovative analytical procedure for the accurate determination of the production age of various Pu materials (Pu powder, cardiac pacemaker battery, (242)Cm heat source, etc.) was developed and validated. This undertaking was based on the fact that the α decay of (238)Pu present in the investigated samples produced (234)U and both mother and daughter could be identified unequivocally using HR-ICP-OES. Benefiting from the high spectral resolution of the instrument (<5 pm) and the isotope shift of the emission lines of both nuclides, (234)U and (238)Pu were selectively and directly determined in the dissolved samples, i.e., without a chemical separation of the two analytes from each other. Exact emission wavelengths as well as emission spectra of (234)U centered around λ = 411.590 nm and λ = 424.408 nm are reported here for the first time. Emission spectra of the isotopic standard reference material IRMM-199, comprising about one-third each of (233)U, (235)U, and (238)U, confirmed the presence of (234)U in the investigated samples. For the assessment of the (234)U/(238)Pu amount ratio, the emission signals of (234)U and (238)Pu were quantified at λ = 424.408 nm and λ = 402.148 nm, respectively. The age of the investigated samples (range: 26.7-44.4 years) was subsequently calculated using the (234)U/(238)Pu chronometer. HR-ICP-OES results were crossed-validated through sector field inductively coupled plasma mass spectrometry (SF-ICPMS) analysis of the (234)U/(238)Pu amount ratio of all samples applying isotope dilution combined with chromatographic separation of U and Pu. Available information on the assumed ages of the analyzed samples was consistent with the ages obtained via the HR-ICP-OES approach. Being based on a different physical detection principle, HR-ICP-OES provides an alternative strategy to the well-established mass

  5. High-Resolution Inductively Coupled Plasma Optical Emission Spectrometry for (234)U/(238)Pu Age Dating of Plutonium Materials and Comparison to Sector Field Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Krachler, Michael; Alvarez-Sarandes, Rafael; Rasmussen, Gert

    2016-09-01

    Employing a commercial high-resolution inductively coupled plasma optical emission spectrometry (HR-ICP-OES) instrument, an innovative analytical procedure for the accurate determination of the production age of various Pu materials (Pu powder, cardiac pacemaker battery, (242)Cm heat source, etc.) was developed and validated. This undertaking was based on the fact that the α decay of (238)Pu present in the investigated samples produced (234)U and both mother and daughter could be identified unequivocally using HR-ICP-OES. Benefiting from the high spectral resolution of the instrument (<5 pm) and the isotope shift of the emission lines of both nuclides, (234)U and (238)Pu were selectively and directly determined in the dissolved samples, i.e., without a chemical separation of the two analytes from each other. Exact emission wavelengths as well as emission spectra of (234)U centered around λ = 411.590 nm and λ = 424.408 nm are reported here for the first time. Emission spectra of the isotopic standard reference material IRMM-199, comprising about one-third each of (233)U, (235)U, and (238)U, confirmed the presence of (234)U in the investigated samples. For the assessment of the (234)U/(238)Pu amount ratio, the emission signals of (234)U and (238)Pu were quantified at λ = 424.408 nm and λ = 402.148 nm, respectively. The age of the investigated samples (range: 26.7-44.4 years) was subsequently calculated using the (234)U/(238)Pu chronometer. HR-ICP-OES results were crossed-validated through sector field inductively coupled plasma mass spectrometry (SF-ICPMS) analysis of the (234)U/(238)Pu amount ratio of all samples applying isotope dilution combined with chromatographic separation of U and Pu. Available information on the assumed ages of the analyzed samples was consistent with the ages obtained via the HR-ICP-OES approach. Being based on a different physical detection principle, HR-ICP-OES provides an alternative strategy to the well-established mass

  6. 87Sr/86Sr isotope ratio measurements by laser ablation multicollector inductively coupled plasma mass spectrometry: Reconsidering matrix interferences in bioapatites and biogenic carbonates

    NASA Astrophysics Data System (ADS)

    Irrgeher, Johanna; Galler, Patrick; Prohaska, Thomas

    2016-11-01

    This study is dedicated to the systematic investigation of the effect of interferences on Sr isotopic analyses in biological apatite and carbonate matrices using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC ICP-MS). Trends towards higher 87Sr/86Sr ratios for LA-MC ICP-MS compared to solution-nebulization based MC ICP-MS when analysing bioapatite matrices (e.g. human teeth) and lower ratios in case of calcium carbonates (e.g. fish ear stones) were observed. This effect can be related to the presence of significant matrix-related interferences such as molecular ions (e.g. (40Ca-31P-16O)+, (40Ar-31P-16O)+, (42Ca-44Ca)+, (46Ca40Ar)+) as well as in many cases concomitant atomic ions (e.g. 87Rb+, 174Hf2 +). Direct 87Sr/86Sr ratio measurements in Ca-rich samples are conducted without the possibility of prior sample separation, which can be accomplished routinely for solution-based analysis. The presence of Ca-Ar and Ca-Ca molecular ion interferences in the mass range of Sr isotopes is shown using the mass resolving capabilities of a single collector inductively coupled plasma sector field mass spectrometer operated in medium mass resolution when analysing bioapatites and calcium carbonate samples. The major focus was set on analysing human tooth samples, fish hard parts and geological carbonates. Potential sources of interferences were identified and corrected for. The combined corrections of interferences and adequate instrumental isotopic fractionation correction procedures lead to accurate data even though increased uncertainties have to be taken into account. The results are discussed along with approaches presented in literature for data correction in laser ablation analysis.

  7. Determination of 234U/238U, 235U/238U and 236U/238U isotope ratios in urine using sector field inductively coupled plasma mass spectrometry.

    PubMed

    Xiao, Ge; Jones, Robert L; Saunders, David; Caldwell, Kathleen L

    2014-12-01

    Quantification of the isotopic composition of uranium in urine at low levels of concentration is important for assessing both military and civilian populations' exposures to uranium. However, until now there has been no convenient, precise method established for rapid determination of multiple uranium isotope ratios. Here, the authors report a new method to measure (234)U/(238)U, (235)U/(238)U and (236)U/(238)U. It uses solid-phase chelation extraction (via TRU columns) of actinides from the urine matrix, followed by measurement using a magnetic sector field inductively coupled plasma mass spectrometer (SF-ICP-MS-Thermo Element XR) equipped with a high-efficiency nebulizer (Apex PFA microflow) and coupled with a membrane desolvating nebulizer system (Aridus II™). This method provides rapid and reliable results and has been used successfully to analyse Certified Reference Materials. PMID:24563523

  8. Characterization of the aerosol produced by infrared femtosecond laser ablation of polyacrylamide gels for the sensitive inductively coupled plasma mass spectrometry detection of selenoproteins

    NASA Astrophysics Data System (ADS)

    Claverie, Fanny; Pécheyran, Christophe; Mounicou, Sandra; Ballihaut, Guillaume; Fernandez, Beatriz; Alexis, Joël; Lobinski, Ryszard; Donard, Olivier F. X.

    2009-07-01

    A 2D high repetition rate femtosecond laser ablation strategy (2-mm wide lane) previously developed for the detection of selenoproteins in gel electrophoresis by inductively coupled plasma mass spectrometry was found to increase signal sensitivity by a factor of 40 compared to conventional nanosecond ablation (0.12-mm wide lane) [G. Ballihaut, F. Claverie, C. Pécheyran, S. Mounicou, R. Grimaud and R. Lobinski, Sensitive Detection of Selenoproteins in Gel Electrophoresis by High Repetition Rate Femtosecond Laser Ablation-Inductively Coupled Plasma Mass Spectrometry, Anal. Chem. 79 (2007) 6874-6880]. Such improvement couldn't be explained solely by the difference of amount of material ablated, and then, was attributed to the aerosol properties. In order to validate this hypothesis, the characterization of the aerosol produced by nanosecond and high repetition rate femtosecond laser ablation of polyacrylamide gels was investigated. Our 2D high repetition rate femtosecond laser ablation strategy of 2-mm wide lane was found to produce aerosols of similar particle size distribution compared to nanosecond laser ablation of 0.12-mm wide lane, with 38% mass of particles < 1 µm. However, at high repetition rate, when the ablated surface was reduced, the particle size distribution was shifted toward thinner particle diameter (up to 77% for a 0.12-mm wide lane at 285 µm depth). Meanwhile, scanning electron microscopy was employed to visualize the morphology of the aerosol. In the case of larger ablation, the fine particles ejected from the sample were found to form agglomerates due to higher ablation rate and then higher collision probability. Additionally, investigations of the plasma temperature changes during the ablation demonstrated that the introduction of such amount of polyacrylamide gel particles had very limited impact on the ICP source (Δ T~ 25 ± 5 K). This suggests that the cohesion forces between the thin particles composing these large aggregates were weak

  9. Reduction of Matrix-Induced Oxide Interferences on Rare Earth Elements and Platinum Using a Desolvating Nebulizer System with Quadrupole Inductively Coupled Plasma Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Smith, F.

    2013-12-01

    This paper will examine the use of a specialized low-flow desolvating nebulizer system for reduction of oxide mass spectral interferences that can occur in quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). This nebulizer system uses an inert low-flow nebulizer (100 microliters/min) coupled to an inert, heated membrane desolvator for efficient water vapor removal before sample aerosol injection to the Q-ICP-MS instrument. Water vapor from conventional nebulizer / spray chamber systems used with Q-ICP-MS can cause numerous mass spectral interferences. One general example is metal oxides formed from the combination of oxygen (from injected water) with sample matrix components. Two specific examples of metal oxide interferences will be investigated with and without membrane desolvation: Ba and Ce oxides on several low-mass rare earth elements (Sm, Eu, and Gd) and Hf oxides on platinum. Rare earth elements are critically important components of modern electronics (ex. magnets, lasers, cell phones, computers) and platinum is a widely used catalyst. Figures of merit for both a conventional nebulizer/spray chamber and the desolvating nebulizer systems will include operating conditions, interference intensities and reduction factors, background equivalent concentrations (BECs), and instrument detection limits (IDLs).

  10. Evaluation of Laser Ablation Inductively Coupled Plasma Mass Spectrometry for the Quantitative Determination of Lead in Different Parts of Archeological Human Teeth

    PubMed Central

    Bellis, David J.; Parsons, Patrick J.; Jones, Joseph; Amarasiriwardena, Dula

    2011-01-01

    The lead content of teeth or tooth-parts has been used as a biomarker of cumulative lead exposure in clinical, epidemiological, environmental, and archaeological studies. Through the application of laser ablation inductively coupled plasma mass spectrometry, a pilot study of the micrometer-scale distribution and quantification of lead was conducted for two human teeth obtained from an archeological burial site in Manhattan, New York, USA. Lead was highly localized within each tooth, with accumulation in circumpulpal dentine and cementum. The maximum localized lead content in circumpulpal dentine was remarkably high, almost 2000 μg g-1, compared to the mean enamel and dentine content of about 5 μg g-1. The maximum lead content in cementum was approximately 700 μg g-1. The large quantity of cementum found in the teeth suggested that the subjects had hypercementosis (excess cementum formation) of the root, a condition reported to have been prevalent among African-American slave populations. The distribution of lead in these human teeth was remarkably similar to the distribution that we previously reported in the teeth of present-day lead-dosed goats. The data shown demonstrate the feasibility of using laser ablation inductively coupled plasma mass spectrometry to examine lead exposure in archaeological studies. PMID:22467976

  11. Method validation and proficiency testing for determination of total arsenic in apple juice by inductively coupled plasma/ mass spectrometry.

    PubMed

    Chen, Yang; Reddy, Ravinder M; McLaughlin, Michael A; Al-Taher, Fadwa; Yettella, Ramesh R; Uhlig, Steffen; Bläul, Christian

    2014-01-01

    A proficiency test (PT) program for determination of total As in apple juice samples was conducted by the Food Emergency Response Network (FERN) laboratories. An analytical method using inductively coupled plasma (ICP)-MS was validated for this project. The LOD and LOQ were determined to be 0.315 and 2.32 ng/g, respectively. A total of eight apple juice samples were sent to 38 FERN laboratories, and results were statistically evaluated according to ISO 13528:2005. The total As concentrations in the PT samples reported by the participating laboratories were very close to those obtained in the homogeneity and stability tests. The reproducibility, repeatability, interlaboratory, and intralaboratory variability results led to 69% of participating laboratories being rated as satisfactory using the widely accepted Izl score

  12. Total zinc quantification by inductively coupled plasma-mass spectrometry and its speciation by size exclusion chromatography-inductively coupled plasma-mass spectrometry in human milk and commercial formulas: Importance in infant nutrition.

    PubMed

    Fernández-Menéndez, Sonia; Fernández-Sánchez, María L; Fernández-Colomer, Belén; de la Flor St Remy, Rafael R; Cotallo, Gil Daniel Coto; Freire, Aline Soares; Braz, Bernardo Ferreira; Santelli, Ricardo Erthal; Sanz-Medel, Alfredo

    2016-01-01

    This paper summarises results of zinc content and its speciation in human milk from mothers of preterm and full-term infants at different stages of lactation and from synthetic formula milks. Human milk samples (colostrum, 7th, 14th, and 28th day after delivery) from Spanish and Brazilian mothers of preterm and full-term infants (and also formula milks) were collected. After adequate treatment of the sample, total Zn was determined, while speciation analysis of the Zn was accomplished by size exclusion chromatography coupled online with the ICP-MS. It is observed that total zinc content in human milk decreases continuously during the first month of lactation, both for preterm and full term gestations. All infant formulas analysed for total Zn were within the currently legislated levels. For Zn speciation analysis, there were no differences between preterm and full term human milk samples. Moreover Zn species elute mainly associated with immunoglobulins and citrate in human milk whey. Interestingly the speciation in formula milk whey turned out to be completely different as the observed Zn(2+) was bound almost exclusively to low molecular weight ligands (citrate) and only comparatively very low amounts of the metal appeared to be associated with higher mass biomolecules (e.g. proteins).

  13. Ultra-trace determination of iodine in sediments and biological material using UV photochemical generation-inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Grinberg, Patricia; Sturgeon, Ralph E.

    2009-03-01

    Several sample preparation techniques have been evaluated for the determination of iodine using UV-photochemical generation-quadrupole inductively coupled plasma mass spectrometry. Thermal decomposition of samples at 1000 °C followed by capture of the liberated iodine in dilute acetic acid permitted subsequent UV-photochemical generation of a volatile iodine species that serves to enhance sensitivity 25-fold over conventional solution nebulization, delivering reagent blank detection limits of 8.75 pg g -1 127I and 0.075 pg g -1 129I for solid samples (400 mg test mass). The methodology was validated through determination of total iodine in several Standard Reference Materials, including NIST 1572 Citrus leaves, NIST 1549 Non-fat milk powder, NIST 1566a Oyster tissue and NIST 2709 San Joaquin Soil. Liberation of iodine from samples and its collection as well as photochemical generation were quantitative, permitting calibration to be achieved using standards prepared in dilute acetic acid.

  14. Inductively coupled plasma-mass spectrometry for elemental analysis and isotope ratio determinations in individual organic compounds separated by gas chromatography

    SciTech Connect

    Chong, N.S.; Houk, R.S.

    1987-01-01

    A gas chromatograph (GC) with a packed column was interfaced to an inductively coupled plasma-mass spectrometer (ICP-MS) to yield atomic mass spectra from volatile organic compounds. Atomization of injected compounds was nearly complete and independent of molecular structure, so that elemental ratios could be determined. Detection limits were in the range 0.001 to 400 ng s/sup -1/, depending on the ionization energy of the element and its abundance in the background spectrum. The relative standard deviation of measured isotope ratios varied from 0.4% for Br (i.e., a ratio close to unity) to 18% for N (a very large ratio). Thus, GC-ICP-MS provides elemental and isotope ratio information that is complementary to the molecular information derived from GC-MS with conventional ionization methods.

  15. A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

    USGS Publications Warehouse

    Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

    1989-01-01

    Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

  16. Laser ablation inductively coupled plasma-mass spectrometry in combination with gel electrophoresis: a new strategy for speciation of metal binding serum proteins

    NASA Astrophysics Data System (ADS)

    Neilsen, J. L.; Abildtrup, A.; Christensen, J.; Watson, P.; Cox, A.; McLeod, C. W.

    1998-02-01

    A new hyphenated technique-crossed immunoelectrophoresis in combination with laser ablation inductively coupled plasma (ICP)-mass spectrometry—for the identification and quantitation of metal binding proteins in blood serum is described. Human serum enriched with Co was subjected to electrophoresis and the agarose gels corresponding to the first and second dimensions were interrogated and analysed using a Nd Yag laser (1064 nm) interfaced to ICP-mass spectrometry. Comparison of the distribution map for Co with the protein distribution map obtained via Coommassie Brilliant Blue staining allowed identification of main Co binding serum proteins. Signals for Co (single ion monitoring, mle 59) were transient in nature and for gels enriched with increasing concentrations of Co, peak area response was linear with concentration. Precision for replicate analyses was 6% R.S.D. and the limit of detection was - 0.29 ng.

  17. Analysis of plasma protein adsorption onto DC-Chol-DOPE cationic liposomes by HPLC-CHIP coupled to a Q-TOF mass spectrometer.

    PubMed

    Capriotti, Anna Laura; Caracciolo, Giulio; Caruso, Giuseppe; Cavaliere, Chiara; Pozzi, Daniela; Samperi, Roberto; Laganà, Aldo

    2010-12-01

    Plasma protein adsorption is regarded as a key factor in the in vivo organ distribution of intravenously administered drug carriers, and strongly depends on vector surface characteristics. The present study aimed to characterize the "protein corona" absorbed onto DC-Chol-DOPE cationic liposomes. This system was chosen because it is one of the most efficient and widely used non-viral formulations in vitro and a potential candidate for in vivo transfection of genetic material. After incubation of human plasma with cationic liposomes, nanoparticle-protein complex was separated from plasma by centrifugation. An integrated approach based on protein separation by one-dimensional 12% polyacrylamide gel electrophoresis followed by the automated HPLC-Chip technology coupled to a high-resolution mass spectrometer was employed for protein corona characterization. Thirty gel lanes, approximately 2 mm, were cut, digested and analyzed by HPLC-MS/MS. Fifty-eight human plasma proteins adsorbed onto DC-Chol-DOPE cationic liposomes were identified. The knowledge of the interactions of proteins with liposomes can be exploited for future controlled design of colloidal drug carriers and possibly in the controlled creation of biocompatible surfaces of other devices that come into contact with proteins in body fluids.

  18. Beam plasma interaction in strongly coupled plasmas

    NASA Astrophysics Data System (ADS)

    Rosenberg, Marlene; Kalman, Gabor J.; Kyrkos, Stamatios; Donko, Zoltan

    2006-04-01

    The well-known problem of beam-plasma instability acquires new aspects when one or both of the two components (the beam and the plasma) are strongly interacting. We have now theoretically considered the case when the plasma is in the solid phase and forms a lattice. In this situation, the inherent anisotropy of the lattice leads to a coupling between the longitudinal and transverse polarizations. One of the novel features of the beam-plasma instability in this scenario is the possible excitation of transverse modes, which should be an experimentally observable signature of the instability. We have initially concentrated on a 2D toy model with the beam lying in the lattice plane. At the same time, we have initiated a molecular dynamics simulation program for studying various aspects of the penetration of a beam into a plasma lattice. The beam parameters can be adjusted in order to see the effects of increasing coupling strength within the beam and to distinguish between collective phenomena and scattering on individual particles. When both components are strongly interacting, a number of remarkable phenomena—trapping of beam particles, creation of dislocations, local melting of the lattice—may be observed.

  19. Speciation of manganese binding to biomolecules in pine nuts (Pinus pinea) by two-dimensional liquid chromatography coupled to ultraviolet and inductively coupled plasma mass spectrometry detectors followed by identification by electrospray ionization mass spectrometry.

    PubMed

    Arias-Borrego, Ana; García-Barrera, Tamara; Gómez-Ariza, José L

    2008-10-01

    Advances in analytical methodology for speciation of manganese in pine nuts are presented in this work. The approach is based on the use of orthogonal chromatographic systems, namely size-exclusion chromatography (SEC) of the extracts and strong anion exchange (IEC) of the fractions collected by the first column. In both columns, manganese elution is first monitored by a quadrupole inductively coupled plasma mass spectrometry (ICP-MS) instrument equipped with an octopole reaction cell and an ultraviolet (UV) detector. SEC is performed by using two columns covering the molecular weight range from <10 to 70 kDa that allows an initial screening of the molecular weight of the Mn species. The higher resolution capability of the low molecular weight range column is the reason to use the latter for further experiments. The fraction from SEC-ICP-MS in which Mn is present at highest concentration is submitted to IEC-ICP-MS allowing Mn-citrate and MnCl(2) identification by retention time matching with standards. The concentration of these species is estimated to be 75 and 125 microg kg(-1) (as Mn), respectively, in the pine nuts samples and the presence of Mn-citrate is confirmed by nanoelectrospray ionization quadrupole time-of-flight mass spectrometry (nESI-QqTOF-MS). In the same fraction, a third Mn-containing peak is detected in the IEC-UV-ICP-MS chromatogram. This peak corresponds to a protein containing Mn that was later submitted to a tryptic digestion and analyzed by nESI-QqTOF. The MS/MS data of a doubly charged peptide are used to obtain the sequence of the protein with the Mascot search engine. The peak turned out to be isocitrate dehydrogenase, a protein commonly associated with Mn.

  20. Identification and quantification of electrochemically generated metabolites of thyroxine by means of liquid chromatography/electrospray-mass spectrometry and countergradient liquid chromatography/inductively coupled plasma-mass spectrometry.

    PubMed

    Mak, Chun Kong; Wehe, Christoph A; Sperling, Michael; Karst, Uwe

    2015-11-01

    Thyroxine (T4) is one of the major thyroid hormones, which regulates cellular metabolism, central nervous system development, body temperature, reproduction and growth. The simulation of oxidation reactions of T4 may provide further information about the fate of T4 in cells without using laborious in vitro and susceptible in vivo tests. In this study, oxidation products of T4, generated inside an electrochemical (EC) cell, were separated and identified by on-line EC/liquid chromatography/electrospray ionization-mass spectrometry (EC/LC/ESI-MS). In another experimental setup, the electrogenerated metabolites were separated by LC, subsequently mixed with a compensating countergradient (cg), and finally introduced into an inductively coupled plasma-mass spectrometer (ICP-MS). The gradient compensation was achieved by an additional pump module which generated a reversed gradient to the analytical gradient used for the separation. This setup enabled a constant composition of the LC eluent flowing into the plasma so that stable plasma conditions and a uniform response over the complete elution time could be achieved. Combined with identification information from online-coupled EC/LC/ESI-MS, robust and reliable quantification of T4 and its oxidation products was accomplished by on-line coupled EC/cgLC/ICP-MS, with LOD of 33nM of iodine.

  1. Flow-injection technique for determination of uranium and thorium isotopes in urine by inductively coupled plasma mass spectrometry.

    PubMed

    Benkhedda, Karima; Epov, Vladimir N; Evans, R Douglas

    2005-04-01

    A sensitive and efficient flow-injection (FI) preconcentration and matrix-separation technique coupled to sector field ICP-mass spectrometry (SF-ICP-MS) has been developed and validated for simultaneous determination of ultra-low levels of uranium (U) and thorium (Th) in human urine. The method is based on selective retention of U and Th from a urine matrix, after microwave digestion, on an extraction chromatographic TRU resin, as an alternative to U/TEVA resin, and their subsequent elution with ammonium oxalate. Using a 10 mL sample, the limits of detection achieved for 238U and 232Th were 0.02 and 0.03 ng L(-1), respectively. The accuracy of the method was checked by spike-recovery measurements. Levels of U and Th in human urine were found to be in the ranges 1.86-5.50 and 0.176-2.35 ng L(-1), respectively, well in agreement with levels considered normal for non-occupationally exposed persons. The precision obtained for five replicate measurements of a urine sample was 2 and 3% for U and Th, respectively. The method also enables on-line measurements of the 235U/238U isotope ratios in urine. Precision of 0.82-1.04% (RSD) was obtained for 235U/238U at low ng L(-1) levels, using the FI transient signal approach.

  2. Reference measurements for total mercury and methyl mercury content in marine biota samples using direct or species-specific isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Krata, Agnieszka; Vassileva, Emilia; Bulska, Ewa

    2016-11-01

    The analytical procedures for reference measurements of the total Hg and methyl mercury (MeHg) mass fractions at various concentration levels in marine biota samples, candidates for certified reference materials (oyster and clam Gafrarium tumidum), were evaluated. Two modes of application of isotope dilution inductively coupled plasma mass spectrometry method (ID ICP-MS), namely direct isotope dilution and species-specific isotope dilution analysis with the use of two different quantification mass spectrometry techniques were compared. The entire ID ICP-MS measurement procedure was described by mathematical modelling and the combined uncertainty of measurement results was estimated. All factors influencing the final results as well as isotopic equilibrium were systematically investigated. This included the procedural blank, the moisture content in the biota samples and all factors affecting the blend ratio measurements (instrumental background, spectral interferences, dead time and mass discrimination effects as well as the repeatability of measured isotopic ratios). Modelling of the entire measurement procedures and the use of appropriate certified reference materials enable to assure the traceability of obtained values to the International System of Units (SI): the mole or the kilogram. The total mass fraction of mercury in oyster and clam biota samples, after correction for moisture contents, was found to be: 21.1 (1.1) 10(-9) kg kg(-1) (U =5.1% relative, k=2) and 390.0 (9.4) 10(-9) kg kg(-1) (U=2.4% relative, k=2), respectively. For the determination of mercury being present as methyl mercury, the non-chromatographic separation on anion-exchange resin AG1-X8 of the blended samples was applied. The content of MeHg (as Hg) in oyster sample was found: 4.81 (24) 10(-9)kgkg(-1) (U=5.0%, k=2) and 4.84 (21) 10(-9)kgkg(-1) (U=4.3%, k=2) with the use of quadrupole (ICP QMS) or sector field (ICP SFMS) inductively coupled plasma mass spectrometers, respectively. In the

  3. Reference measurements for total mercury and methyl mercury content in marine biota samples using direct or species-specific isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Krata, Agnieszka; Vassileva, Emilia; Bulska, Ewa

    2016-11-01

    The analytical procedures for reference measurements of the total Hg and methyl mercury (MeHg) mass fractions at various concentration levels in marine biota samples, candidates for certified reference materials (oyster and clam Gafrarium tumidum), were evaluated. Two modes of application of isotope dilution inductively coupled plasma mass spectrometry method (ID ICP-MS), namely direct isotope dilution and species-specific isotope dilution analysis with the use of two different quantification mass spectrometry techniques were compared. The entire ID ICP-MS measurement procedure was described by mathematical modelling and the combined uncertainty of measurement results was estimated. All factors influencing the final results as well as isotopic equilibrium were systematically investigated. This included the procedural blank, the moisture content in the biota samples and all factors affecting the blend ratio measurements (instrumental background, spectral interferences, dead time and mass discrimination effects as well as the repeatability of measured isotopic ratios). Modelling of the entire measurement procedures and the use of appropriate certified reference materials enable to assure the traceability of obtained values to the International System of Units (SI): the mole or the kilogram. The total mass fraction of mercury in oyster and clam biota samples, after correction for moisture contents, was found to be: 21.1 (1.1) 10(-9) kg kg(-1) (U =5.1% relative, k=2) and 390.0 (9.4) 10(-9) kg kg(-1) (U=2.4% relative, k=2), respectively. For the determination of mercury being present as methyl mercury, the non-chromatographic separation on anion-exchange resin AG1-X8 of the blended samples was applied. The content of MeHg (as Hg) in oyster sample was found: 4.81 (24) 10(-9)kgkg(-1) (U=5.0%, k=2) and 4.84 (21) 10(-9)kgkg(-1) (U=4.3%, k=2) with the use of quadrupole (ICP QMS) or sector field (ICP SFMS) inductively coupled plasma mass spectrometers, respectively. In the

  4. Application of high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for determination of chromium compounds in the air at the workplace.

    PubMed

    Stanislawska, Magdalena; Janasik, Beata; Wasowicz, Wojciech

    2013-12-15

    The toxicity and bioavailability of chromium species are highly dependable on the form or species, therefore determination of total chromium is insufficient for a complete toxicological evaluation and risk assessment. An analytical method for determination of soluble and insoluble Cr (III) and Cr (VI) compounds in welding fume at workplace air has been developed. The total chromium (Cr) was determined by using quadruple inductively coupled plasma mass spectrometry (ICP-MS) equipped with a dynamic reaction cell (DRC(®)). Soluble trivalent and hexavalent chromium compounds were determined by high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A high-speed, reversed-phase CR C8 column (PerkinElmer, Inc., Shelton, CT, USA) was used for the speciation of soluble Cr (III) and soluble Cr (VI). The separation was accomplished by interaction of the chromium species with the different components of the mobile phase. Cr (III) formed a complex with EDTA, i.e. retained on the column, while Cr (VI) existed in the solutions as dichromate. Alkaline extraction (2% KOH and 3% Na2CO3) and anion exchange column (PRP-X100, PEEK, Hamilton) were used for the separation of the total Cr (VI). The results of the determination of Cr (VI) were confirmed by the analysis of the certified reference material BCR CRM 545 (Cr (VI) in welding dust). The results obtained for the certified material (40.2±0.6 g kg(-1)) and the values recorded in the examined samples (40.7±0.6 g kg(-1)) were highly consistent. This analytical method was applied for the determination of chromium in the samples in the workplace air collected onto glass (Whatman, Ø 37 mm) and membrane filters (Sartorius, 0.8 μm, Ø 37 mm). High performance liquid chromatography with inductively coupled plasma mass spectrometry is a remarkably powerful and versatile technique for determination of chromium species in welding fume at workplace air. PMID:24209303

  5. A simple solution to expanding available reference materials for Laser Ablation Inductively Coupled Plasma Mass Spectrometry analysis: Applications to sedimentary materials

    NASA Astrophysics Data System (ADS)

    Shaheen, Mohamed E.; Fryer, Brian J.

    2011-08-01

    Analytical data on sediments are of great importance in understanding and documenting environmental issues. For laboratories interested in in-situ chemical analysis of sediments by LA-ICP-MS, a major issue is the lack of appropriate matrix matched sediment reference materials. Those available were largely designed for partial extractions which generally do not reflect the total elemental compositions. In this work we provide a comprehensive study on chemical compositions of seven currently available sediment reference materials (Lake sediments: LKSD-1, LKSD-2, LKSD-3, Stream sediments: STSD-2, STSD-3, and Marine sediments: PACS-2, MESS-3) as determined by Solution Nebulization Inductively Coupled Plasma Mass Spectrometry (SN-ICP-MS) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) after digestion in a mixture of concentrated HNO 3 and HF acids. We also report a simple method to prepare these sediment reference materials and more generally appropriate sediment cores for LA-ICP-MS analysis using epoxy resin. This sample preparation method maintains sediment integrity for high spatial resolution analysis which is required for tracing changes in environmental conditions over short time periods. This work also demonstrates the application of fs-LA-ICP-MS as a tool for direct, rapid and high spatial resolution analysis of sediments.

  6. Fast Determination of Toxic Arsenic Species in Food Samples Using Narrow-bore High-Performance Liquid-Chromatography Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Terol, Amanda; Marcinkowska, Monika; Ardini, Francisco; Grotti, Marco

    2016-01-01

    A new method for the speciation analysis of arsenic in food using narrow-bore high-performance liquid-chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) has been developed. Fast separation of arsenite, arsenate, monomethylarsonic acid and dimethylarsinic acid was carried out in 7 min using an anion-exchange narrow-bore Nucleosil 100 SB column and 12 mM ammonium dihydrogen phosphate of pH 5.2 as the mobile phase, at a flow rate of 0.3 mL min(-1). A PFA-ST micronebulizer jointed to a cyclonic spray chamber was used for HPLC-ICP-MS coupling. Compared with standard-bore HPLC-ICP-MS, the new method has provided higher sensitivity, reduced mobile-phase consumption, a lower matrix plasma load and a shorter analysis time. The achieved instrumental limits of detection were in the 0.3 - 0.4 ng As mL(-1) range, and the precision was better than 3%. The arsenic compounds were efficiently (>80%) extracted from various food samples using a 1:5 methanol/water solution, with additional ultrasonic treatment for rice products. The applicability of this method was demonstrated by the analysis of several samples, such as seafood (fish, mussels, shrimps, edible algae) and rice-based products (Jasmine and Arborio rice, spaghetti, flour, crackers), including three certified reference materials. PMID:27506720

  7. Analysis of radium-226 in high salinity wastewater from unconventional gas extraction by inductively coupled plasma-mass spectrometry.

    PubMed

    Zhang, Tieyuan; Bain, Daniel; Hammack, Richard; Vidic, Radisav D

    2015-03-01

    Elevated concentration of naturally occurring radioactive material (NORM) in wastewater generated from Marcellus Shale gas extraction is of great concern due to potential environmental and public health impacts. Development of a rapid and robust method for analysis of Ra-226, which is the major NORM component in this water, is critical for the selection of appropriate management approaches to properly address regulatory and public concerns. Traditional methods for Ra-226 determination require long sample holding time or long detection time. A novel method combining Inductively Coupled Mass Spectrometry (ICP-MS) with solid-phase extraction (SPE) to separate and purify radium isotopes from the matrix elements in high salinity solutions is developed in this study. This method reduces analysis time while maintaining requisite precision and detection limit. Radium separation is accomplished using a combination of a strong-acid cation exchange resin to separate barium and radium from other ions in the solution and a strontium-specific resin to isolate radium from barium and obtain a sample suitable for analysis by ICP-MS. Method optimization achieved high radium recovery (101 ± 6% for standard mode and 97 ± 7% for collision mode) for synthetic Marcellus Shale wastewater (MSW) samples with total dissolved solids as high as 171,000 mg/L. Ra-226 concentration in actual MSW samples with TDS as high as 415,000 mg/L measured using ICP-MS matched very well with the results from gamma spectrometry. The Ra-226 analysis method developed in this study requires several hours for sample preparation and several minutes for analysis with the detection limit of 100 pCi/L with RSD of 45% (standard mode) and 67% (collision mode). The RSD decreased to below 15% when Ra-226 concentration increased over 500 pCi/L.

  8. Analysis of radium-226 in high salinity wastewater from unconventional gas extraction by inductively coupled plasma-mass spectrometry.

    PubMed

    Zhang, Tieyuan; Bain, Daniel; Hammack, Richard; Vidic, Radisav D

    2015-03-01

    Elevated concentration of naturally occurring radioactive material (NORM) in wastewater generated from Marcellus Shale gas extraction is of great concern due to potential environmental and public health impacts. Development of a rapid and robust method for analysis of Ra-226, which is the major NORM component in this water, is critical for the selection of appropriate management approaches to properly address regulatory and public concerns. Traditional methods for Ra-226 determination require long sample holding time or long detection time. A novel method combining Inductively Coupled Mass Spectrometry (ICP-MS) with solid-phase extraction (SPE) to separate and purify radium isotopes from the matrix elements in high salinity solutions is developed in this study. This method reduces analysis time while maintaining requisite precision and detection limit. Radium separation is accomplished using a combination of a strong-acid cation exchange resin to separate barium and radium from other ions in the solution and a strontium-specific resin to isolate radium from barium and obtain a sample suitable for analysis by ICP-MS. Method optimization achieved high radium recovery (101 ± 6% for standard mode and 97 ± 7% for collision mode) for synthetic Marcellus Shale wastewater (MSW) samples with total dissolved solids as high as 171,000 mg/L. Ra-226 concentration in actual MSW samples with TDS as high as 415,000 mg/L measured using ICP-MS matched very well with the results from gamma spectrometry. The Ra-226 analysis method developed in this study requires several hours for sample preparation and several minutes for analysis with the detection limit of 100 pCi/L with RSD of 45% (standard mode) and 67% (collision mode). The RSD decreased to below 15% when Ra-226 concentration increased over 500 pCi/L. PMID:25642997

  9. Total introduction of microsamples in inductively coupled plasma mass spectrometry by high-temperature evaporation chamber with a sheathing gas stream.

    PubMed

    Grotti, Marco; Ardini, Francisco; Todolì, Josè Luis

    2013-03-12

    A systematic study on the high-temperature Torch Integrated Sample Introduction System (TISIS) for use in Inductively Coupled Plasma Mass Spectrometry (ICP-MS) has been performed. The investigation included the optimization of the relevant parameters (chamber temperature, sheathing gas flow rate, nebulizer gas flow rate, sample uptake rate), the evaluation of its performance characteristics (sensitivity, limits of detection, stability, memory effects, use with the dynamic reaction cell) and representative applications to environmental, biological and clinical samples. Under the optimal conditions (T=150°C; nebulizer gas flow rate of 0.7Lmin(-1) along with sheathing gas flow rate of 0.35Lmin(-1) and a sample uptake rate of 20μLmin(-1)), the sensitivity was from 2 to 8 times higher than that measured using a conventional micronebulizer/mini-spray chamber system, due to the enhanced analyte mass transport toward the plasma and the solvent introduction in the vapour form. In addition, for several elements, TISIS provided lower limits of detection than the conventional system, even when the latter worked at 5-fold higher sample uptake rate. Short-term and long-term precision was better than 5%. Spectroscopic interferences arising from common matrices were efficiently removed by the dynamic reaction cell technique. The application of TISIS/ICP-MS to representative certified reference samples (spinach leaves, marine plankton, bone tissue, human blood) proved the suitability of this system for the accurate analysis of limited-size samples.

  10. Simultaneous speciation of selenium and sulfur species in selenized odorless garlic (Allium sativum L. Shiro) and shallot (Allium ascalonicum) by HPLC-inductively coupled plasma-(octopole reaction system)-mass spectrometry and electrospray ionization-tandem mass spectrometry.

    PubMed

    Ogra, Yasumitsu; Ishiwata, Kazuya; Iwashita, Yuji; Suzuki, Kazuo T

    2005-11-01

    The simultaneous speciation of selenium and sulfur in selenized odorless garlic (Allium sativum L. Shiro) and a weakly odorous Allium plant, shallot (Allium ascalonicum), was performed by means of a hyphenated technique, a HPLC coupled with an inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) equipped with an octopole reaction system (ORS). The aqueous extracts of them contained the common seleno compound that was identified as gamma-glutamylmethylselenocysteine by an electrospray ionization-tandem mass spectrometry (ESI-MS/MS). Normal garlic contains alliin as the major sulfur-containing compound, which is the biological precursor of the garlic odorant, allicin. Alliin, however, was not detected in the extracts of the selenized odorless garlic. At least, four unidentified sulfur-containing compounds were detected in odorless garlic and shallot. Moreover, these Allium plants showed chemopreventive effects against human leukemia cells.

  11. A new strategy of solution calibration in laser ablation inductively coupled plasma mass spectrometry for multielement trace analysis of geological samples.

    PubMed

    Pickhardt, C; Becker, J S; Dietze, H J

    2000-01-01

    Because multielement trace analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is often limited by the lack of suitable reference materials with a similar matrix composition, a novel quantification strategy using solution calibration was developed. For mass spectrometric multielement determination in geological samples a quadrupole-based LA-ICP-MS is coupled with an ultrasonic nebulizer (USN). In order to arrange matrix matching the standard solutions are nebulized with a USN during solution calibration and simultaneously a blank target (e.g. lithium borate) is ablated with a focused laser beam. The homogeneous geological samples were measured using the same experimental arrangement where a 2% nitric acid is simultaneously nebulized with the USN. Homogeneous targets were prepared from inhomogeneous geological samples by powdering, homogenizing and fusing with a lithium borate mixture in a muffle furnace at 1050 degrees C. Furthermore, a homogeneous geological glass was also investigated. The quantification of analytical results was performed by external calibration using calibration curves measured on standard solutions. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS, measured concentrations in homogeneous geological targets were also corrected with relative sensitivity coefficients (RSCs) determined using one standard solution only. The analytical results of LA-ICP-MS on various geological samples are in good agreement with the reference values and the results of other trace analytical methods. The relative standard deviation (RSD) for trace element determination (N = 6) is between 2 and 10%. PMID:11220576

  12. Identification and quantitation of cocaine, benzoylecgonine, and cocaethylene in blood, serum, and plasma using ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS).

    PubMed

    Kriger, Scott; Gunn, Josh; Terrell, Andrea R

    2010-01-01

    Cocaine is a widely abused stimulant. Numerous methods exist for the identification of the drug, or more commonly, one of its metabolites in urine. Urine testing is useful for most cases, but it is necessary to use other matrices in forensic situations and when subjects are anuric. We describe a novel method for the analysis of cocaine, benzoylecgonine, and cocaethylene in blood, serum, and plasma utilizing ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS). Sample preparation has been minimized to a simple deproteinization step in which each specimen is mixed with an acetonitrile-internal standard mixture. The method has excellent precision across the linear range of 25-2,000 ng/mL for each analyte. With a run-time of 4 min, this method provides a significant improvement over traditional GC/MS methods. PMID:20077068

  13. Determination of rare earth elements in human hair and wheat flour reference materials by inductively coupled plasma mass spectrometry with dry ashing and microwave digestion

    NASA Astrophysics Data System (ADS)

    Ming, Yin; Bing, Li

    1998-09-01

    A method was developed for the determination of all rare earth elements (REEs) at sub ng g -1 levels in human hair (GBW 09101, SRM, Republic of China) and wheat flour (GBW 08503, SRM, Republic of China) by Inductively coupled plasma mass spectrometry (ICP-MS). The values obtained by dry ashing and microwave oven digestion procedures were compared with those obtained by traditional open vessel acid digestion method. The validity of the analytical procedure was examined by analyzing spiked samples and two vegetables (GBW 07603 and GBW 07605, SRMs, Republic of China). The results are satisfactory. The detection limits for 14 REEs ranged from 0.0039 to 0.0003 ng cm -3 in solution and the quantification limits ranged from 0.16 to 0.01 ng g -1 in solid sample. The precision for most REEs were less than 10% RSD.

  14. Quantification of modifiers in advanced materials based on zinc oxide by total reflection X-ray fluorescence and inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Filatova, Daria G.; Alov, Nikolai V.; Vorobyeva, Natalia A.; Rumyantseva, Marina N.; Sharanov, Pavel Yu.; Seregina, Irina F.; Gaskov, Alexander M.

    2016-04-01

    A novel approach to quantification of Ga and Zn modifiers in advanced materials based on zinc oxide is presented. The approach includes a combination of total reflection X-ray fluorescence (TXRF) and inductively coupled plasma mass spectrometry (ICP-MS) for determination and validation of the results. It is suggested to use aqueous standards for the direct determination of elements in powder samples by TXRF with a relative standard deviation no more than sr = 0.11. The accuracy of these results was proved by ICP-MS after the sample decomposition, sr(In) = 0.05, sr(Ga) = 0.06 and sr(Zn) = 0.06. It was established that there is a possibility to determine indium above 300 ppb on the background of K-M3 line of argon.

  15. Demonstration of femtosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements in U-10Mo nuclear fuel foils

    SciTech Connect

    Havrilla, George Joseph; Gonzalez, Jhanis

    2015-06-10

    The use of femtosecond laser ablation inductively coupled plasma mass spectrometry was used to demonstrate the feasibility of measuring the isotopic ratio of uranium directly in U-10Mo fuel foils. The measurements were done on both the flat surface and cross sections of bare and Zr clad U-10Mo fuel foil samples. The results for the depleted uranium content measurements were less than 10% of the accepted U235/238 ratio of 0.0020. Sampling was demonstrated for line scans and elemental mapping over large areas. In addition to the U isotopic ratio measurement, the Zr thickness could be measured as well as trace elemental composition if required. A number of interesting features were observed during the feasibility measurements which could provide the basis for further investigation using this methodology. The results demonstrate the feasibility of using fs-LA-ICP-MS for measuring the U isotopic ratio in U-10Mo fuel foils.

  16. Investigation of heavy-metal accumulation in selected plant samples using laser induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Galiová, M.; Kaiser, J.; Novotný, K.; Novotný, J.; Vaculovič, T.; Liška, M.; Malina, R.; Stejskal, K.; Adam, V.; Kizek, R.

    2008-12-01

    Single-pulse Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass-Spectrometry (LA-ICP-MS) were applied for mapping the silver and copper distribution in Helianthus Annuus L. samples treated with contaminant in controlled conditions. For Ag and Cu detection the 328.07 nm Ag(I) and 324.75 nm Cu(I) lines were used, respectively. The LIBS experimental conditions (mainly the laser energy and the observation window) were optimized in order to avoid self-absorption effect in the measured spectra. In the LA-ICP-MS analysis the Ag 107 and Cu 63 isotopes were detected. The capability of these two analytical techniques for high-resolution mapping of selected trace chemical elements was demonstrated.

  17. Sectional power-law correction for the accurate determination of lutetium by isotope dilution multiple collector-inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Yuan, Hong-Lin; Gao, Shan; Zong, Chun-Lei; Dai, Meng-Ning

    2009-11-01

    In this study, we employ a sectional power-law (SPL) correction that provides accurate and precise measurements of 176Lu/ 175Lu ratios in geological samples using multiple collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Three independent power laws were adopted based on the 176Lu/ 176Yb ratios of samples measured after chemical chromatography. Using isotope dilution (ID) techniques and the SPL correction method, the measured lutetium contents of United States Geological Survey rock standards (BHVO-1, BHVO-2, BCR-2, AGV-1, and G-2) agree well with the recommended values. Results obtained by conventional ICP-MS and INAA are generally higher than those obtained by ID-TIMS and ID-MC-ICP-MS; this discrepancy probably reflects oxide interference and inaccurate corrections.

  18. A novel assay method for the trace determination of Th and U in copper and lead using inductively coupled plasma mass spectrometry

    SciTech Connect

    LaFerriere, Brian D.; Maiti, Tapas C.; Arnquist, Isaac J.; Hoppe, Eric W.

    2015-03-01

    This study describes a novel sample preparation and assay method developed in support of the MAJORANA DEMONSTRATOR experiment for the determination of thorium and uranium levels in copper and lead shielding components. Meticulously clean sample preparation methods combined with novel anion exchange separations for analyte pre-concentration and matrix removal were developed. Quantification was performed by inductively coupled plasma mass spectrometry. Detection limits of 0.0084 pg 232Th/g and 0.0106 pg 238U/g were determined for copper, while detection limits of 0.23 pg 232Th/g and 0.46 pg 238U/g were achieved for lead. These methods allow the Majorana Collaboration to accurately assay detector components and ensure that the experiment’s stringent radiopurity requirements are met.

  19. Intercomparison of inductively coupled plasma mass spectrometry, quantitative neutron capture radiography, and prompt gamma activation analysis for the determination of boron in biological samples.

    PubMed

    Schütz, C L; Brochhausen, C; Hampel, G; Iffland, D; Kuczewski, B; Otto, G; Schmitz, T; Stieghorst, C; Kratz, J V

    2012-10-01

    Boron determination in blood and tissue samples is a crucial task especially for treatment planning, preclinical research, and clinical application of boron neutron capture therapy (BNCT). Comparison of clinical findings remains difficult due to a variety of analytical methods, protocols, and standard reference materials in use. This paper addresses the comparability of inductively coupled plasma mass spectrometry, quantitative neutron capture radiography, and prompt gamma activation analysis for the determination of boron in biological samples. It was possible to demonstrate that three different methods relying on three different principles of sample preparation and boron detection can be validated against each other and yield consistent results for both blood and tissue samples. The samples were obtained during a clinical study for the application of BNCT for liver malignancies and therefore represent a realistic situation for boron analysis.

  20. The use of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of toxic and essential elements in different types of food samples

    NASA Astrophysics Data System (ADS)

    Voica, C.; Dehelean, A.; Kovacs, M. H.

    2012-02-01

    Food is the primary source of essential elements for humans and it is an important source of exposure to toxic elements. In this context, levels of essential and toxic elements must be determined routinely in consumed food products. The content of trace elements (As, Pb, Cu, Cd, Zn, Sn, Hg) in different types of food samples (e.g. rice, bread, sugar, cheese, milk, butter, wheat, coffee, chocolate, biscuits pasta, etc.) was determined, using inductively coupled plasma mass spectrometry (ICP-MS). Trace element contents in some foods were higher than maximum permissible levels of toxic metals in human food (Cd in bread, Zn in cheese, Cu in coffee, Hg in carrots and peppers).

  1. Characterization of cobalt pigments found in traditional Valencian ceramics by means of laser ablation-inductively coupled plasma mass spectrometry and portable X-ray fluorescence spectrometry.

    PubMed

    Pérez-Arantegui, J; Resano, M; García-Ruiz, E; Vanhaecke, F; Roldán, C; Ferrero, J; Coll, J

    2008-02-15

    In this work, a comparison of the performances of laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) and portable X-ray fluorescence (XRF) spectrometry for the characterization of cobalt blue pigments used in the decoration of Valencian ceramics is presented. Qualitative data on the elemental composition of the blue pigments obtained using both techniques show a good agreement. Moreover, the results clearly illustrate that potters utilized different kinds of cobalt pigments in different historical periods. While both techniques seem suitable for the proposed task, they show different strengths and weaknesses. Portable X-ray fluorescence spectrometry is a cheaper and totally non-destructive technique, capable of providing fast and reliable results at the mgg(-1) level. LA-ICPMS, on the other hand, offers a much higher detection power and better spatial resolution, but its use results in some sample damage (sample consumption at the mug level), while it is a more expensive and non-portable technique.

  2. Portable x-ray fluorescence for assessing trace elements in rice and rice products: Comparison with inductively coupled plasma-mass spectrometry.

    PubMed

    Fleming, David E B; Foran, Kelly A; Kim, Jong Sung; Guernsey, Judy R

    2015-10-01

    Portable x-ray fluorescence (XRF) was investigated as a means of assessing trace elements in rice and rice products. Using five measurement trials of 180 s real time, portable XRF was first used to detect arsenic (As), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), and zinc (Zn) in a variety of rice samples. The same samples were then microwave-digested and used to determine elemental concentrations using inductively coupled plasma-mass spectrometry (ICP-MS). The concentrations of As, Mn, Fe, Cu, and Zn determined by ICP-MS were found to be consistent with other recent studies involving various types of rice and rice products. When assessing for As, Mn, Fe, Cu, and Zn, comparison of results between XRF amplitude and ICP-MS concentration (wet weight) demonstrated a linear relationship with a significant correlation. A significant correlation between XRF amplitude and ICP-MS concentration was not found when assessing for Ni.

  3. Laser ablation-inductively coupled plasma-mass spectrometry: Examinations of the origins of polyatomic ions and advances in the sampling of particulates

    SciTech Connect

    Witte, Travis

    2011-01-01

    This dissertation provides a general introduction to Inductively coupled plasma-mass spectrometry (ICP-MS) and laser ablation (LA) sampling, with an examination of analytical challenges in the employment of this technique. It discusses the origin of metal oxide ions (MO+) in LA-ICP-MS, as well as the effect of introducing helium and nitrogen to the aerosol gas flow on the formation of these polyatomic interferences. It extends the study of polyatomic ions in LA-ICP-MS to metal argide (MAr+) species, an additional source of possible significant interferences in the spectrum. It describes the application of fs-LA-ICP-MS to the determination of uranium isotope ratios in particulate samples.

  4. Analysis of toxic metals in seafood sold in New York state by inductively coupled plasma mass spectrometry and direct combustion analysis.

    PubMed

    King, Thomas J; Sheridan, Robert S; Rice, Daniel H

    2010-09-01

    Concentrations of 12 metals (As, Be, Cd, Cr, Pb, Mo, Ni, Tl, Th, U, V, Hg) were determined in samples of fish and lobster obtained from various stores and markets in New York State. The seafood samples were chosen based on their popularity as a food source and the potential of the species to contain high levels of mercury based on past research results. A total of 177 fish and lobster samples were initially analyzed using combustion for Hg. The samples were then reanalyzed for several elements using microwave digestion followed by inductively coupled plasma mass spectrometry. The detection limits were as follows: 20 ng/g for Th, U, and Hg; 100 ng/g for Be, Cd, V, and As; and 300 ng/g for Cr, Mo, Tl, Pb, and Ni. Twenty-two samples had mercury concentrations greater than the 1,000 ng/g limit set by the Commission of the European Communities. The highest Cd concentration (511 ng/g) was found in a lobster. This level is greater than the 500 ng/g limit set by the Commission of the European Communities. All levels of As, Cd, Cr, Pb, and Ni were below the U.S. Food and Drug Administration action levels for these metals in crustaceans and shellfish. The highest average mercury level (1,190 ng/g) was found in swordfish. The highest average arsenic level (13,400 ng/g) was found in monkfish. Inductively coupled plasma mass spectrometry with microwave digestion was demonstrated to be a very effective technique for analyzing fish and lobster for Hg and other toxic metals.

  5. Qualitative and quantitative spectro-chemical analysis of dates using UV-pulsed laser induced breakdown spectroscopy and inductively coupled plasma mass spectrometry.

    PubMed

    Mehder, A O; Habibullah, Y B; Gondal, M A; Baig, Umair

    2016-08-01

    Laser Induced Breakdown Spectroscopy (LIBS) is demonstrated for the spectral analysis of nutritional and toxic elements present in several varieties of date fruit samples available in the Saudi Arabia market. The method analyzes the optical emission of a test sample when subjected to pulsed laser ablation. In this demonstration, our primary focus is on calcium (Ca) and magnesium (Mg), as nutritional elements, and on chromium (Cr), as a toxic element. The local thermodynamic equilibrium (LTE) condition was confirmed prior to the elemental characterization of date samples to ensure accuracy of the LIBS analysis. This was achieved by measuring parameters associated with the plasma, such as the electron temperature and the electron number density. These plasma parameters aid interpretation of processes such as ionization, dissociation, and excitation occurring in the plasma plume formed by ablating the date palm sample. The minimum detection limit was established from calibration curves that involved plotting the LIBS signal intensity as a function of standard date samples with known concentrations. The concentration of Ca and Mg detected in different varieties of date samples was between 187 and 515 and 35-196mgL(-1) respectively, while Cr concentration measured between 1.72 and 7.76mgL(-1). In order to optimize our LIBS system, we have studied how the LIBS signal intensity depends on the incident laser energy and the delay time. In order to validate our LIBS analysis results, standard techniques such as inductively coupled plasma mass spectrometry (ICP-MS) were also applied on an identical (duplicate) date samples as those used for the LIBS analysis. The LIBS results exhibit remarkable agreement with those obtained from the ICP-MS analysis. In addition, the finger print wavelengths of other elements present in date samples were also identified and are reported here, which has not been previously reported, to the best of our knowledge.

  6. Qualitative and quantitative spectro-chemical analysis of dates using UV-pulsed laser induced breakdown spectroscopy and inductively coupled plasma mass spectrometry.

    PubMed

    Mehder, A O; Habibullah, Y B; Gondal, M A; Baig, Umair

    2016-08-01

    Laser Induced Breakdown Spectroscopy (LIBS) is demonstrated for the spectral analysis of nutritional and toxic elements present in several varieties of date fruit samples available in the Saudi Arabia market. The method analyzes the optical emission of a test sample when subjected to pulsed laser ablation. In this demonstration, our primary focus is on calcium (Ca) and magnesium (Mg), as nutritional elements, and on chromium (Cr), as a toxic element. The local thermodynamic equilibrium (LTE) condition was confirmed prior to the elemental characterization of date samples to ensure accuracy of the LIBS analysis. This was achieved by measuring parameters associated with the plasma, such as the electron temperature and the electron number density. These plasma parameters aid interpretation of processes such as ionization, dissociation, and excitation occurring in the plasma plume formed by ablating the date palm sample. The minimum detection limit was established from calibration curves that involved plotting the LIBS signal intensity as a function of standard date samples with known concentrations. The concentration of Ca and Mg detected in different varieties of date samples was between 187 and 515 and 35-196mgL(-1) respectively, while Cr concentration measured between 1.72 and 7.76mgL(-1). In order to optimize our LIBS system, we have studied how the LIBS signal intensity depends on the incident laser energy and the delay time. In order to validate our LIBS analysis results, standard techniques such as inductively coupled plasma mass spectrometry (ICP-MS) were also applied on an identical (duplicate) date samples as those used for the LIBS analysis. The LIBS results exhibit remarkable agreement with those obtained from the ICP-MS analysis. In addition, the finger print wavelengths of other elements present in date samples were also identified and are reported here, which has not been previously reported, to the best of our knowledge. PMID:27216665

  7. Direct determination of cadmium in foods by solid sampling electrothermal vaporization inductively coupled plasma mass spectrometry using a tungsten coil trap

    NASA Astrophysics Data System (ADS)

    Zhang, Ying; Mao, Xuefei; Liu, Jixin; Wang, Min; Qian, Yongzhong; Gao, Chengling; Qi, Yuehan

    2016-04-01

    In this work, a solid sampling device consisting of a tungsten coil trap, porous carbon vaporizer and on-line ashing furnace of a Ni-Cr coil was interfaced with inductively coupled plasma mass spectrometry (ICP-MS). A modified double gas circuit system was employed that was composed of carrier and supplemental gas lines controlled by separate gas mass flow controllers. For Cd determination in food samples using the assembled solid sampling ICP-MS, the optimal ashing and vaporization conditions, flow rate of the argon-hydrogen (Ar/H2) (v:v = 24:1) carrier gas and supplemental gas, and minimum sampling mass were investigated. Under the optimized conditions, the limit of quantification was 0.5 pg and the relative standard deviation was within a 10.0% error range (n = 10). Furthermore, the mean spiked recoveries for various food samples were 99.4%-105.9% (n = 6). The Cd concentrations measured by the proposed method were all within the certified values of the reference materials or were not significantly different (P > 0.05) from those of the microwave digestion ICP-MS method, demonstrating the good accuracy and precision of the solid sampling ICP-MS method for Cd determination in food samples.

  8. Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS for isotope analysis of long-lived radionuclides

    NASA Astrophysics Data System (ADS)

    Becker, J. Sabine

    2005-04-01

    For a few years now inductively coupled plasma mass spectrometry has been increasingly used for precise and accurate determination of isotope ratios of long-lived radionuclides at the trace and ultratrace level due to its excellent sensitivity, good precision and accuracy. At present, ICP-MS and also laser ablation ICP-MS are applied as powerful analytical techniques in different fields such as the characterization of nuclear materials, recycled and by-products (e.g., spent nuclear fuel or depleted uranium ammunitions), radioactive waste control, in environmental monitoring and in bioassay measurements, in health control, in geochemistry and geochronology. Especially double-focusing sector field ICP mass spectrometers with single ion detector or with multiple ion collector device have been used for the precise determination of long-lived radionuclides isotope ratios at very low concentration levels. Progress has been achieved by the combination of ultrasensitive mass spectrometric techniques with effective separation and enrichment procedures in order to improve detection limits or by the introduction of the collision cell in ICP-MS for reducing disturbing interfering ions (e.g., of 129Xe+ for the determination of 129I). This review describes the state of the art and the progress of ICP-MS and laser ablation ICP-MS for isotope ratio measurements of long-lived radionuclides in different sample types, especially in the main application fields of characterization of nuclear and radioactive waste material, environmental research and health controls.

  9. Determination of the total arsenic concentration in human urine by inductively coupled plasma mass spectrometry: a comparison of the accuracy of three analytical methods.

    PubMed

    Amarasiriwardena, C J; Lupoli, N; Potula, V; Korrick, S; Hu, H

    1998-03-01

    Measurement of arsenic (As) in biological samples such as urine has important clinical applications and is being undertaken more frequently in epidemiologic studies because of concern about the carcinogenicity of low to moderate levels of As exposure. The objective of this study was to evaluate and improve the accuracy of As determination in urine by inductively coupled plasma mass spectrometry (ICP-MS). Determination of As in biological samples by ICP-MS is difficult for two reasons: the formation of the molecular ion 40Ar35Cl, which overlaps with monoisotopic As at a mass-to-charge ratio (m/z) of 75 (causing spectral interference), and signal enhancement due to organic matrix (nonspectral interference). Available procedures were examined, including the application of different correction procedures using 40Ar37Cl and 16O35Cl molecular-ion formation; the addition of N2 into plasma or nebulizer gas flows; and the addition of organic molecules to the sample and to calibration standards to eliminate or correct for interference due to molecular-ion formation. The accuracy and precision of determination of As [m/z 75, ionization potential (IP) 9.81 eV] with use of an internal standard was also investigated. Three elements were studied as candidate internal standards: germanium (Ge: m/z 74, IP 7.90 eV), indium (In: m/z 115, IP 5.79 eV), and tellurium (Te: m/z 128, IP 9.01 eV). It was found that these three elements performed more or less equally well with Ar-N2 plasma; it was also found that accuracy was significantly improved when Te was used as the internal standard instead of Ge or In for ethanol-added samples. Our results indicate that accurate and precise measurement of As in urine by ICP-MS can be obtained by either of two methods (< 5% error, approximately 2% RSD, limit of detection 0.1 ng ml-1): (1) the addition of 1% N2 to plasma gas flow or 3% N2 to nebulizer gas flow, along with use of any of the internal standards tested, or (2) the addition of ethanol to

  10. Effects of liquid chromatography mobile phases and buffer salts on phosphorus inductively coupled plasma atomic emission and mass spectrometries utilizing ultrasonic nebulization and membrane desolvation.

    PubMed

    Carr, John E; Kwok, Kaho; Webster, Gregory K; Carnahan, Jon W

    2006-01-23

    Atomic spectrometry, specifically inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) show promise for heteroatom-based detection of pharmaceutical compounds. The combination of ultrasonic nebulization (USN) with membrane desolvation (MD) greatly enhances detection limits with these approaches. Because pharmaceutical analyses often incorporate liquid chromatography, the study herein was performed to examine the effects of solvent composition on the analytical behaviors of these approaches. The target analyte was phosphorus, introduced as phosphomycin. AES response was examined at the 253.7 nm atom line and mass 31 ions were monitored for the MS experiments. With pure aqueous solutions, detection limits of 5 ppb (0.5 ng in 0.1 mL injection volumes) were obtained with ICP-MS. The ICP-AES detection limit was 150 ppb. Solvent compositions were varied from 0 to 80% organic (acetonitrile and methanol) with nine buffers at concentrations typically used in liquid chromatography. In general, solvents and buffers had statistically significant, albeit small, effects on ICP-AES sensitivities. A few exceptions occurred in cases where typical liquid chromatography buffer concentrations produced higher mass loadings on the plasma. Indications are that isocratic separations can be reliably performed. Within reasonable accuracy tolerances, it appears that gradient chromatography can be performed without the need for signal response normalization. Organic solvent and buffer effects were more significant with ICP-MS. Sensitivities varied significantly with different buffers and organic solvent content. In these cases, gradient chromatography will require careful analytical calibration as solvent and buffer content is varied. However, for most buffer and solvent combinations, signal and detection limits are only moderately affected. Isocratic separations and detection are feasible.

  11. Comparison of 265 nm Femtosecond and 213 nm Nanosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry for Pb Isotope Ratio Measurements.

    PubMed

    Ohata, Masaki; Nonose, Naoko; Dorta, Ladina; Günther, Detlef

    2015-01-01

    The analytical performance of 265 nm femtosecond laser ablation (fs-LA) and 213 nm nanosecond laser ablation (ns-LA) systems coupled with multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) for Pb isotope ratio measurements of solder were compared. Although the time-resolved signals of Pb measured by fs-LA-MC-ICPMS showed smoother signals compared to those obtained by ns-LA-MC-ICPMS, similar precisions on Pb isotope ratio measurements were obtained between them, even though their operating conditions were slightly different. The mass bias correction of the Pb isotope ratio measurement was carried out by a comparison method using a Pb standard solution prepared from NIST SRM 981 Pb metal isotopic standard, which was introduced into the ICP by a desolvation nebulizer (DSN) via a dual-sample introduction system, and it was successfully demonstrated for Pb isotope ratio measurements for either NIST 981 metal isotopic standard or solder by fs-LA-MC-ICPMS since the analytical results agreed well with the certified value as well as the determined value within their standard deviations obtained and the expanded uncertainty of the certified or determined value. The Pb isotope ratios of solder obtained by ns-LA-MC-ICPMS also showed agreement with respect to the determined value within their standard deviations and expanded uncertainty. From these results, it was evaluated that the mass bias correction applied in the present study was useful and both LA-MC-ICPMS could show similar analytical performance for the Pb isotope ratio microanalysis of metallic samples such as solder.

  12. Comparison of 265 nm Femtosecond and 213 nm Nanosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry for Pb Isotope Ratio Measurements.

    PubMed

    Ohata, Masaki; Nonose, Naoko; Dorta, Ladina; Günther, Detlef

    2015-01-01

    The analytical performance of 265 nm femtosecond laser ablation (fs-LA) and 213 nm nanosecond laser ablation (ns-LA) systems coupled with multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) for Pb isotope ratio measurements of solder were compared. Although the time-resolved signals of Pb measured by fs-LA-MC-ICPMS showed smoother signals compared to those obtained by ns-LA-MC-ICPMS, similar precisions on Pb isotope ratio measurements were obtained between them, even though their operating conditions were slightly different. The mass bias correction of the Pb isotope ratio measurement was carried out by a comparison method using a Pb standard solution prepared from NIST SRM 981 Pb metal isotopic standard, which was introduced into the ICP by a desolvation nebulizer (DSN) via a dual-sample introduction system, and it was successfully demonstrated for Pb isotope ratio measurements for either NIST 981 metal isotopic standard or solder by fs-LA-MC-ICPMS since the analytical results agreed well with the certified value as well as the determined value within their standard deviations obtained and the expanded uncertainty of the certified or determined value. The Pb isotope ratios of solder obtained by ns-LA-MC-ICPMS also showed agreement with respect to the determined value within their standard deviations and expanded uncertainty. From these results, it was evaluated that the mass bias correction applied in the present study was useful and both LA-MC-ICPMS could show similar analytical performance for the Pb isotope ratio microanalysis of metallic samples such as solder. PMID:26656823

  13. Application of nanosecond-UV laser ablation-inductively coupled plasma mass spectrometry for the isotopic analysis of single submicrometer-size uranium particles.

    PubMed

    Pointurier, Fabien; Pottin, Anne-Claire; Hubert, Amélie

    2011-10-15

    For the first time, laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) was used to carry out isotopic measurement on single submicrometer-size uranium particles. The analytical procedure was applied on two particle-containing samples already analyzed in the same laboratory by established techniques for particle analysis: combination of the fission track technique with thermo-ionization mass spectrometry (FT-TIMS) and secondary ion mass spectrometry (SIMS). Particles were extracted from their initial matrix with ethanol and deposited on a polycarbonate disk where they were fixed in a layer of an organic compound (collodion). Prior to the isotopic analysis, particles were precisely located on the disk's surface by scanning electron microscopy (SEM) for one sample and using the fission track technique for the other sample. Most of the particles were smaller than 1 μm, and their (235)U content was in the femtogram range. (235)U/(238)U ratios were successfully analyzed for all located particles using a nanosecond-UV laser (Cetac LSX 213 nm) coupled to a quadrupole-based ICPMS (Thermo "X-Series II"). LA-ICPMS results, although less precise and accurate (typically 10%) than the ones obtained by FT-TIMS and SIMS due to short (20-40 s), transient, and noisy signals, are in good agreement with the certified values or with the results obtained with other techniques. Thanks to good measurement efficiency (~6 × 10(-4)) and high signal/noise ratio during the analysis, LA-ICPMS can be considered a very promising technique for fast particle analysis, provided that uranium-bearing particles are fixed on the sample holder and located prior to isotope measurement. PMID:21875035

  14. Development and Evaluation of an Externally Air-Cooled Low-Flow torch and the Attenuation of Space Charge and Matrix Effects in Inductively Coupled Plasma Mass Spectrometry

    SciTech Connect

    Praphairaksit, N.

    2000-09-12

    An externally air-cooled low-flow torch has been constructed and successfully demonstrated for applications in inductively coupled plasma mass spectrometry (ICP-MS). The torch is cooled by pressurized air flowing at {approximately}70 L/min through a quartz air jacket onto the exterior of the outer tube. The outer gas flow rate and operating RF forward power are reduced considerably. Although plasmas can be sustained at the operating power as low as 400 W with a 2 L/min of outer gas flow, somewhat higher power and outer gas flows are advisable. A stable and analytical useful plasma can be obtained at 850 W with an outer gas flow rate of {approximately}4 L/min. Under these conditions, the air-cooled plasma produces comparable sensitivities, doubly charged ion ratios, matrix effects and other analytical merits as those produced by a conventional torch while using significantly less argon and power requirements. Metal oxide ion ratios are slightly higher with the air-cooled plasma but can be mitigated by reducing the aerosol gas flow rate slightly with only minor sacrifice in analyte sensitivity. A methodology to alleviate the space charge and matrix effects in ICP-MS has been developed. A supplemental electron source adapted from a conventional electron impact ionizer is added to the base of the skimmer. Electrons supplied from this source downstream of the skimmer with suitable amount and energy can neutralize the positive ions in the beam extracted from the plasma and diminish the space charge repulsion between them. As a result, the overall ion transmission efficiency and consequent analyte ion sensitivities are significantly improved while other important analytical aspects, such as metal oxide ion ratio, doubly charged ion ratio and background ions remain relatively unchanged with the operation of this electron source. This technique not only improves the ion transmission efficiency but also minimizes the matrix effects drastically. The matrix-induced suppression

  15. Evaluation of on-line desalter-inductively coupled plasma-mass spectrometry system for determination of Cr(III), Cr(VI), and total chromium concentrations in natural water and urine samples

    NASA Astrophysics Data System (ADS)

    Sun, Y. C.; Lin, C. Y.; Wu, S. F.; Chung, Y. T.

    2006-02-01

    We have developed a simple and convenient method for the determination of Cr(III), Cr(VI), and the total chromium concentrations in natural water and urine samples that use a flow injection on-line desalter-inductively coupled plasma-mass spectrometry system. When using aqueous ammonium chloride (pH 8) as the stripping solution, the severe interference from sodium in the matrix can be eliminated prior to inductively coupled plasma-mass spectrometry measurement, and the Cr(VI) level can be determined directly. To determine the total concentration of Cr in natural water and urine samples, we used H 2O 2 or HNO 3 to decompose the organic matter and convert all chromium species into the Cr(VI) oxidation state. To overcome the spectral interference caused by the matrix chloride ion in the resulting solutions, we employed cool plasma to successfully suppress chloride-based molecular ion interference during the inductively coupled plasma-mass spectrometry measurement. By significantly eliminating interference from the cationic and anionic components in the matrices prior to the inductively coupled plasma-mass spectrometry measurement, we found that the detection limit reached 0.18 μg L - 1 (based on 3 sigma). We validated this method through the analysis of the total chromium content in two reference materials (NIST 1643c and 2670E) and through measuring the recovery in spiked samples.

  16. Accurate determination of ultra-trace impurities, including europium, in ultra-pure barium carbonate materials through inductively coupled plasma-tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Wu, Shuchao; Zeng, Xiangcheng; Dai, Xuefeng; Hu, Yongping; Li, Gang; Zheng, Cunjiang

    2016-09-01

    Impurities, especially ultra-trace europium (Eu), in ultra-pure barium carbonate materials were accurately determined through inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). Two reaction modes, namely, mass shift (with O2 as reaction gas) and on-mass modes(with NH3/He and He as reaction gases), were extensively investigated using Eu+ as target analyte. The use of Eu+ → EuO2+, instead of Eu+ → EuO+, as ion pairs in mass shift mode eliminated polyatomic interferences based on Ba matrix ions (135Ba16O2+ on 151Eu16O+ and 137Ba16O2+ on 153Eu16O+). This procedure exhibited enhanced sensitivity and selectivity. When the ICP-MS/MS was operated in NH3 on-mass mode, Eu+ can be determined in its original mass in interference-free conditions because NH3 did not react with Eu+ but with BaO+ to form a neutral product (BaO). The two reaction modes, especially NH3 on mass mode, were validated to be accurate because their resultant isotope ratios of 153Eu/151Eu matched well with that of the natural abundance ratio. The proposed ICP-MS/MS method is a sensitive technique with a limit of detection as low as 2.0 ng L- 1 for 153Eu+. Compared with conventional single-quadrupole (SQ) ICP-MS, both NH3 on-mass mode and O2 mass shift mode in ICP-MS/MS can be used to accurately determine Eu+ in ultra-pure BaCO3 materials. The detected concentration of Eu+ was 4.0 ng L- 1 to 15 ng L- 1, with spiked recoveries ranging from 100%-110%. ICP-MS/MS was also used to eliminate polyatomic interferences, particularly Ba-based interferences, prior to measurement of Gd and Sm. Impurities, including Na, Mg, Al, K, Mn, Fe, Cr, Sr, and Cs, in ultra-pure BaCO3 materials were also determined using ICP-MS/MS in conventional SQ mode.

  17. Method for the quantification of vanadyl porphyrins in fractions of crude oils by High Performance Liquid Chromatography-Flow Injection-Inductively Coupled Plasma Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Wandekoken, Flávia G.; Duyck, Christiane B.; Fonseca, Teresa C. O.; Saint'Pierre, Tatiana D.

    2016-05-01

    High performance liquid chromatography hyphenated by flow injection to inductively coupled plasma mass spectrometry (HPLC-FI-ICP-MS) was used to investigate V linked to porphyrins present in fractions of crude oil. First, the crude oil sample was submitted to fractionation by preparative liquid chromatography with UV detection, at the porphyrin Soret band wavelength (400 nm). The obtained porphyrin fractions were then separated in a 250 mm single column, in the HPLC, and eluted with different mobile phases (methanol or methanol:toluene (80:20; v:v)). The quantification of V-porphyrins in the fractions eluted from HPLC was carried out by online measuring the 51V isotope in the ICP-MS, against vanadyl octaethylporphine standard solutions (VO-OEP), prepared in the same solvent as the mobile phase, and injected post-column directly into the plasma. A 20 μg L- 1 Ge in methanol was used as internal standard for minimizing non-spectral interference, such as short-term variations due to injection. The mathematical treatment of the signal based on Fast Fourier Transform smoothing algorithm was employed to improve the precision. The concentrations of V as V-porphyrins were between 2.7 and 11 mg kg- 1 in the fractions, which were close to the total concentration of V in the porphyrin fractions of the studied crude oil.

  18. Direct introduction of volatile carbon compounds into the spray chamber of an inductively coupled plasma mass spectrometer: Sensitivity enhancement for selenium

    NASA Astrophysics Data System (ADS)

    Kovačevič, Miroslav; Goessler, Walter

    2005-10-01

    The effect of signal enhancement of elements with ionization potentials in the range from 9 to 11 eV by carbon-containing compounds is a well-known phenomenon in inductively coupled plasma mass spectrometry (ICPMS). It has traditionally been exploited through the addition of organic solvents to the sample matrix or to the mobile phase to improve sensitivity. In the present work, aqueous solutions of volatile carbon compounds (acetone, methanol and acetic acid) were directly introduced into the thermostatted spray chamber rather than being added to the sample matrix. It is presumed that no aerosol is produced from these solutions and only vapors of organic compounds are swept into the plasma together with the sample aerosol. When a 0.40 mol l - 1 aqueous solution of acetone was introduced directly into the spray chamber, the signals for arsenic and selenium were enhanced by a factor of 4.2. The usefulness of this approach was demonstrated through the achievement of lower instrumental detection limits for selenium at m/z 82 (0.1 ng ml - 1 ) compared to the system without direct introduction of volatile carbon compounds (0.5 ng ml - 1 ). The method was successfully applied in the determination of traces of selenium in natural water, urine and bovine liver reference material.

  19. Direct analysis of carbohydrates in animal plasma by ion chromatography coupled with mass spectrometry and pulsed amperometric detection for use as a non-invasive diagnostic tool.

    PubMed

    Kotnik, Darja; Smidovnik, Andrej; Jazbec-Križman, Petra; Križman, Mitja; Prošek, Mirko

    2011-12-01

    The present paper demonstrates that electrochemical detection (ECD) coupled to ion chromatography and electrospray ionization tandem mass spectrometry (IC-ECD-ESI/MS/MS) can be used to rapidly estimate some indications of the health status of organisms. The lactulose to mannitol ratio (L/M) is used as a non-invasive assay to investigate small intestinal absorption pathways and mucosal integrity. In the present study, an evaluation of the negative effects of nonsteroidal anti-inflammatory drug meloxicam perorally administrated to a group of dogs was carried out by determining the lactulose/mannitol index using the IC-ECD-ESI/MS/MS hyphenated technique. According to the results of the study, meloxicam altered gastrointestinal permeability. Coenzyme Q(10) (CoQ(10)) was tested to determine if it could prevent meloxicam induced gastrointestinal damage and it was found that CoQ(10) could be an effective preventive treatment. Furthermore, plasma glucose concentration level was determined to be an indirect indicator of the oxidative state in the blood. To find out the beneficial effects of a double antioxidant combination (α-lipoic acid (ALA) and CoQ(10)) on the total glucose level in chickens, ALA and CoQ(10) were provided as food additives in factory farm raised chicken. The results of the pilot study indicate that the glucose level in the plasma of chickens group fed with CoQ(10) and ALA was significantly decreased compared to the control group. Ion chromatography (IC) utilizing pulsed amperometric detection (PAD) was compared to ion chromatography coupled with tandem mass spectrometry (MS/MS) as an analytical tool for monitoring the carbohydrate level in biological fluids. In electrochemical detection, the newly developed two-pulse waveform successfully withstands matrix effects in biological samples. Continuous on-line desalting of the high salt concentrations used as the eluent for carbohydrate separation from the anion-exchange column allows coupling of IC and MS

  20. Soluble arsenic and selenium species in fly ash/organic waste-amended soils using ion chromatography-inductively coupled plasma mass spectrometry

    SciTech Connect

    Jackson, B.P.; Miller, W.P.

    1999-01-15

    Mixing coal fly ash with an organic waste increases macronutrient content and may make land application of fly ash a viable disposal alternative. However, trace element chemistry of these mixed waste products warrants investigation. Speciation of As and Se in soil solutions of fly ash-, poultry litter- and sewage sludge-amended soils was determined over a 10-day period by ion chromatography coupled to inductively coupled plasma mass spectrometry (IC-ICP-MS). Detection limits were 0.031, 0.028, 0.051, 0.161, 0.497, and 0.660 {micro}g L{sup {minus}1} for dimethylarsinate (DMA), As(III), monomethylarsonate (MMA), As(V), Se(IV), and Se(VI), respectively. Arsenic was highly water-soluble from poultry litter and appeared to be predominantly As(V). Arsenic(V) was the predominant species in soil amended with two fly ashes. Application of fly ash/poultry litter mixtures increased As solubility and led to the prevalence of DMA as the major As species. DMA concentrations of these soil solutions decreased rapidly over the sampling period relative to As(V), suggesting that DMA readily underwent mineralization in the soil solution. Se(VI) was the predominant soluble Se species in all treatments indicating rapid oxidation of Se(IV) initially solubilized from the fly ashes.

  1. Arsenic speciation in rice by capillary electrophoresis/inductively coupled plasma mass spectrometry: enzyme-assisted water-phase microwave digestion.

    PubMed

    Qu, Haiou; Mudalige, Thilak K; Linder, Sean W

    2015-04-01

    We report an analytical methodology for the quantification of common arsenic species in rice and rice cereal using capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICPMS). An enzyme (i.e., α-amylase)-assisted water-phase microwave extraction procedure was used to extract four common arsenic species, including dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), arsenite [As(III)], and arsenate [As(V)] from the rice matrices. The addition of the enzyme α-amylase during the extraction process was necessary to reduce the sample viscosity, which subsequently increased the injection volume and enhanced the signal response. o-Arsanilic acid (o-ASA) was added to the sample solution as a mobility marker and internal standard. The obtained repeatability [i.e., relative standard deviation (RSD %)] of the four arsenic analytes of interest was less than 1.23% for elution time and 2.91% for peak area. The detection limits were determined to be 0.15-0.27 ng g(-1). Rice standard reference materials SRM 1568b and CRM 7503-a were used to validate this method. The quantitative concentrations of each organic arsenic and summed inorganic arsenic were found within 5% difference of the certified values of the two reference materials.

  2. Development of a novel low-flow ion source/sampling cone geometry for inductively coupled plasma mass spectrometry and application in hyphenated techniques

    NASA Astrophysics Data System (ADS)

    Pfeifer, Thorben; Janzen, Rasmus; Steingrobe, Tobias; Sperling, Michael; Franze, Bastian; Engelhard, Carsten; Buscher, Wolfgang

    2012-10-01

    A novel ion source/sampling cone device for inductively coupled plasma mass spectrometry (ICP-MS) especially operated in the hyphenated mode as a detection system coupled with different separation modules is presented. Its technical setup is described in detail. Its main feature is the very low total argon consumption of less than 1.5 L min- 1, leading to significant reduction of operational costs especially when time-consuming speciation analysis is performed. The figures of merit of the new system with respect to sensitivity, detection power, long-term stability and working range were explored. Despite the profound differences of argon consumption of the new system in comparison to the conventional ICP-MS system, many of the characteristic features of the conventional ICP-MS could be maintained to a great extent. To demonstrate the ion source's capabilities, it was used as an element-selective detector for gas (GC) and high performance liquid chromatography (HPLC) where organic compounds of mercury and cobalt, respectively, were separated and detected with the new low-flow ICP-MS detection system. The corresponding chromatograms are shown. The applicability for trace element analysis has been validated with the certified reference material NIST 1643e.

  3. Application of the Zr/Hf ratio in the determination of hafnium in geochemical samples by high-resolution inductively coupled plasma mass spectrometry.

    PubMed

    Liu, Ya Xuan; Li, Qing Xia; Ma, Na; Sun, Xiao Ling; Bai, Jin Feng; Zhang, Qin

    2014-12-01

    Hafnium content and its change are of significance in geochemistry and cosmochemistry; however, the determination of hafnium has always been problematic in analytical chemistry. In this paper, a new idea is proposed for the determination of hafnium in geochemical samples, including rocks, soils, and stream sediments. Through the comparison of two conventional open-type acid digestion methods (HF-HNO3-HClO4 and HF-HNO3-H2SO4), it was found that although neither of these methods could fully digest the zirconium and hafnium in a sample, the zirconium and hafnium digestion behaviors in one sample were consistent in the 60 experimental geochemical reference materials with different properties, so the experimentally determined Zr/Hf ratio in solution could be used to calculate the hafnium content in a sample. In addition, possible mass spectral interferences during the determination of zirconium and hafnium by high resolution inductively coupled plasma mass spectrometry (HR-ICPMS) were studied, and it was found that the mass spectral interferences of the selected isotopes (90)Zr and (178)Hf could be neglected. The mass spectral behaviors of (90)Zr and (178)Hf were also very consistent during the determination by HR-ICPMS. Since the hafnium content was calculated using the ratio value, all of the errors (including the errors in weighing process, the accidental errors during operation and the instrument fluctuation in the determination) of the Zr/Hf ratio could be effectively reduced or even eliminated. The relative standard deviation of the actual samples was lower than 3.2%, and the detection limit of the method (considering the dilution effect and matrix effect during measurement of the Zr/Hf ratio and zirconium content) was 0.04 μg/g. The proposed method could satisfy the requirement for the determination of hafnium in geochemical samples.

  4. Application of Microwave-Induced Combustion and Isotope Dilution Strategies for Quantification of Sulfur in Coals via Sector-Field Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Christopher, Steven J; Vetter, Thomas W

    2016-05-01

    In recent years, microwave-induced combustion (MIC) has proved to be a robust sample preparation technique for difficult-to-digest samples containing high carbon content, especially for determination of halogens and sulfur. National Institute of Standards and Technology (NIST) has applied the MIC methodology in combination with isotope dilution analysis for sulfur determinations, representing the first-reported combination of this robust sample preparation methodology and high-accuracy quantification approach. Medium-resolution mode sector-field inductively coupled plasma mass spectrometry was invoked to avoid spectral interferences on the sulfur isotopes. The sample preparation and instrumental analysis scheme was used for the value assignment of total sulfur in Standard Reference Material (SRM) 2682c Subbituminous Coal (nominal mass fraction 0.5% sulfur). A description of the analytical procedures required is provided, along with metrological results, including an estimation of the overall method uncertainty (<1.5% relative expanded uncertainty) calculated using the IDMS measurement function and a Kragten spreadsheet approach. PMID:27032706

  5. Measurements of natural uranium concentration and isotopic composition with permil-level precision by inductively coupled plasma-quadrupole mass spectrometry

    NASA Astrophysics Data System (ADS)

    Shen, Chuan-Chou; Lin, Huei-Ting; Chu, Mei-Fei; Yu, Ein-Fen; Wang, Xianfeng; Dorale, Jeffrey A.

    2006-09-01

    A new analytical technique using inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) has been developed that produces permil-level precision in the measurement of uranium concentration ([U]) and isotopic composition (δ234U) in natural materials. A 233U-236U double spike method was used to correct for mass fractionation during analysis. To correct for ratio drifting, samples were bracketed by uranium standard measurements. A sensitivity of 6-7 × 108 cps/ppm was generated with a sample solution uptake rate of 30 μL/min. With a measurement time of 15-20 min, standards of 30-ng uranium produced a within-run precision better than 3‰ (±2 R.S.D.) for δ234U and better than 2‰ for [U]. Replicate measurements made on standards show that a between-run reproducibility of 3.5‰ for δ234U and 2‰ for [U] can be achieved. ICP-QMS data of δ234U and [U] in seawater, coral, and speleothem materials are consistent with the data measured by other ICP-MS and TIMS techniques. Advantages of the ICP-QMS method include low cost, easy maintenance, simple instrumental operation, and few sample preparation steps. Sample size requirements are small, such as 10-14 mg of coral material. The results demonstrate that this technique can be applied to natural samples with various matrices.

  6. Determination of impurities in thoria (ThO 2) using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

    NASA Astrophysics Data System (ADS)

    Alamelu, Devanathan; Choudhary, Ashwini Kumar; Aggarwal, Suresh Kumar

    2010-11-01

    Elemental impurities in nuclear grade thoria were determined using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) employing ArF laser (20 ns, 193 nm, 20 Hz). Three certified standards of thoria, prepared in the Department of Atomic Energy (DAE), India were used for this work. Magnesium was used as an internal standard for quantification in view of its addition during fuel fabrication. The concentrations determined for 16 different elements (Al, B, Cd, Ce, Cu, Dy, Er, Eu, Fe, Gd, Mg, Mn, Mo, Ni, Sb, Sm and V), spanning four orders of magnitude, were within 20% of the certified values in the standards. The methodology is of interest to reduce the analytical effort with regard to dissolution of thoria samples, avoid the production of radioactive liquid waste streams and relatively simple mass spectrum as compared to complex emission spectra in atomic emission spectroscopy (AES) and laser induced breakdown spectroscopy (LIBS). The development and validation of analytical methodologies based on independent physico-chemical principles is of great relevance to characterize the in-house prepared working standards for routine applications.

  7. Application of Microwave-Induced Combustion and Isotope Dilution Strategies for Quantification of Sulfur in Coals via Sector-Field Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Christopher, Steven J; Vetter, Thomas W

    2016-05-01

    In recent years, microwave-induced combustion (MIC) has proved to be a robust sample preparation technique for difficult-to-digest samples containing high carbon content, especially for determination of halogens and sulfur. National Institute of Standards and Technology (NIST) has applied the MIC methodology in combination with isotope dilution analysis for sulfur determinations, representing the first-reported combination of this robust sample preparation methodology and high-accuracy quantification approach. Medium-resolution mode sector-field inductively coupled plasma mass spectrometry was invoked to avoid spectral interferences on the sulfur isotopes. The sample preparation and instrumental analysis scheme was used for the value assignment of total sulfur in Standard Reference Material (SRM) 2682c Subbituminous Coal (nominal mass fraction 0.5% sulfur). A description of the analytical procedures required is provided, along with metrological results, including an estimation of the overall method uncertainty (<1.5% relative expanded uncertainty) calculated using the IDMS measurement function and a Kragten spreadsheet approach.

  8. Spatial location of the space charge effect in individual ion clouds using monodisperse dried microparticulate injection with a twin quadrupole inductively coupled plasma mass spectrometer.

    PubMed

    Allen, L A; Leach, J J; Houk, R S

    1997-07-01

    Pulses of analyte and matrix ions from individual drops are measured simultaneously using a twin quadrupole inductively coupled plasma mass spectrometer (ICP-MS). The sample solution is introduced by monodisperse dried microparticulate injection (MDMI). At modest Pb concentrations (500 ppm), a shoulder on the leading edge of the Li(+) signal appears. At higher matrix concentrations (1000 to at least 1500 ppm), a dip in the leading edge of the Li(+) signal develops. These changes in the shapes of the Li(+) pulses are attributed to space charge effects in the extraction system and ion optics of the mass spectrometer. A qualitative depiction for this behavior is proposed, in which the Li(+) ions are deflected out of the preferred ion path and then refocused by the ion optics. Part of the Li(+) ion cloud is driven ahead of the Pb(+) cloud, and part is trapped behind the Pb(+) cloud. The result is a shoulder on the leading edge of the Li(+) signal. With the Pb matrix present, the shapes of the analyte ion pulses are sensitive to the voltages applied to the first two ion lenses, especially the extractor lens. This observation shows that the part of the matrix effect that occurs in the ion optics takes place mainly in the first two lenses.

  9. Determination of chromium in human lung fibroblast cells using a large bore-direct injection high-efficiency nebulizer with inductively coupled plasma mass spectrometry

    SciTech Connect

    McLean, John A.; Acon, Billy W.; Montaser, Akbar; Singh, Jatinder; Pritchard, Daryl E.; Patierno, Steven R.

    2000-05-01

    A novel method for the determination of chromium in suspensions of human lung fibroblast cells is described by using a large bore-direct injection high efficiency nebulizer (LB-DIHEN) with microscale flow injection analysis and inductively coupled plasma mass spectrometric detection. Chromium (VI)-treated cells were first counted and then suspended in a phosphate buffer saline solution. With the use of the method of standard additions, the relative concentration of Cr in {approx}100 HLF cells/peak was determined at m/z=50. Because the cells tend to clump and can yield inhomogeneities in the total number analyzed, Mg was used as an internal standard to compensate for the total cell mass. The level of Cr in HLF cells grown in a medium of 100 {mu}M Na{sub 2}CrO{sub 4} for two hours is on the order of 180 fg Cr/cell after correction for the number of cells in each injection. (c) 2000 Society for Applied Spectroscopy.

  10. Validation of the determination of the B isotopic composition in Roman glasses with laser ablation multi-collector inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Devulder, Veerle; Gerdes, Axel; Vanhaecke, Frank; Degryse, Patrick

    2015-03-01

    The applicability of laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) for the determination of the B isotopic composition in Roman glasses was investigated. The δ11B values thus obtained provide information on the natron flux used during the glass-making process. The glass samples used for this purpose were previously characterized using pneumatic nebulization (PN) MC-ICP-MS. Unfortunately, this method is time-consuming and labor-intensive and consumes some 100 mg of sample, which is a rather high amount for ancient materials. Therefore, the use of the less invasive and faster LA-MC-ICP-MS approach was explored. In this work, the results for 29 Roman glasses and 4 home-made glasses obtained using both techniques were compared to assess the suitability of LA-MC-ICP-MS in this context. The results are in excellent agreement within experimental uncertainty. No difference in overall mass discrimination was observed between the Roman glasses, NIST SRM 610 reference glass and B6 obsidian. The expanded uncertainty of the LA-MC-ICP-MS approach was estimated to be < 2‰, which is similar to that obtained upon sample digestion and PN-MC-ICP-MS measurement.

  11. Simultaneous determination of bromine and chlorine in coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis.

    PubMed

    de Gois, Jefferson S; Pereira, Éderson R; Welz, Bernhard; Borges, Daniel L G

    2014-12-10

    A new method for the direct analysis of coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis was developed, aiming at the determination of Br and Cl. The procedure does not require any significant sample pretreatment and allows simultaneous determination of both elements to be carried out, requiring small mass aliquots of sample (about 0.5 mg). All operating parameters, including carrier gas flow-rate and RF power, were optimized for maximum sensitivity. The use of modifiers/aerosol carriers (Pd, Pd+Al and Pd+Ca) was evaluated, and the mixture of Pd and Ca was chosen, allowing pyrolysis and vaporization temperatures of 700°C and 1900°C, respectively. Chlorine was accurately determined using calibration against solid standards, whereas Br could also be determined using calibration against aqueous standard solutions. The limits of quantification were 0.03 μg g(-1) for Br and 7 μg g(-1) for Cl, and no spectral interferences were observed.

  12. Improving Precision and Accuracy of Isotope Ratios from Short Transient Laser Ablation-Multicollector-Inductively Coupled Plasma Mass Spectrometry Signals: Application to Micrometer-Size Uranium Particles.

    PubMed

    Claverie, Fanny; Hubert, Amélie; Berail, Sylvain; Donard, Ariane; Pointurier, Fabien; Pécheyran, Christophe

    2016-04-19

    The isotope drift encountered on short transient signals measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) is related to differences in detector time responses. Faraday to Faraday and Faraday to ion counter time lags were determined and corrected using VBA data processing based on the synchronization of the isotope signals. The coefficient of determination of the linear fit between the two isotopes was selected as the best criterion to obtain accurate detector time lag. The procedure was applied to the analysis by laser ablation-MC-ICPMS of micrometer sized uranium particles (1-3.5 μm). Linear regression slope (LRS) (one isotope plotted over the other), point-by-point, and integration methods were tested to calculate the (235)U/(238)U and (234)U/(238)U ratios. Relative internal precisions of 0.86 to 1.7% and 1.2 to 2.4% were obtained for (235)U/(238)U and (234)U/(238)U, respectively, using LRS calculation, time lag, and mass bias corrections. A relative external precision of 2.1% was obtained for (235)U/(238)U ratios with good accuracy (relative difference with respect to the reference value below 1%). PMID:27031645

  13. Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Malherbe, Julien; Claverie, Fanny; Alvarez, Aitor; Fernandez, Beatriz; Pereiro, Rosario; Molloy, John L

    2013-09-01

    Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n=3, 1σ). A good agreement between experimental results and the certified values was also observed.

  14. Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Malherbe, Julien; Claverie, Fanny; Alvarez, Aitor; Fernandez, Beatriz; Pereiro, Rosario; Molloy, John L

    2013-09-01

    Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n=3, 1σ). A good agreement between experimental results and the certified values was also observed. PMID:23953208

  15. Ultrasound-assisted enzymatic hydrolysis for iodinated amino acid extraction from edible seaweed before reversed-phase high performance liquid chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Romarís-Hortas, Vanessa; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

    2013-09-27

    The combination of reverse phase high performance liquid chromatography (RP-HPLC) with inductively coupled plasma mass spectrometry (ICP-MS) was used for the determination of monoiodotyrosine (MIT) and diiodotyrosine (DIT) in edible seaweed. A sample pre-treatment based on ultrasound assisted enzymatic hydrolysis was optimized for the extraction of these iodinated amino acids. Pancreatin was selected as the most adequate type of enzyme, and parameters affecting the extraction efficiency (pH, temperature, mass of enzyme and extraction time) were evaluated by univariate approaches. In addition, extractable inorganic iodine (iodide) was also quantified by anion exchange high performance liquid chromatography (AE-HPLC) coupled with ICP-MS. The proposed procedure offered limits of detection of 1.1 and 4.3ngg(-1) for MIT and DIT, respectively. Total iodine contents in seaweed, as well as total iodine in enzymatic digests were measured by ICP-MS after microwave assisted alkaline digestion with tetramethylamonium hydroxide (TMAH) for total iodine assessment, and also by treating the pancreatin extracts (extractable total iodine assessment). The optimized procedure was successfully applied to five different types of edible seaweed. The highest total iodine content, and also the highest iodide levels, was found in the brown seaweed Kombu (6646±45μgg(-1)). Regarding iodinated amino acids, Nori (a red seaweed) was by far the one with the highest amount of both species (42±3 and 0.41±0.024μgg(-1) for MIT and DIT, respectively). In general, MIT concentrations were much higher than the amounts of DIT, which suggests that iodine from iodinated proteins in seaweed is most likely bound in the form of MIT residues.

  16. Laser ablation inductively coupled plasma mass spectrometry for imaging of copper, zinc, and platinum in thin sections of a kidney from a mouse treated with cis-platin

    NASA Astrophysics Data System (ADS)

    Zoriy, Myroslav; Matusch, Andreas; Spruss, Thilo; Becker, J. Sabine

    2007-02-01

    Platinum complexes are used for the treatment of several types of cancer. High platinum concentrations in the target tissue and low concentrations in dose-limiting tissue structures such as renal tubules are desirable to assure selective toxicity. Microlocal analysis of platinum distribution in tissue sections may thus contribute to the optimization of platinum therapy. Scanning laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to produce images of element distribution in 14-[mu]m thin sections of kidney tissue from a mouse treated with cis-platin 60 min prior to victimization. The sample surface was scanned (raster area 300 mm2) with a focused laser beam (wavelength 266 nm, diameter of laser crater 50 [mu]m, inter line distance 50 [mu]m and laser power density 3 x 109 W cm-2) in a cooled laser ablation chamber (about -15 [degree sign]C) developed for these measurements. The laser ablation system was coupled to a double-focusing sector field ICP-MS. Ion intensities of 63Cu+, 64Zn+, and 196Pt+ were measured within the tissue by LA-ICP-MS. Matrix-matched laboratory standards served for calibration of analytical data. The mass spectrometric analysis yielded an inhomogeneous distribution for Cu, Zn, and Pt in thin kidney sections. Copper was enriched in the capsule and outer cortex, zinc in the inner cortex and the platinum concentration followed a centripetal gradient with clear medullar enrichment. Thus, scanning LA-ICP-MS may be a useful tool in the preclinical development of new and less nephrotoxic platinum complexes.

  17. Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

    PubMed

    Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

    2010-07-30

    The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification. PMID:20552700

  18. Application of laser ablation multicollector inductively coupled plasma mass spectrometry for the measurement of calcium and lead isotope ratios in packaging for discriminatory purposes.

    PubMed

    Santamaria-Fernandez, Rebeca; Wolff, Jean-Claude

    2010-07-30

    The potential of high-precision calcium and lead isotope ratio measurements using laser ablation coupled to multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to aid distinction between four genuine and five counterfeit pharmaceutical packaging samples and further classification of counterfeit packaging samples has been evaluated. We highlight the lack of reference materials for LA-MC-ICP-MS isotope ratio measurements in solids. In this case the problem is minimised by using National Institute of Standards and Technology Standard Reference Material (NIST SRM) 915a calcium carbonate (as solid pellets) and NIST SRM610 glass disc for sample bracketing external standardisation. In addition, a new reference material, NIST SRM915b calcium carbonate, has been characterised in-house for Ca isotope ratios and is used as a reference sample. Significant differences have been found between genuine and counterfeit samples; the method allows detection of counterfeits and aids further classification of packaging samples. Typical expanded uncertainties for measured-corrected Ca isotope ratio values ((43)Ca/(44)Ca and (42)Ca/(44)Ca) were found to be below 0.06% (k = 2, 95% confidence) and below 0.2% for measured-corrected Pb isotope ratios ((207)Pb/(206)Pb and (208)Pb/(206)Pb). This is the first time that Ca isotope ratios have been measured in packaging materials using LA coupled to a multicollector (MC)-ICP-MS instrument. The use of LA-MC-ICP-MS for direct measurement of Ca and Pb isotopic variations in cardboard/ink in packaging has definitive potential to aid counterfeit detection and classification.

  19. SPECIATION OF SELENIUM AND ARSENIC COMPOUNDS BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW AND ON-LINE REDUCTION OF SELENIUM(VI) TO SELENIUM(IV) WITH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

    EPA Science Inventory

    Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV') by mixing the CE effluent with concentrated HCl. A microporo...

  20. In situ location and U-Pb dating of small zircon grains in igneous rocks using laser ablation-inductively coupled plasma-quadrupole mass spectrometry

    NASA Astrophysics Data System (ADS)

    Sack, Patrick J.; Berry, Ron F.; Meffre, Sebastien; Falloon, Trevor J.; Gemmell, J. Bruce; Friedman, Richard M.

    2011-05-01

    A new U-Pb zircon dating protocol for small (10-50 μm) zircons has been developed using an automated searching method to locate zircon grains in a polished rock mount. The scanning electron microscope-energy-dispersive X ray spectrum-based automated searching method can routinely find in situ zircon grains larger than 5 μm across. A selection of these grains was ablated using a 10 μm laser spot and analyzed in an inductively coupled plasma-quadrupole mass spectrometer (ICP-QMS). The technique has lower precision (˜6% uncertainty at 95% confidence on individual spot analyses) than typical laser ablation ICP-MS (˜2%), secondary ion mass spectrometry (<1%), and isotope dilution-thermal ionization mass spectrometry (˜0.4%) methods. However, it is accurate and has been used successfully on fine-grained lithologies, including mafic rocks from island arcs, ocean basins, and ophiolites, which have traditionally been considered devoid of dateable zircons. This technique is particularly well suited for medium- to fine-grained mafic volcanic rocks where zircon separation is challenging and can also be used to date rocks where only small amounts of sample are available (clasts, xenoliths, dredge rocks). The most significant problem with dating small in situ zircon grains is Pb loss. In our study, many of the small zircons analyzed have high U contents, and the isotopic compositions of these grains are consistent with Pb loss resulting from internal α radiation damage. This problem is not significant in very young rocks and can be minimized in older rocks by avoiding high-U zircon grains.

  1. Metabolic profile of Fructus Gardeniae in human plasma and urine using ultra high-performance liquid chromatography coupled with high-resolution LTQ-orbitrap mass spectrometry.

    PubMed

    Wang, Gao-Wa; Bao, Burenbatu; Han, Zhi-Qiang; Han, Qing-Yu; Yang, Xiu-Lan

    2016-10-01

    1. In China, Fructus Gardeniae was used as a traditional Chinese medicine (TCM) with a wide array of biological activities. The bioactive components identified in Fructus Gardeniae mainly included iridoids, flavonids, pigments, and so on. Among them, iridoids were regarded as important compounds in Fructus Gardeniae. Though analyses of the constituents in biological samples after oral administration of Fructus Gardeniae effective fraction or its active compounds have been reported, few efforts have been made to investigate the metabolic profile of Fructus Gardeniae in humans. In this study, the constituents and metabolites of Fructus Gardeniae in human blood and urine after oral administration of Fructus Gardeniae were investigated using ultra high-performance liquid chromatography (UHPLC) coupled with high-resolution LTQ-Orbitrap mass spectrometery. 2. Totally, 14 constituents (two parent compounds and 12 metabolites) of Fructus Gardeniae were identified in human plasma and urine either by comparing the retention time and mass spectrometry data with that of reference compounds or by the accurate high-resolution MS/MS data of the chemicals. The compounds identified were mainly iridoid glycosides such as geniposide and the derivatives of genipin-O-glucuronide. Among them, 11 metabolites were detected in human plasma and urine while the other three metabolites including geniposidic acid (M1), demethylation derivative of genipin-O-glucuronide (M2), and dehydration product of mono-hydroxylated genipin-O-glucuronide (M9) were only discovered in human urine. Further, the possible metabolic pathways of Fructus Gardeniae in vivo were proposed and the peak area-time curve of the most abundant metabolite genipin-O-glucuronide (M13) in human plasma after oral administration of Fructus Gardeniae was depicted. The results suggested that a metabolic difference existed between rats and humans. 3. The results obtained in the present research would provide basic information to

  2. Quantification of cyproheptadine in human plasma by high-performance liquid chromatography coupled to electrospray tandem mass spectrometry in a bioequivalence study.

    PubMed

    Mendes, Gustavo Duarte; Arruda, André; Chen, Lu Shi; de Almeida Magalhães, José Cássio; Alkharfy, Khalid M; De Nucci, Gilberto

    2012-01-01

    A rapid, sensitive and specific method to quantify cyproheptadine in human plasma using amitriptyline as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using a diethyl-ether/dichloromethane (70/30; v/v) solvent. After removing and drying the organic phase, the extracts were reconstituted with a fixed volume of acetonitrile/water (50/50 v/v)+0.1% of acetic acid. The extracts were analyzed by high performance liquid chromatography coupled to electrospray tandem mass spectrometry (LC-MS/MS). Chromatography was performed isocratically using an Alltech Prevail C18 5 µm analytical column, (150 mm x 4.6 mm I.D.). The method had a chromatographic run time of 4 min and a linear calibration curve ranging from 0.05 to 10 ng/mL (r2 > 0.99). The limit of quantification was 0.05 ng/mL. This HPLC/MS/MS procedure was used to assess the bioequivalence of cyproheptadine in two cyproheptadine + cobamamide (4 mg + 1 mg) tablet formulations (Cobactin® [cyproheptadine + cobamamide] test formulation supplied from Zambon Laboratórios Farmacêuticos Ltda. and Cobavital® from Solvay Farma (standard reference formulation)). A single 4 mg + 1 mg [cyproheptadine + cobamamide] dose of each formulation was administered to healthy volunteers. The study was conducted using an open, randomized, two-period crossover design with a 1-week washout interval. Since the 90% CI for Cmax and AUCs ratios were all within the 80-125% bioequivalence limit proposed by the US Food and Drug Administration, it was concluded that the cyproheptadine test formulation (Cobactin®) is bioequivalent to the Cobavital® formulation for both the rate and the extent of absorption of cyproheptadine.

  3. Determination of Cd, Cr, Hg and Pb in plastics from waste electrical and electronic equipment by inductively coupled plasma mass spectrometry with collision-reaction interface technology.

    PubMed

    Santos, Mirian C; Nóbrega, Joaquim A; Cadore, Solange

    2011-06-15

    A procedure based on the use of a quadrupole inductively coupled plasma-mass spectrometer equipped with a collision-reaction interface (CRI) for control of spectral overlap interferences was developed for simultaneous determination of Cd, Cr, Hg, and Pb in plastics from waste electrical and electronic equipment (WEEE). The injection of H(2) and He (80 and 60 mL min(-1), respectively) into the sampled plasma, colliding and reacting with potentially interfering polyatomic ions, allows interference-free determination of chromium via its isotopes (52)Cr and (53)Cr that are freed from overlap due to the occurrence of (40)Ar(12)C(+), (40)Ar(12)C(1)H(+), (36)S(16)O(+) or (1)H(36)S(16)O(+). Cadmium, Hg and Pb were directly determined via their isotopes (110)Cd, (111)Cd, (112)Cd, (199)Hg, (200)Hg, (201)Hg, (202)Hg, (206)Pb, (207)Pb, and (208)Pb, without using CRI. The CRI can be quickly activated or deactivated before each analyte measurement. Limits of detection for (52)Cr were 0.04 or 0.14 μg L(-1) with He or H(2) injected in CRI. Cadmium and Pb have LODs between 0.02 and 0.08 μg L(-1) and Hg had 0.93-0.98 μg L(-1), without using CRI. Analyte concentrations for samples varied from 16 to 43, 1 to 11, 4 to 12, and 5 to 13 mg kg(-1) for Cr, Cd, Hg and Pb, respectively.

  4. Isotope ratio analysis of lead in blood and environmental samples by multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Takagi, Mai; Yoshinaga, Jun; Tanaka, Atsushi; Seyama, Haruhiko

    2011-01-01

    It is widely recognized that lead (Pb) affects children's cognitive function, even at relatively low blood lead levels (<10 µg dL(-1)). The determination of the source of Pb in children is essential for effective risk management. The use of multi-collector ICPMS (MC-ICPMS) for isotope ratio measurements of Pb in environmental and biological samples was examined for this purpose. MC-ICPMS with an instrumental mass fractionation correction by Tl allowed accurate isotope ratio measurements of the Pb isotopic reference material NIST SRM 981. However, the presence of matrix elements (Al, Ca, Fe and Na) at more than 10 mg kg(-1) in the sample solution significantly deteriorated the accuracy. The separation of Pb from the matrix is necessary for accurate measurements of the isotope ratio of Pb in environmental and biological samples. Bromide-complexation, followed by anion exchange was found to be satisfactory in terms of the recovery of Pb (90 to 104%) and the efficiency of matrix separation. The procedure was applied to a preliminary source analysis of Pb in the blood of Japanese children, and a significant contribution of indoor dust was demonstrated.

  5. Study of the size-based environmental availability of metals associated to natural organic matter by stable isotope exchange and quadrupole inductively coupled plasma mass spectrometry coupled to asymmetrical flow field flow fractionation.

    PubMed

    Laborda, F; Ruiz-Beguería, S; Bolea, E; Castillo, J R

    2011-07-01

    The determination of the isotopically exchangeable fraction of metals in environmental solid samples (soils, composts, sediments, sludges, etc.) is used to know the amount of metal potentially available (E-value). Stable isotopes can be used for determination of E-values through the analysis of the aqueous phases from spiked suspensions. However, the presence of isotopically non-exchangeable metal forms in the aqueous phase led to overestimation of the E-values. In this paper, a method for monitoring the degree of isotopic exchange in function of the molecular mass and/or size of the metal form has been developed based on the direct coupling of asymmetrical flow field flow fractionation (AsFlFFF) with inductively coupled plasma mass spectrometry (ICP-MS) for on-line isotope ratio measurements. ICP-MS data acquisition parameters were stressed to avoid degradation of isotope ratio precision. Two sets of fractionation conditions were selected: a colloids separation, which allowed the separation of substances up to 1 μm, and a macromolecules separation, designed to resolve small size substances up to 50 kDa. The methodology was applied to study the environmental availability of copper and lead in compost samples, where metals are mainly associated to different forms of organic matter. No significant differences on isotopic exchange were observed over the size range studied, validating the E-values determined by direct analysis of the aqueous phases.

  6. Forensic discrimination of blue ballpoint pens on documents by laser ablation inductively coupled plasma mass spectrometry and multivariate analysis.

    PubMed

    Alamilla, Francisco; Calcerrada, Matías; García-Ruiz, Carmen; Torre, Mercedes

    2013-05-10

    The differentiation of blue ballpoint pen inks written on documents through an LA-ICP-MS methodology is proposed. Small common office paper portions containing ink strokes from 21 blue pens of known origin were cut and measured without any sample preparation. In a first step, Mg, Ca and Sr were proposed as internal standards (ISs) and used in order to normalize elemental intensities and subtract background signals from the paper. Then, specific criteria were designed and employed to identify target elements (Li, V, Mn, Co, Ni, Cu, Zn, Zr, Sn, W and Pb) which resulted independent of the IS chosen in a 98% of the cases and allowed a qualitative clustering of the samples. In a second step, an elemental-related ratio (ink ratio) based on the targets previously identified was used to obtain mass independent intensities and perform pairwise comparisons by means of multivariate statistical analyses (MANOVA, Tukey's HSD and T2 Hotelling). This treatment improved the discrimination power (DP) and provided objective results, achieving a complete differentiation among different brands and a partial differentiation within pen inks from the same brands. The designed data treatment, together with the use of multivariate statistical tools, represents an easy and useful tool for differentiating among blue ballpoint pen inks, with hardly sample destruction and without the need for methodological calibrations, being its use potentially advantageous from a forensic-practice standpoint. To test the procedure, it was applied to analyze real handwritten questioned contracts, previously studied by the Department of Forensic Document Exams of the Criminalistics Service of Civil Guard (Spain). The results showed that all questioned ink entries were clustered in the same group, being those different from the remaining ink on the document. PMID:23597731

  7. Evaluation of microwave and ultrasound extraction procedures for arsenic speciation in bivalve mollusks by liquid chromatography-inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Santos, Clarissa M. M.; Nunes, Matheus A. G.; Barbosa, Isa S.; Santos, Gabriel L.; Peso-Aguiar, Marlene C.; Korn, Maria G. A.; Flores, Erico M. M.; Dressler, Valderi L.

    2013-08-01

    Liquid chromatography-inductively coupled plasma-mass spectrometry (LC-ICP-MS) was used for arsenic speciation analysis in tissues of bivalve mollusks (Anomalocardia brasiliana sp. and Macoma constricta sp.). Microwave and ultrasound radiation, combined with different extraction conditions (solvent, sample amount, time, and temperature), were evaluated for As-species extraction from the mollusks' tissues. Accuracy, extraction efficiency, and the stability of As species were evaluated by analyzing certified reference materials (DORM-2, dogfish muscle; BCR-627, tuna fish tissue; and SRM 1566b, oyster tissue) and analyte recovery tests. The best conditions were found to be microwave-assisted extraction using 200 mg of samples and water at 80 °C for 6 min. The agreement of As-species concentration in samples ranged from 97% to 102%. Arsenobetaine (AsB) was the main species present in bivalve mollusk tissues, while monomethylarsonic acid (MMA) and arsenate (As(V)) were below the limit of quantification (0.001 and 0.003 μg g- 1, respectively). Two unidentified As species also were detected and quantified. The sum of the As-species concentration was in agreement (90 to 104%), with the total As content determined by ICP-MS after sample digestion.

  8. Mercury speciation analysis in sea water by solid phase microextraction?gas chromatography?inductively coupled plasma mass spectrometry using ethyl and propyl derivatization. Matrix effects evaluation

    NASA Astrophysics Data System (ADS)

    Bravo-Sánchez, Luis R.; Ruiz Encinar, Jorge; Fidalgo Martínez, José I.; Sanz-Medel, Alfredo

    2004-01-01

    An approach to the speciation analysis of mercury in sea-water samples at sub-ppt levels by means of the hyphenation of solid phase microextraction to gas chromatography-inductively coupled plasma mass spectrometry was developed. Blank values turned out to be the limiting factor for lower detection limits of inorganic mercury. Thus, all the reagents were thoroughly cleaned using laboratory made microcolumns packed with 8-hydroxyquinoline on TSK gel. Sodium tetrapropylborate (NaBPr 4) synthesized for the purpose of derivatization of the mercury species resulted in better analytical performances of the method, probably due to lower mercury contamination, than commercial sodium tetraethylborate (NaBEt 4). Detection limits down to a few picogram per liter for both mercury and methylmercury were obtained using NaBPr 4. The high salt content of sea-water samples was responsible for strong matrix effects, which were overcome by using standards additions to the samples. The validation of the methodology was carried out by direct comparison of the results for inorganic mercury with those obtained using a flow injection system followed by preconcentration/trapping of the species and its detection by atomic absorption spectrometry. The proposed method was applied to the determination of mercury and methylmercury in coastal sea-water samples from Gijón (Asturias, Spain) and results obtained are discussed in the light of the butyltin levels previously determined in the same area.

  9. Multivariate classification of edible salts: Simultaneous Laser-Induced Breakdown Spectroscopy and Laser-Ablation Inductively Coupled Plasma Mass Spectrometry Analysis

    NASA Astrophysics Data System (ADS)

    Lee, Yonghoon; Nam, Sang-Ho; Ham, Kyung-Sik; Gonzalez, Jhanis; Oropeza, Dayana; Quarles, Derrick; Yoo, Jonghyun; Russo, Richard E.

    2016-04-01

    Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), both based on laser ablation sampling, can be employed simultaneously to obtain different chemical fingerprints from a sample. We demonstrated that this analysis approach can provide complementary information for improved classification of edible salts. LIBS could detect several of the minor metallic elements along with Na and Cl, while LA-ICP-MS spectra were used to measure non-metallic and trace heavy metal elements. Principal component analysis using LIBS and LA-ICP-MS spectra showed that their major spectral variations classified the sample salts in different ways. Three classification models were developed by using partial least squares-discriminant analysis based on the LIBS, LA-ICP-MS, and their fused data. From the cross-validation performances and confusion matrices of these models, the minor metallic elements (Mg, Ca, and K) detected by LIBS and the non-metallic (I) and trace heavy metal (Ba, W, and Pb) elements detected by LA-ICP-MS provided complementary chemical information to distinguish particular salt samples.

  10. Evaluation of Dietary Supplement Contamination by Xenobiotic and Essential Elements Using Microwave-Enhanced Sample Digestion and Inductively Coupled Plasma-Mass Spectrometry.

    PubMed

    Zinn, Gregory M; Rahman, G M Mizanur; Faber, Scott; Wolle, Mesay Mulugeta; Pamuku, Matt; Kingston, H M Skip

    2016-01-01

    Dietary supplements were analyzed by evaluating the elemental content in six widely consumed products manufactured by four well-known companies. The elements included the neurotoxic and carcinogenic elements cadmium, mercury, aluminum, lead, arsenic, and antimony, as well as the essential elements zinc, selenium, chromium, iron, and copper, which were often not listed as ingredients on the product labels. Contamination from either xenobiotic or essential elements was found in all samples analyzed. The samples were prepared using US Environmental Protection Agency (EPA) Method 3052, microwave-enhanced digestion. The resulting digests were analyzed by Inductively Coupled Plasma-Mass Spectrometry based on EPA Method 6020B. The analytical protocols were validated by analyzing a multivitamin standard reference material, the National Institute of Standards and Technology Standard Reference Material 3280. The application of EPA standard methods demonstrated their utility in making accurate and precise measurements in complex matrices with multiple ingredients and excipients. In the future, the use of these methods could provide a uniform quality assurance protocol that can be implemented along with other industry guidelines to improve the production of dietary supplements.

  11. Determination of Os by isotope dilution-inductively coupled plasma-mass spectrometry with the combination of laser ablation to introduce chemically separated geological samples

    NASA Astrophysics Data System (ADS)

    Sun, Yali; Ren, Minghao; Xia, Xiaoping; Li, Congying; Sun, Weidong

    2015-11-01

    A method was developed for the determination of trace Os in geological samples by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) with the combination of chemical separation and preconcentration. Samples are digested using aqua regia in Carius tubes, and the Os analyte is converted into volatile OsO4, which is distilled and absorbed with HBr. The HBr solution is concentrated for further Os purification using the microdistillation technique. The purified Os is dissolved in 10 μl of 0.02% sucrose-0.005% H3PO4 solution and then evaporated on pieces of perfluoroalkoxy (PFA) film, resulting in the formation of a tiny object (< 3 × 104 μm2 superficial area). Using LA-ICP-MS measurements, the object can give Os signals at least 100 times higher than those provided by routine solution-ICP-MS while successfully avoiding the memory effect. The procedural blank and detection limit in the developed technique are 3.0 pg and 1.8 pg for Os, respectively when 1 g of samples is taken. Reference materials (RM) are analyzed, and their Os concentrations obtained by isotope dilution are comparable to reference or literature values. Based on the individual RM results, the precision is estimated within the range of 0.6 to 9.4% relative standard deviation (RSD), revealing that this method is applicable to the determination of trace Os in geological samples.

  12. A comparison of continuous pneumatic nebulization and flow injection-direction injection nebulization for sample introduction in inductively coupled plasma-mass spectrometry

    SciTech Connect

    Crain, J.S.; Kiely, J.T.

    1997-08-01

    Samples containing Ni, Cd, Pb, and U were analyzed eighteen times over a two-month period using inductively coupled plasma-mass spectrometry (ICP-MS). Sample introduction was accomplished by either flow injection-direct injection nebulization (FI-DIN) or continuous pneumatic nebulization (CPN). Using comparable instrumental measurement procedures, FI-DIN analyses were 33% faster and generated 52% less waste than CPN analyses. Instrumental limits of detection obtained with FI-DIN and CPN were comparable but not equivalent (except in the case of Pb) because of nebulizer-related differences in sensitivity (i.e., signal per unit analyte concentration) and background. Substantial and statistically significant differences were found between FI-DIN and CPN Ni determinations, and in the case of laboratory waste samples, there were also small but statistically significant differences between Cd determinations. These small (2 to 3%) differences were not related to polyatomic ion interference (e.g., {sup 95}Mo{sup 16}O{sup +}), but in light of the time and waste savings to be realized, they should not preclude the use of FI-DIN in place of CPN for determination of Cd, Pb, U, and similar elements present at trace concentrations.

  13. Analysis of Cu, Co, V and Zn in coastal waters of the East China Sea by inductively coupled plasma mass spectrometry (ICP-MS)

    NASA Astrophysics Data System (ADS)

    Yang, Rujun; Ning, Yutong; Zhang, Aibin; Li, Yan; Su, Han

    2016-10-01

    In this study, a simple method for the simultaneous determination of trace metals (Cu, V, Co, Zn) in coastal seawater using the Mg(OH)2 coprecipitation inductively coupled plasma mass spectrometry (ICP-MS) was developed. This multi-element method enables the simultaneous extraction of four metals, particularly Co and V. The recoveries of Cu, Co, V and Zn after Mg(OH)2 coprecipitation were 73%, 96%, 94% and 92%, which means that our procedure was well-suited to the determination of these four trace metals. The detection limits were 3.81, 0.18, 6.09 and 1.91 nmol L-1, respectively. Then, applying this method to the simultaneous determination of these four metals in coastal water samples from the East China Sea revealed that the concentrations of Cu, Zn, Co and V were higher in bottom waters compared to water at other depths, and higher concentrations were generally observed at the Yangtze River estuary. Additionally, example vertical profiles of dissolved trace metal concentrations for the East China Sea in spring and autumn are compared. These findings indicate that Zn had the greatest seasonal variation followed by Cu, V and Co. For Zn and Co, the concentrations were higher during spring than during autumn. For Cu and V, the seasonal variation in the concentrations was opposite.

  14. Trace element analysis of synthetic mono- and poly-crystalline CaF 2 by ultraviolet laser ablation inductively coupled plasma mass spectrometry at 266 and 193 nm

    NASA Astrophysics Data System (ADS)

    Koch, J.; Feldmann, I.; Hattendorf, B.; Günther, D.; Engel, U.; Jakubowski, N.; Bolshov, M.; Niemax, K.; Hergenröder, R.

    2002-06-01

    The analytical figures of merit for ultraviolet laser ablation-inductively coupled plasma mass spectrometry (UV-LA-ICP-MS) at 266 nm with respect to the trace element analysis of high-purity, UV-transmitting alkaline earth halides are investigated and discussed. Ablation threshold energy density values and ablation rates for mono- and poly-crystalline CaF 2 samples were determined. Furthermore, Pb-, Rb-, Sr-, Ba- and Yb-specific analysis was performed. For these purposes, a pulsed Nd:YAG laser operated at the fourth harmonic of the fundamental wavelength (λ=266 nm) and a double-focusing sector field ICP-MS detector were employed. Depending on the background noise and isotope-specific sensitivity, the detection limits typically varied from 0.7 ng/g for Sr to 7 ng/g in the case of Pb. The concentrations were determined using a glass standard reference material (SRM NIST612). In order to demonstrate the sensitivity of the arrangement described, comparative measurements by means of a commercial ablation system consisting of an ArF excimer laser (λ=193 nm) and a quadrupole-type ICP-MS (ICP-QMS) instrument were carried out. The accuracy of both analyses was in good agreement, whereas ablation at 266 nm and detection using sector-field ICP-MS led to a sensitivity that was one order of magnitude above that obtained at 193 nm with ICP-QMS.

  15. Measurement of vanadium, nickel, and arsenic in seawater and urine reference materials by inductively coupled plasma mass spectrometry with cryogenic desolvation

    SciTech Connect

    Alves, L.C.; Allen, L.A.; Houk, R.S. Iowa State Univ., Ames, IA )

    1993-09-15

    Addition of a small dose (2%) of H[sub 2] to the aerosol gas flow enhanced analyte signals by a factor of 2-3, which compensated for the loss of analyte signal that accompanied earlier efforts at cryogenic desolvation with inductively coupled plasma mass spectrometry (ICP-MS). Vanadium, nickel, and arsenic at microgram per liter levels in urine, river, and seawater reference materials were determined. The polyatomic ions ClO[sup +], CaO[sup +], and ArCl[sup +], which normally cause severe overlap interferences for these elements, were attenuated to manageable levels by cryogenic desolvation. The samples were simply diluted with 1% HNO[sub 2] so that the chloride could be removed as HCl. The analytical results obtained for these standard reference materials agreed closely with the certified or recommended values. The detection limit ranges (3[sigma]) obtained were 10-1000 ng L[sup [minus]1] for V, 0.03-20 [mu]g L[sup [minus]1] for Ni, and 4-7000 ng L[sup [minus]1] for As in the original samples. The samples were introduced by flow injection to minimize clogging of the sampling orifice. 29 refs., 2 figs., 5 tabs.

  16. Diverse accumulation and distribution of nutrient elements in developing wheat grain studied by laser ablation inductively coupled plasma mass spectrometry imaging.

    PubMed

    Wu, Bei; Andersch, Franka; Weschke, Winfriede; Weber, Hans; Becker, J Sabine

    2013-09-01

    The present study focused on the elemental distribution in the developing wheat grain by using the laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) imaging technique. Our studies show that the embryo accumulated high concentrations of nutrient elements, such as Fe, K, Cu, and Zn, while Ca was accumulated in the bran of the wheat grain which might be attributed to its function of structural maintenance. In the endosperm the majority of the nutrients were located in the aleurone layer. Within the grain, the embryo could be considered as a nutrient pool for macro- and micro-elements essential for the development of the seedling. Elemental images showed that considerable amounts of nutrients were stored in the scutellum of the embryo, which might be related to the high gene expression of element transporters in the scutellum. Root primordia and leaf primordia were enriched in particular elements, such as Mn and Zn respectively. In total 34 cross sections were analyzed and used for generation of a sequence of elemental distribution images to demonstrate elemental changes along the perpendicular axis of the wheat grain embryo. Further development of three-dimensional modeling will be combined with physiological studies to better understand the mechanisms of elemental distribution and storage in the wheat grain. These studies will provide fundamental knowledge on improving the nutritional value and agronomic practices.

  17. Single-step solubilization of milk samples with N,N-dimethylformamide for inductively coupled plasma-mass spectrometry analysis and classification based on their elemental composition.

    PubMed

    Azcarate, Silvana M; Savio, Marianela; Smichowski, Patricia; Martinez, Luis D; Camiña, José M; Gil, Raúl A

    2015-10-01

    A single-step procedure for trace elements analysis of milk samples is presented. Solubilization with small amounts of dymethylformamide (DMF) was assayed prior to inductively coupled plasma mass spectrometry (ICPMS) detection with a high efficiency sample introduction system. All main instrumental conditions were optimized in order to readily introduce the samples without matrix elimination. In order to assess and mitigate matrix effects in the determination of As, Cd, Co, Cu, Eu, Ga, Gd, Ge, Mn, Mo, Nb, Nd, Ni, Pb, Pr, Rb, Sm, S, Sr, Ta, Tb, V, Zn, and Zr, matrix matching calibration with (103)Rh as internal standard (IS) was performed. The obtained limits of detection were between 0.68 (Tb) and 30 (Zn) μg L(-1). For accuracy verification, certified Skim milk powder reference material (BCR 063R) was employed. The developed method was applied to trace elements analysis of commercially available milks. Principal components analysis was used to correlate the content of trace metals with the kind of milk, obtaining a classification according to adults, baby or baby fortified milks. The outcomes highlight a simple and fast approach that could be trustworthy for routine analysis, quality control and traceability of milks. PMID:26078129

  18. Speciation analysis of tellurium by solid-phase extraction in the presence of ammonium pyrrolidine dithiocarbamate and inductively coupled plasma mass spectrometry.

    PubMed

    Yu, Chunhai; Cai, Qiantao; Guo, Zhong-Xian; Yang, Zhaoguang; Khoo, Soo Beng

    2003-05-01

    Under acidic conditions tellurium(IV) formed a complex with ammonium pyrrolidine dithiocarbamate (APDC). The tellurium(IV) complex was completely retained on a non-polar Isolute silica-based octadecyl (C(18)) sorbent-containing solid-phase extraction (SPE) cartridge, while the uncomplexed Te(VI) passed through the cartridge and remained as a free species in the solution. Only partial Te(IV) was retained on the SPE cartridge for samples without addition of APDC. On the basis of different retention behaviours of the complexed Te(IV) and uncomplexed Te(VI), a simple and highly sensitive method is proposed for the determination of total tellurium and Te(VI) by SPE separation and inductively coupled plasma mass spectrometry (ICP-MS) detection. The Te(IV) concentration was calculated as the difference between total tellurium and Te(VI) concentrations. The detection limit (3 sigma) is 3 ng L(-1) tellurium. Factors affecting the separation and detection of tellurium species were investigated. Coexisting ions did not show significant interferences with the Te(IV)-APDC complex retention and the subsequent ICP-MS detection of Te. The method has been successfully applied to the tellurium speciation analysis in waters with spiked recoveries for Te(IV) and Te(VI) of 86.0-108% and 87.1-97.4%, respectively.

  19. Separation and characterization of metallothionein in the liver of sea turtles by high performance liquid chromatographylinductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Shinsuke, T.; Yasumi, A.; Takashi, K.

    2003-05-01

    To investigate whether trace metals bind to metallothioneins (MTs) in the hepatocytosol of green turtles (Chelonia mydas) and hawksbill turtles (Eretmochelys imbricata), MT fraction was obtained by ultracentrifugation and gel filtration methods. MTs separated from hepatocytosol were further purified and characterized by high performance liquid chromatography/inductively coupled plasma-mass spectrometry. In addition, the involvement of MTs in the accumulation of trace metals in the liver of sea turtle was examine. Gel filtration analysis showed that significant amounts of Cu, Zn, Ag and Cd were bound to MT in the cytosol of sea turtles, suggesting that such trace metals were primarily detoxified by interaction with MTs in the liver. Elution profiles of these trace metals by anion-exchange chromatography were different between green turtles and hawksbill turtles. These results suggest the presence of multiple isoforms of MT in the liver of both sea turtles; however, constituents of isoforms were different between green and hawksbill turtles. In both species, we observed the elevation of the height of a specific peak in elution profile with an increase in Cu concentration in hepatocytosol. This result suggests the presence of a novel MT isoform related to copper accumulation in the liver of sea turtles.

  20. A high-throughput solid-phase extraction microchip combined with inductively coupled plasma-mass spectrometry for rapid determination of trace heavy metals in natural water.

    PubMed

    Shih, Tsung-Ting; Hsieh, Cheng-Chuan; Luo, Yu-Ting; Su, Yi-An; Chen, Ping-Hung; Chuang, Yu-Chen; Sun, Yuh-Chang

    2016-04-15

    Herein, a hyphenated system combining a high-throughput solid-phase extraction (htSPE) microchip with inductively coupled plasma-mass spectrometry (ICP-MS) for rapid determination of trace heavy metals was developed. Rather than performing multiple analyses in parallel for the enhancement of analytical throughput, we improved the processing speed for individual samples by increasing the operation flow rate during SPE procedures. To this end, an innovative device combining a micromixer and a multi-channeled extraction unit was designed. Furthermore, a programmable valve manifold was used to interface the developed microchip and ICP-MS instrumentation in order to fully automate the system, leading to a dramatic reduction in operation time and human error. Under the optimized operation conditions for the established system, detection limits of 1.64-42.54 ng L(-1) for the analyte ions were achieved. Validation procedures demonstrated that the developed method could be satisfactorily applied to the determination of trace heavy metals in natural water. Each analysis could be readily accomplished within just 186 s using the established system. This represents, to the best of our knowledge, an unprecedented speed for the analysis of trace heavy metal ions. PMID:27016435

  1. Speciation and determination of bioavailable arsenic species in soil samples by one-step solvent extraction and high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

    PubMed

    Sun, Jing; Ma, Li; Yang, Zhaoguang; Lee, Hsiaowan; Wang, Lin

    2015-03-01

    A new analytical method was developed to determine the bioavailable arsenic species (arsenite, arsenate, monomethylarsonic acid, and dimethylarsonic acid) in soil samples using high-performance liquid chromatography with inductively coupled plasma mass spectrometry. Bioavailable arsenic was extracted with ammonium phosphate buffer by a simplified one-step solvent extraction procedure. To estimate the effect of variables on arsenic extraction, a two-level Plackett-Burman factorial design was conducted to screen the significant factors that were further investigated by a separate univariate approach. The optimum conditions were confirmed by compromising the stability of arsenic species and the extraction efficiency. The concentration of arsenic species was determined in method blank and soil-certified reference materials both spiked with standard solutions of arsenic species. All the target arsenic species were stable during the whole extraction procedure. Furthermore, the proposed method was applied to release bioavailable arsenic from contaminated soil samples, showing that the major arsenic species in soil samples were inorganic arsenic: arsenite and arsenate, of which the latter was dominant. PMID:25594186

  2. Determination of minor and trace elements in aromatic spices by micro-wave assisted digestion and inductively coupled plasma-mass spectrometry.

    PubMed

    Khan, Naeem; Choi, Ji Yeon; Nho, Eun Yeong; Jamila, Nargis; Habte, Girum; Hong, Joon Ho; Hwang, In Min; Kim, Kyong Su

    2014-09-01

    This study aimed at analyzing the concentrations of 23 minor and trace elements in aromatic spices by inductively coupled plasma-mass spectrometry (ICP-MS), after wet digestion by microwave system. The analytical method was validated by linearity, detection limits, precision, accuracy and recovery experiments, obtaining satisfactory values in all cases. Results indicated the presence of variable amounts of both minor and trace elements in the selected aromatic spices. Manganese was high in cinnamon (879.8 μg/g) followed by cardamom (758.1 μg/g) and clove (649.9 μg/g), strontium and zinc were high in ajwain (489.9 μg/g and 84.95 μg/g, respectively), while copper was high in mango powder (77.68 μg/g). On the whole some of the minor and essential trace elements were found to have good nutritional contribution in accordance to RDA. The levels of toxic trace elements, including As, Cd, and Pb were very low and did not found to pose any threat to consumers. PMID:24731332

  3. Study on quantitative analysis of Ti, Al and V in clinical soft tissues after placing the dental implants by laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Sajnóg, Adam; Hanć, Anetta; Makuch, Krzysztof; Koczorowski, Ryszard; Barałkiewicz, Danuta

    2016-11-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for in-situ quantitative analysis of oral mucosa of patients before and after implantation with titanium implants and a closing screw based on Ti6Al4V alloy. Two calibration strategies were applied, both were based on matrix matched solid standards with analytes addition. A novel approach was the application of powdered egg white proteins as a matrix material which have a similar composition to the examined tissue. In the another approach, certified reference material Bovine Muscle ERM-BB184 was used. The isotope 34S was found to be the most appropriate as an internal standard since it is homogenously distributed in the examined tissues and resulted in lower relative standard deviation values of signal of analytes of interest. Other isotopes (13C, 26Mg, 43Ca) were also evaluated as potential internal standards. The analytical performance parameters and microwave digestion of solid standards followed by solution nebulization ICP-MS analysis proved that both calibration methods are fit for their intended purpose. The LA-ICP-MS analysis on the surface of tissues after the implantation process revealed an elevated content of elements in comparison to the control group. Analytes are distributed inhomogeneously and display local maximal content of Ti up to ca. 900 μg g- 1, Al up to ca. 760 μg g- 1 and for V up to 160 μg g- 1.

  4. Determination of trace elements in medicinal activated charcoal using slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry with low vaporization temperature.

    PubMed

    Chen, Chien-Chou; Jiang, Shiuh-Jen; Sahayam, A C

    2015-01-01

    The determination of Cd, Sb, Te, Hg, Tl and Pb in medicinal activated charcoal by ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) was described. EDTA was used as the modifier to enhance the volatility of elements studied. The influences of instrument operating conditions and slurry preparation on the ion signals were studied. A relatively low vaporization temperature of 1000°C was used, which separated the analyte from the major matrix components that improved ion signals. The method has been applied to determine Cd, Sb, Te, Hg, Tl and Pb in an NIST SRM 1633b Coal Fly Ash reference material and three brands of medicinal activated charcoal capsules using isotope dilution and standard addition calibration methods. The concentrations that are in ng g(-1) levels were in good agreement between different calibration methods. The precision between sample replicates was better than 7% with USS-ETV-ICP-MS technique. The method detection limit estimated from standard addition curves was 0.4, 0.3, 0.3, 0.3, 0.04 and 0.9 ng g(-1) for Cd, Sb, Te, Hg, Tl and Pb, respectively, in original medicinal activated charcoal.

  5. Chemometric classification of gunshot residues based on energy dispersive X-ray microanalysis and inductively coupled plasma analysis with mass-spectrometric detection

    NASA Astrophysics Data System (ADS)

    Steffen, S.; Otto, M.; Niewoehner, L.; Barth, M.; Bro¿żek-Mucha, Z.; Biegstraaten, J.; Horváth, R.

    2007-09-01

    A gunshot residue sample that was collected from an object or a suspected person is automatically searched for gunshot residue relevant particles. Particle data (such as size, morphology, position on the sample for manual relocation, etc.) as well as the corresponding X-ray spectra and images are stored. According to these data, particles are classified by the analysis-software into different groups: 'gunshot residue characteristic', 'consistent with gunshot residue' and environmental particles, respectively. Potential gunshot residue particles are manually checked and - if necessary - confirmed by the operating forensic scientist. As there are continuing developments on the ammunition market worldwide, it becomes more and more difficult to assign a detected particle to a particular ammunition brand. As well, the differentiation towards environmental particles similar to gunshot residue is getting more complex. To keep external conditions unchanged, gunshot residue particles were collected using a specially designed shooting device for the test shots revealing defined shooting distances between the weapon's muzzle and the target. The data obtained as X-ray spectra of a number of particles (3000 per ammunition brand) were reduced by Fast Fourier Transformation and subjected to a chemometric evaluation by means of regularized discriminant analysis. In addition to the scanning electron microscopy in combination with energy dispersive X-ray microanalysis results, isotope ratio measurements based on inductively coupled plasma analysis with mass-spectrometric detection were carried out to provide a supplementary feature for an even lower risk of misclassification.

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

    PubMed

    Veyseh, Somayeh; Niazi, Ali

    2016-01-15

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

  7. Determination of traces of uranium and thorium in titanium and copper used for the construction of the Russian Emission Detector 100 by inductively coupled plasma mass spectrometry.

    PubMed

    Poteshin, Sergey S; Sysoev, Alexey A; Lagunov, Sergey S; Sereda, Andrei; Sosnovtsev, Valery V; Bolozdynya, Alexander I; Efremenko, Yuriy B

    2015-01-01

    The Russian Emission Detector 100 (RED-100) under construction at the National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) is designed to detect the presently undiscovered effect of coherent neutrino scattering. One of the factors limiting the sensitivity of the detector is the spontaneous decay of uranium and thorium in the detector materials. Radioactive impurities in detector materials at levels of parts per billion can significantly affect the sensitivity. Five random samples of titanium and one of copper from materials used in the construction of the detector were selected for assay. The concentration of (232)Th and (238)U were measured by inductively coupled plasma mass spectrometry (ICP- MS) in solid titanium using both: solutions in acids and direct sampling by laser ablation (LA-ICP-MS). The LA- ICP-MS method allowed us to determine (238)U and (232)Th at subnanogram per gram levels. This method is much faster than ICP-MS with liquid injection. The titanium samples studied have impurities in the range between 1 ng g(-1) and 21 ng g(-1) for (238)U and 3 ng g(-1) and 31 ng g(-1) for (232)Th. In copper we set upper limits of 0.4 ng g(-1) for (238)U and 1 ng g(-1)for (232)Th. The total activity of the cryostat constructed from materials studied was estimated to be 43 Bq.

  8. Validation of an optimized method for the determination of iodine in human breast milk by inductively coupled plasma mass spectrometry (ICPMS) after tetramethylammonium hydroxide extraction.

    PubMed

    Huynh, Dao; Zhou, Shao Jia; Gibson, Robert; Palmer, Lyndon; Muhlhausler, Beverly

    2015-01-01

    In this study a novel method to determine iodine concentrations in human breast milk was developed and validated. The iodine was analyzed by inductively coupled plasma mass spectrometry (ICPMS) following tetramethylammonium hydroxide (TMAH) extraction at 90°C in disposable polypropylene tubes. While similar approaches have been used previously, this method adopted a shorter extraction time (1h vs. 3h) and used antimony (Sb) as the internal standard, which exhibited greater stability in breast milk and milk powder matrices compared to tellurium (Te). Method validation included: defining iodine linearity up to 200μgL(-1); confirming recovery of iodine from NIST 1549 milk powder. A recovery of 94-98% was also achieved for the NIST 1549 milk powder and human breast milk samples spiked with sodium iodide and thyroxine (T4) solutions. The method quantitation limit (MQL) for human breast milk was 1.6μgL(-1). The intra-assay and inter-assay coefficient of variation for the breast milk samples and NIST powder were <1% and <3.5%, respectively. NIST 1549 milk powder, human breast milk samples and calibration standards spiked with the internal standard were all stable for at least 2.5 months after extraction. The results of the validation process confirmed that this newly developed method provides greater accuracy and precision in the assessment of iodine concentrations in human breast milk than previous methods and therefore offers a more reliable approach for assessing iodine concentrations in human breast milk.

  9. Gold nanoparticles labeling with hybridization chain reaction amplification strategy for the sensitive detection of HepG2 cells by inductively coupled plasma mass spectrometry.

    PubMed

    Zhang, Xing; Chen, Beibei; He, Man; Wang, Han; Hu, Bin

    2016-12-15

    Sensitive detection of circulating tumor cells (CTCs) is of great significance in the early detection of cancer and cancer metastasis. This work reported an efficient, specific, and sensitive immunoassay protocol for detection of tumor cells by using inductively coupled plasma mass spectrometry (ICP-MS) with gold nanoparticles (AuNPs) labeling and hybridization chain reaction (HCR) amplification. In the established approach, antibodies against epithelial cell adhesion molecule (anti-EpCAM) conjugated magnetic beads (MBs) were used for selective capture of tumor cells from peripheral blood, aptamer was applied for the recognition of captured tumor cells, and AuNPs labeled DNA concatamer was used as the signal probe for tumor cell labeling and ICP-MS detection. Due to the dual amplification effect of AuNPs and HCR, the limit of detection of this ICP-MS based method for HepG2 cells was as low as 15 cells, and the linear range was 40-8000 cells with the relative standard deviation for seven replicate detections of 200 HepG2 cells was 8.7%. Furthermore, the applicability of the method for the analysis of peripheral blood samples was demonstrated by the spiking tests. The established method was highly specific and sensitive for the detection of HepG2 cells, and has a good application potential in clinical diagnosis.

  10. Study on the in vivo toxic mechanism of xixin based on trace elements determination by inductively coupled plasma-mass spectrometry

    PubMed Central

    Yong-Rui, Bao; Xin-Xin, Yang; Shuai, Wang; Xian-Sheng, Meng; Rui-Qing, Zhu; Yue-Ming, Xia; Lin, Cai

    2014-01-01

    Background: Xixin has been widely used as a traditional Chinese medicine for headache, toothache and inflammatory diseases. Clinical investigation indicated that adverse drug reactions occurred with an overdose of xixin, but the toxic mechanism of xixin in vivo based on trace elements has not been researched yet. Objective: To explore the in vivo toxic mechanism of xixin induced by trace elements. Materials and Methods: The contents of trace elements in the serum and liver of mice were determined by inductively coupled plasma-mass spectrometry (ICP-MS) after obtaining xixin extracts. Principal component analysis (PCA) and cluster analysis (CA) were performed between the trace elements’ content and dosage using the software GeneSpring 12.1 to analyze the main toxic elements in vivo. Results: Trace elements’ contents were obviously raised after xixin extracts were taken as a dosage of 150 mg/mL and 50 mg/mL, respectively. Na, Ca, Cu and Cd in serum and Ca and Zn in liver were the main trace elements inducing the toxic reaction of xixin. Conclusion: Xixin possesses the potential function of indirectly upregulating trace elements in vivo. This study, for the first time, elucidated the in vivo toxic mechanism of xixin based on trace elements. This method could also be utilized in the research of corresponding aspects. PMID:24914279

  11. Arsenic Species in Edible Seaweeds Using In Vitro Biomimetic Digestion Determined by High-Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Zhao, Yan-Fang; Wu, Ji-Fa; Shang, De-Rong; Ning, Jin-Song; Ding, Hai-Yan; Zhai, Yu-Xiu

    2014-01-01

    Arsenite [As (III)], arsenate [As (V)], methylarsonate (MMA), and dimethylarsinate (DMA) in five edible seaweeds (the brown algae Laminaria japonica, red algae Porphyra yezoensis, brown algae Undaria pinnatifida, brown algae Hizikia fusiformis, and green algae Enteromorpha prolifera) were analyzed using in vitro digestion method determined by high-performance liquid chromatography inductively coupled plasma mass spectrometry. The results showed that DMA was found in the water extracts of all samples; As (III) were detected in L. japonica and U. pinnatifida and about 23.0 and 0.15 mg/kg of As (V) were found in H. fusiformis and E. prolifera respectively. However, after the gastrointestinal digestion, As (V) was not detected in any of the five seaweeds. About 0.19 and 1.47 mg/kg of As (III) was detected in the gastric extracts of L. japonica and H. fusiformis, respectively, and about 0.31 and 0.10 mg/kg of As (III) were extracted from the intestinal extracts of Porphyra yezoensis and U. pinnatifida, respectively. The present results successfully reveal the differences of As species and levels in the water and biomimetic extracts of five edible seaweeds. The risk assessment of the inorganic arsenic in the five edible seaweeds based on present data showed almost no hazards to human health. PMID:26904630

  12. Quantitative imaging of platinum based on laser ablation-inductively coupled plasma-mass spectrometry to investigate toxic side effects of cisplatin.

    PubMed

    Köppen, C; Reifschneider, O; Castanheira, I; Sperling, M; Karst, U; Ciarimboli, G

    2015-12-01

    This work presents a quantitative bioimaging method for platinum based on laser ablation-inductively coupled plasma-mass spectrometry and its application for a biomedical study concerning toxic side effects of cisplatin. To trace the histopathology back to cisplatin, platinum was localized and quantified in major functional units of testicle, cochlea, kidney, nerve and brain sections from cisplatin treated mice. The direct consideration of the histology enables precise interpretation of the Pt images and the novel quantitative evaluation approach allows significantly more precise investigations than the pure image. For the first time, platinum was detected and quantified in all major injured structures including organ of Corti of cochlea and seminiferous tubule of testicle. In this way, proximal tubule in kidney, Leydig cells in testicle, stria vascularis and organ of Corti in cochlea and nerve fibers in sciatic nerves are confirmed as targets of cisplatin in these organs. However, the accumulation of platinum in almost all investigated structures also raises questions about more complex pathogenesis including direct and indirect interruption of several biological processes.

  13. Microwave-assisted Extraction of Rare Earth Elements from Petroleum Refining Catalysts and Ambient Fine Aerosols Prior to Inductively Coupled Plasma - Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, David W.; Kulkarni, Pranav; Chellam, Shankar

    2006-01-01

    In the absence of a certified reference material, a robust microwave-assisted acid digestion procedure followed by inductively coupled plasma - mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM2.5). High temperature (200 C), high pressure (200 psig), acid digestion (HNO3, HF, and H3BO3) with 20 minute dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst, and PM2.5. This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb, and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy, and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using 115In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu, and Dy in ambient PM2.5 in an industrial area of Houston, TX.

  14. Sensitive determination of thallium species in drinking and natural water by ionic liquid-assisted ion-pairing liquid-liquid microextraction and inductively coupled plasma mass spectrometry.

    PubMed

    Escudero, Leticia B; Wuilloud, Rodolfo G; Olsina, Roberto A

    2013-01-15

    A fast and simple method involving separation and determination of thallium (Tl) species, based on novel ionic liquid-assisted ion pairing dispersive liquid-liquid microextraction (DLLME) method, was developed. Initially, Tl(III) was selectively complexed with chloride ion to form [TlCl(4)](-) chlorocomplex. Subsequently, tetradecyl(trihexyl)phosphonium chloride ionic liquid (CYPHOS(®) IL 101) was used to form the ion-pair with [TlCl(4)](-) anion followed by extraction. The DLLME procedure was developed by dispersing 80 μL of carbon tetrachloride with 100 μL of ethanol added to the aqueous solution. After DLLME, the upper aqueous phase containing Tl(I) only was removed and analysed by inductively coupled plasma-mass spectrometry (ICP-MS). In contrast to Tl(III), Tl(I) species does not form neither stable nor anionic complexes with chloride ions and it was not extracted into the organic phase. Total Tl concentration was obtained by direct introduction of sample into ICP-MS instrument. The calibration graph for the analyte was linear with a correlation coefficient of 0.9989. Under optimal conditions, detection limit of Tl species was 0.4 ng L(-1). The relative standard deviation (n=10) at 1 ng mL(-1) Tl concentration level was 1.3% for Tl(I) and 1.5% for Tl(III). The method was successfully applied for fast speciation analysis of Tl at ultratrace levels in real water samples.

  15. Simultaneous determination of arsenic and mercury species in rice by ion-pairing reversed phase chromatography with inductively coupled plasma mass spectrometry.

    PubMed

    Fang, Yong; Pan, Yushi; Li, Peng; Xue, Mei; Pei, Fei; Yang, Wenjian; Ma, Ning; Hu, Qiuhui

    2016-12-15

    An analytical method using reversed phase chromatography-inductively coupled plasma mass spectrometry for arsenic and mercury speciation analysis was described. The effect of ion-pairing reagent on simultaneous separation of four arsenic (arsenite, arsenate, monomethlyarsonate and dimethylarsinate) and three mercury species (inorganic mercury (Hg(II)), methylmecury and ethylmercury) was investigated. Parameters including concentrations and pH of the mobile phase were optimized. The separation and re-equilibration time was attained within 20min. Meanwhile, a sequential extraction method for arsenic and mercury in rice was tested. Subsequently, 1% HNO3 microwave-assisted extraction was chosen. Calibration curves based on peak area measurements were linear with correlation coefficient greater than 0.9958 for each species in the range studied. The detection limits of the species were in the range of 0.84-2.41μg/L for arsenic and 0.01-0.04μg/L for mercury, respectively. The proposed method was then successfully applied for the simultaneous determination of arsenic and mercury species in rice flour standard material and two kinds of rice from local markets. PMID:27451225

  16. Microwave-assisted extraction of rare earth elements from petroleum refining catalysts and ambient fine aerosols prior to inductively coupled plasma-mass spectrometry.

    PubMed

    Kulkarni, Pranav; Chellam, Shankararaman; Mittlefehldt, David W

    2007-01-01

    A robust microwave-assisted acid digestion procedure followed by inductively coupled plasma-mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM(2.5)). High temperature (200 degrees C), high pressure (200 psig), acid digestion (HNO(3), HF and H(3)BO(3)) with 20 min dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst and PM(2.5). This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using (115)In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu and Dy in ambient PM(2.5) in an industrial area of Houston, TX. PMID:17386451

  17. Direct trace-elemental analysis of urine samples by laser ablation-inductively coupled plasma mass spectrometry after sample deposition on clinical filter papers.

    PubMed

    Aramendía, Maite; Rello, Luis; Vanhaecke, Frank; Resano, Martín

    2012-10-16

    Collection of biological fluids on clinical filter papers shows important advantages from a logistic point of view, although analysis of these specimens is far from straightforward. Concerning urine analysis, and particularly when direct trace elemental analysis by laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) is aimed at, several problems arise, such as lack of sensitivity or different distribution of the analytes on the filter paper, rendering obtaining reliable quantitative results quite difficult. In this paper, a novel approach for urine collection is proposed, which circumvents many of these problems. This methodology consists on the use of precut filter paper discs where large amounts of sample can be retained upon a single deposition. This provides higher amounts of the target analytes and, thus, sufficient sensitivity, and allows addition of an adequate internal standard at the clinical lab prior to analysis, therefore making it suitable for a strategy based on unsupervised sample collection and ulterior analysis at referral centers. On the basis of this sampling methodology, an analytical method was developed for the direct determination of several elements in urine (Be, Bi, Cd, Co, Cu, Ni, Sb, Sn, Tl, Pb, and V) at the low μg L(-1) level by means of LA-ICPMS. The method developed provides good results in terms of accuracy and LODs (≤1 μg L(-1) for most of the analytes tested), with a precision in the range of 15%, fit-for-purpose for clinical control analysis.

  18. Comparison of laser ablation-inductively coupled plasma-mass spectrometry and micro-X-ray fluorescence spectrometry for elemental imaging in Daphnia magna.

    PubMed

    Gholap, Deepti S; Izmer, Andrei; De Samber, Björn; van Elteren, Johannes T; Selih, Vid S; Evens, Roel; De Schamphelaere, Karel; Janssen, Colin; Balcaen, Lieve; Lindemann, Inge; Vincze, Laszlo; Vanhaecke, Frank

    2010-04-01

    Visualization of elemental distributions in thin sections of biological tissue is gaining importance in many disciplines of biological and medical research. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and scanning micro-X-ray fluorescence spectrometry (micro-XRF) are two widely used microanalytical techniques for elemental mapping. This article compares the capabilities of the two techniques for imaging the distribution of selected elements in the model organism Daphnia magna in terms of detection power and spatial resolution. Sections with a thickness of 10 and 20 microm of the fresh water crustacean Daphnia magna were subjected to LA-ICP-MS and micro-XRF analysis. The elemental distributions obtained for Ca, P, S and Zn allow element-to-tissue correlation. LA-ICP-MS and micro-XRF offer similar limits of detection for the elements Ca and P and thus, allow a cross-validation of the imaging results. LA-ICP-MS was particularly sensitive for determining Zn (LOD 20 microg g(-1), 15 microm spot size) in Daphnia magna, while the detection power of micro-XRF was insufficient in this context. However, LA-ICP-MS was inadequate for the measurement of the S distributions, which could be better visualized with micro-XRF (LOD 160 microg g(-1), 5 s live time). Both techniques are thus complementary in providing an exhaustive chemical profiling of tissue samples.

  19. Evaluation of the Forensic Utility of Scanning Electron Microscopy-Energy Dispersive Spectroscopy and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry for Printing Ink Examinations.

    PubMed

    Corzo, Ruthmara; Subedi, Kiran; Trejos, Tatiana; Almirall, José R

    2016-05-01

    Improvements in printing technology have exacerbated the problem of document counterfeiting, prompting the need for analytical techniques that better characterize inks for forensic analysis and comparisons. In this study, 319 printing inks (toner, inkjet, offset, and Intaglio) were analyzed directly on the paper substrate using scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). As anticipated, the high sensitivity of LA-ICP-MS pairwise comparisons resulted in excellent discrimination (average of ~ 99.6%) between different ink samples from each of the four ink types and almost 100% correct associations between ink samples known to originate from the same source. SEM-EDS analysis also resulted in very good discrimination for different toner and intaglio inks (>97%) and 100% correct association for samples from the same source. SEM-EDS provided complementary information to LA-ICP-MS for certain ink types but showed limited utility for the discrimination of inkjet and offset inks.

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

    PubMed

    Veyseh, Somayeh; Niazi, Ali

    2016-01-15

    A novel method based on aeration-assisted homogeneous liquid-liquid microextraction using high density solvent is presented, which is combined with inductively coupled plasma-mass spectroscopy in which simultaneous preconcentration and determination of thorium and uranium with arsenazo III as the chelating reagent is carried out. To achieve optimum conditions, several parameters such as pH, concentration of arsenazo III, extraction and homogenous solvent types and their volumes, salt concentration and extraction time were investigated. Under which, the calibration graphs were linear in the range of 0.5-600.0ng L(-1) for thorium and 0.3-550.0ng L(-1) for uranium. Good linearities were obtained for both analytes with R(2) values larger than 0.9990. The limits of detection (LOD, 3Sb/m, n=5) of this method were 0.12 and 0.09ng L(-1), and the enrichment factors were estimated to be 370 and 410 for thorium and uranium, respectively. The proposed method was applied to determine the thorium and uranium in human hair and different environmental water samples. Acceptable recoveries ranged from 99.4% to 100.7% with standard deviation of 0.05 to 0.17. PMID:26592585

  1. Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS).

    PubMed

    Brittain, S R; Cox, A G; Tomos, A D; Paterson, E; Siripinyanond, A; McLeod, C W

    2012-03-01

    Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied. PMID:22237634

  2. Comparison of digestion procedures and methods for quantification of trace lead in breast milk by isotope dilution inductively coupled plasma mass spectrometry

    PubMed Central

    Amarasiriwardena, Chitra J.; Jayawardene, Innocent; Lupoli, Nicola; Barnes, Ramon M.; Hernandez-Avila, Mauricio; Hu, Howard

    2014-01-01

    Measurement of lead in breast milk is an important public health consideration and can be technically quite challenging. The reliable and accurate determination of trace lead in human breast milk is difficult for several reasons including: potential for contamination during sample collection, storage, and analysis; complexities related to the high fat content of human milk; and poor analytic sensitivity at low concentrations. Breast milk lead levels from previous published studies should therefore be reviewed with caution. Due to the difficulty in identifying a method that would successfully digest samples with 100% efficiency, we evaluated three different digestion procedures including: (1) dry ashing in a muffle furnace, (2) microwave oven digestion, and (3) digestion in high pressure asher. High temperature, high pressure asher digestion was selected as the procedure of choice for the breast milk samples. Trace lead analysis was performed using isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS). Measured lead concentrations in breast milk samples (n = 200) from Mexico ranged from 0.2 to 6.7 ng ml−1. The precision for these measurements ranged from 0.27–7.8% RSD. Use of strict contamination control techniques and of a very powerful digestion procedure, along with an ID-ICP-MS method for lead determination, enables us to measure trace lead levels as low as 0.2 ng ml−1 in milk (instrument detection limit = 0.01 ng ml−1). PMID:24808927

  3. Determination of minor and trace elements in aromatic spices by micro-wave assisted digestion and inductively coupled plasma-mass spectrometry.

    PubMed

    Khan, Naeem; Choi, Ji Yeon; Nho, Eun Yeong; Jamila, Nargis; Habte, Girum; Hong, Joon Ho; Hwang, In Min; Kim, Kyong Su

    2014-09-01

    This study aimed at analyzing the concentrations of 23 minor and trace elements in aromatic spices by inductively coupled plasma-mass spectrometry (ICP-MS), after wet digestion by microwave system. The analytical method was validated by linearity, detection limits, precision, accuracy and recovery experiments, obtaining satisfactory values in all cases. Results indicated the presence of variable amounts of both minor and trace elements in the selected aromatic spices. Manganese was high in cinnamon (879.8 μg/g) followed by cardamom (758.1 μg/g) and clove (649.9 μg/g), strontium and zinc were high in ajwain (489.9 μg/g and 84.95 μg/g, respectively), while copper was high in mango powder (77.68 μg/g). On the whole some of the minor and essential trace elements were found to have good nutritional contribution in accordance to RDA. The levels of toxic trace elements, including As, Cd, and Pb were very low and did not found to pose any threat to consumers.

  4. Determination of isotopic composition of dissolved copper in seawater by multi-collector inductively coupled plasma mass spectrometry after pre-concentration using an ethylenediaminetriacetic acid chelating resin.

    PubMed

    Takano, Shotaro; Tanimizu, Masaharu; Hirata, Takafumi; Sohrin, Yoshiki

    2013-06-19

    Copper is an essential trace metal that shows a vertical recycled-scavenged profile in the ocean. To help elucidate the biogeochemical cycling of Cu in the present and past oceans, it is important to determine the distribution of Cu isotopes in seawater. However, precise isotopic analysis of Cu has been impaired by the low concentrations of Cu as well as co-existing elements that interfere with measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The objective of this study is to develop a simple Cu pre-concentration method using Nobias-chelate PA1 resin (Hitachi High Technologies). This extraction followed by anion exchange, allows precise analysis of the Cu isotopic composition in seawater. Using this method, Cu was quantitatively concentrated from seawater and >99.9999% of the alkali and alkaline earth metals were removed. The technique has a low procedural blank of 0.70 ng for Cu for a 2L sample and the precision of the Cu isotopic analysis was ±0.07‰ (±2SD, n=6). We applied this method to seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples obtained from the northwestern Pacific Ocean. The range of dissolved δ(65)Cu was 0.40-0.68‰.

  5. Characterization of gold nanoparticle uptake by tomato plants using enzymatic extraction followed by single-particle inductively coupled plasma-mass spectrometry analysis.

    PubMed

    Dan, Yongbo; Zhang, Weilan; Xue, Runmiao; Ma, Xingmao; Stephan, Chady; Shi, Honglan

    2015-03-01

    Plant uptake and accumulation of nanoparticles (NPs) represent an important pathway for potential human expose to NPs. Consequently, it is imperative to understand the uptake of accumulation of NPs in plant tissues and their unique physical and chemical properties within plant tissues. Current technologies are limited in revealing the unique characteristics of NPs after they enter plant tissues. An enzymatic digestion method, followed by single-particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) analysis, was developed for simultaneous determination of gold NP (AuNP) size, size distribution, particle concentration, and dissolved Au concentration in tomato plant tissues. The experimental results showed that Macerozyme R-10 enzyme was capable of extracting AuNPs from tomato plants without causing dissolution or aggregation of AuNPs. The detection limit for quantification of AuNP size was 20 nm, and the AuNP particle concentration detection limit was 1000 NPs/mL. The particle concentration recoveries of spiked AuNPs were high (79-96%) in quality control samples. The developed SP-ICP-MS method was able to accurately measure AuNP size, size distribution, and particle concentration in the plant matrix. The dosing study indicated that tomato can uptake AuNPs as intact particles without alternating the AuNP properties.

  6. Determination of mercury compounds in fish by microwave-assisted extraction and liquid chromatography-vapor generation-inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chiou, Chwei-Sheng; Jiang, Shiuh-Jen; Kumar Danadurai, K. Suresh

    2001-07-01

    A method employing a vapor generation system and LC combined with inductively coupled plasma mass spectrometry (LC-ICP-MS) is presented for the determination of mercury in biological tissues. An open vessel microwave digestion system was used to extract the mercury compounds from the sample matrix. The efficiency of the mobile phase, a mixture of L-cysteine and 2-mercaptoethanol, was evaluated for LC separation of inorganic mercury [Hg(II)], methylmercury (methyl-Hg) and ethylmercury (ethyl-Hg). The sensitivity, detection limits and repeatability of the liquid chromatography (LC) ICP-MS system with a vapor generator were comparable to, or better than, that of an LC-ICP-MS system with conventional pneumatic nebulization, or other sample introduction techniques. The experimental detection limits for various mercury species were in the range of 0.05-0.09 ng ml -1 Hg, based on peak height. The proposed method was successfully applied to the determination of mercury compounds in a swordfish sample purchased from the local market. The accuracy of the method was evaluated by analyzing a marine biological certified reference material (DORM-2, NRCC).

  7. A high-throughput solid-phase extraction microchip combined with inductively coupled plasma-mass spectrometry for rapid determination of trace heavy metals in natural water.

    PubMed

    Shih, Tsung-Ting; Hsieh, Cheng-Chuan; Luo, Yu-Ting; Su, Yi-An; Chen, Ping-Hung; Chuang, Yu-Chen; Sun, Yuh-Chang

    2016-04-15

    Herein, a hyphenated system combining a high-throughput solid-phase extraction (htSPE) microchip with inductively coupled plasma-mass spectrometry (ICP-MS) for rapid determination of trace heavy metals was developed. Rather than performing multiple analyses in parallel for the enhancement of analytical throughput, we improved the processing speed for individual samples by increasing the operation flow rate during SPE procedures. To this end, an innovative device combining a micromixer and a multi-channeled extraction unit was designed. Furthermore, a programmable valve manifold was used to interface the developed microchip and ICP-MS instrumentation in order to fully automate the system, leading to a dramatic reduction in operation time and human error. Under the optimized operation conditions for the established system, detection limits of 1.64-42.54 ng L(-1) for the analyte ions were achieved. Validation procedures demonstrated that the developed method could be satisfactorily applied to the determination of trace heavy metals in natural water. Each analysis could be readily accomplished within just 186 s using the established system. This represents, to the best of our knowledge, an unprecedented speed for the analysis of trace heavy metal ions.

  8. Metallomics for drug development: serum protein binding and analysis of an anticancer tris(8-quinolinolato)gallium(III) drug using inductively coupled plasma mass spectrometry.

    PubMed

    Ossipov, Konstantin; Foteeva, Lidia S; Seregina, Irina F; Perevalov, Sergei A; Timerbaev, Andrei R; Bolshov, Mikhail A

    2013-06-27

    The application of an inductively coupled plasma mass spectrometry (ICP-MS) assay for quantifying in vitro binding of a gallium-based anticancer drug, tris(8-quinolinolato)gallium(III), to serum albumin and transferrin and in human serum is described. The distribution of the drug between the protein-rich and protein-free fractions was assessed via ICP-MS measurement of total gallium in ultrafiltrates. Comparative kinetic studies revealed that the drug exhibits a different reactivity toward individual proteins. While the maximum possible binding to albumin (~10%) occurs practically immediately, interaction with transferrin has a step-like character and the equilibrium state (with more than 50% binding) is reached for about 48 h. Drug transformation into the bound form in serum, also very fast, results in almost quantitative binding (~95%). The relative affinity of protein-drug binding was characterized in terms of the association constants ranging from 10(3) to 10(4)M(-1). In order to further promote clinical testing of the gallium drug, the ICP-MS method was applied for direct quantification of gallium in human serum spiked with the drug. The detection limit for gallium was found to be as low as 20 ng L(-1). The repeatability was better than 8% (as RSD) and the achieved recoveries were in the range 99-103%.

  9. Microwave dissolution of plant tissue and the subsequent determination of trace lanthanide and actinide elements by inductively coupled plasma-mass spectrometry

    SciTech Connect

    Alvarado, J.S.; Neal, T.J.; Smith, L.L.; Erickson, M.D.

    1997-08-01

    Recently there has been much concern with the ability of plants to uptake heavy metals from their surroundings. With the development of instrumental techniques with low detection limits such as inductively coupled plasma-mass spectrometry (ICP-MS), attention is shifting toward achieving faster and more elegant ways of oxidizing the organic material inherent in environmental samples. Closed-vessel microwave dissolution was compared with conventional methods for the determination of concentrations of cerium, samarium, europium, terbium, uranium and thorium in a series of samples from the National Institute of Standards and Technology and from fields in Idaho. The ICP-MS technique exhibited detection limits in parts-per-trillion and linear calibration plots over three orders of magnitude for the elements under study. The results obtained by using nitric acid and hydrogen peroxide in a microwave digestion system for the analysis of reference materials showed close agreement with the accepted values. These values were compared with results obtained from dry- and wet-ashing procedures. The findings from an experiment comparing radiometric techniques for the determination of actinide elements to ICP-MS are reported.

  10. Element bioimaging of liver needle biopsy specimens from patients with Wilson's disease by laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Hachmöller, Oliver; Aichler, Michaela; Schwamborn, Kristina; Lutz, Lisa; Werner, Martin; Sperling, Michael; Walch, Axel; Karst, Uwe

    2016-05-01

    A laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method is developed and applied for the analysis of paraffin-embedded liver needle biopsy specimens of patients with Wilson's disease (WD), a rare autosomal recessive disorder of the copper metabolism causing various hepatic, neurological and psychiatric symptoms due to a copper accumulation in the liver and the central nervous system. The sample set includes two WD liver samples and one negative control sample. The imaging analysis was performed with a spatial resolution of 10 μm. Besides copper, iron was monitored because an elevated iron concentration in the liver is known for WD. In addition to this, both elements were quantified using an external calibration based on matrix-matched gelatine standards. The presented method offers low limits of detection of 1 and 5 μg/g for copper and iron, respectively. The high detection power and good spatial resolution allow the analysis of small needle biopsy specimen using this method. The two analyzed WD samples can be well differentiated from the control sample due to their inhomogeneous copper distribution and high copper concentrations of up to 1200 μg/g. Interestingly, the WD samples show an inverse correlation of regions with elevated copper concentrations and regions with high iron concentrations. PMID:27049132

  11. Optimization of a single-drop microextraction method for multielemental determination by electrothermal vaporization inductively coupled plasma mass spectrometry following in situ vapor generation

    NASA Astrophysics Data System (ADS)

    Gil, Sandra; de Loos-Vollebregt, Margaretha T. C.; Bendicho, Carlos

    2009-03-01

    A headspace single-drop microextraction (HS-SDME) method has been developed in combination with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the simultaneous determination of As, Sb, Bi, Pb, Sn and Hg in aqueous solutions. Vapor generation is carried out in a 40 mL volume closed-vial containing a solution with the target analytes in hydrochloric acid and potassium ferricyanide medium. Hydrides (As, Sb, Bi, Pb, Sn) and Hg vapor are trapped onto an aqueous single drop (3 µL volume) containing Pd(II), followed by the subsequent injection in the ETV. Experimental variables such as medium composition, sodium tetrahydroborate (III) volume and concentration, stirring rate, extraction time, sample volume, ascorbic acid concentration and palladium amount in the drop were fully optimized. The limits of detection (LOD) (3 σ criterion) of the proposed method for As, Sb, Bi, Pb, Sn and Hg were 0.2, 0.04, 0.01, 0.07, 0.09 and 0.8 µg/L, respectively. Enrichment factors of 9, 85, 138, 130, 37 and 72 for As, Sb, Bi, Pb, Sn and Hg, respectively, were achieved in 210 s. The relative standard deviations ( N = 5) ranged from 4 to 8%. The proposed HS-SDME-ETV-ICP-MS method has been applied for the determination of As, Sb, Bi, Pb, Sn and Hg in NWRI TM-28.3 certified reference material.

  12. Simultaneous separation of 17 inorganic and organic arsenic compounds in marine biota by means of high-performance liquid chromatography/inductively coupled plasma mass spectrometry.

    PubMed

    Kohlmeyer, Ute; Kuballa, Jürgen; Jantzen, Eckard

    2002-01-01

    A method using high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICP-MS) has been developed to determine inorganic arsenic (arsenite, arsenate) along with organic arsenic compounds (monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, arsenocholine, trimethylarsine oxide, tetramethylarsonium ion and several arsenosugars) in fish, mussel, oyster and marine algae samples. The species were extracted by means of a methanol/water mixture and a dispersion unit in 2 min, with extraction efficiencies ranging from 83 to 107% in the different organisms. Up to 17 different species were determined within 15 min on an anion-exchange column, using a nitric acid gradient and an ion-pairing reagent. As all species are shown in one chromatogram, a clear overview of arsenic distribution patterns in different marine organisms is given. Arsenobetaine is the major compound in marine animals whereas arsenosugars and arsenate are dominant in marine algae. The method was validated with CRM DORM-2 (dogfish muscle). Concentrations were within the certified limits and low detection limits of 8 ng g(-1) (arsenite) to 50 ng g(-1) (arsenate) were obtained. PMID:11968129

  13. Element bioimaging of liver needle biopsy specimens from patients with Wilson's disease by laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Hachmöller, Oliver; Aichler, Michaela; Schwamborn, Kristina; Lutz, Lisa; Werner, Martin; Sperling, Michael; Walch, Axel; Karst, Uwe

    2016-05-01

    A laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method is developed and applied for the analysis of paraffin-embedded liver needle biopsy specimens of patients with Wilson's disease (WD), a rare autosomal recessive disorder of the copper metabolism causing various hepatic, neurological and psychiatric symptoms due to a copper accumulation in the liver and the central nervous system. The sample set includes two WD liver samples and one negative control sample. The imaging analysis was performed with a spatial resolution of 10 μm. Besides copper, iron was monitored because an elevated iron concentration in the liver is known for WD. In addition to this, both elements were quantified using an external calibration based on matrix-matched gelatine standards. The presented method offers low limits of detection of 1 and 5 μg/g for copper and iron, respectively. The high detection power and good spatial resolution allow the analysis of small needle biopsy specimen using this method. The two analyzed WD samples can be well differentiated from the control sample due to their inhomogeneous copper distribution and high copper concentrations of up to 1200 μg/g. Interestingly, the WD samples show an inverse correlation of regions with elevated copper concentrations and regions with high iron concentrations.

  14. Simultaneous determination of seven ginsenosides in rat plasma by high-performance liquid chromatography coupled to time-of-flight mass spectrometry: application to pharmacokinetics of Shenfu injection.

    PubMed

    Li, Zhengguang; Zhang, Rui; Wang, Xiuping; Hu, Xiaofei; Chen, Yuguo; Liu, Qingfei

    2015-02-01

    A high-performance liquid chromatography coupled to time-of-flight mass spectrometry (HPLC-TOF MS) method was successfully developed and validated for the identification and determination of seven ginsenosides, Re , Rf , Rb1 , Rc , Rb2 , Ro and Rd , in a Chinese herbal preparation, Shenfu injection, and rat plasma. Based on the method, the pharmacokinetic profiles of the seven ginsenosides were investigated following intravenous administration of single dose of Shenfu injection to six rats. The established method had high linearity, selectivity, sensitivity, accuracy and precision. The pharmacokinetic results showed that Rb1 , Rc and Rb2 had similar pharmacokinetic profiles and relatively long half-life values (19.29 ± 6.36, 29.54 ± 22.91 and 35.60 ± 30.66 h). The half-lives of Rf and Rd were 4.21 ± 3.68 and 8.49 ± 5.20 h, respectively, indicating that they could be metabolized more rapidly than Rb1 , Rc and Rb2 .

  15. Determination of traces of uranium and thorium in titanium and copper used for the construction of the Russian Emission Detector 100 by inductively coupled plasma mass spectrometry.

    PubMed

    Poteshin, Sergey S; Sysoev, Alexey A; Lagunov, Sergey S; Sereda, Andrei; Sosnovtsev, Valery V; Bolozdynya, Alexander I; Efremenko, Yuriy B

    2015-01-01

    The Russian Emission Detector 100 (RED-100) under construction at the National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) is designed to detect the presently undiscovered effect of coherent neutrino scattering. One of the factors limiting the sensitivity of the detector is the spontaneous decay of uranium and thorium in the detector materials. Radioactive impurities in detector materials at levels of parts per billion can significantly affect the sensitivity. Five random samples of titanium and one of copper from materials used in the construction of the detector were selected for assay. The concentration of (232)Th and (238)U were measured by inductively coupled plasma mass spectrometry (ICP- MS) in solid titanium using both: solutions in acids and direct sampling by laser ablation (LA-ICP-MS). The LA- ICP-MS method allowed us to determine (238)U and (232)Th at subnanogram per gram levels. This method is much faster than ICP-MS with liquid injection. The titanium samples studied have impurities in the range between 1 ng g(-1) and 21 ng g(-1) for (238)U and 3 ng g(-1) and 31 ng g(-1) for (232)Th. In copper we set upper limits of 0.4 ng g(-1) for (238)U and 1 ng g(-1)for (232)Th. The total activity of the cryostat constructed from materials studied was estimated to be 43 Bq. PMID:26307714

  16. Determination of rare earth elements in rock samples by inductively coupled plasma mass-spectrometry after sorption preconcentration using Pol-DETATA sorbent.

    PubMed

    Fedyunina, N N; Ossipov, K B; Seregina, I F; Bolshov, M A; Statkus, M A; Tsysin, G I

    2012-12-15

    Sorption preconcentration of rare earth elements prior to introduction in inductively coupled plasma mass spectrometry is developed. For the first time Pol-DETATA sorbent was used for REEs preconcentration after digestion of wide classes of rock samples. The developed technique is based on lithium metaborate fusion, preconcentration on Pol-DETATA sorbent, elution with nitric acid and flow-injection sample introduction to the ICP-MS spectrometer. The efficiency of REEs extraction from the resulting solutions in the presence of high amounts of iron is examined. 5-sulfosalicylic acid was used as a masking reagent. Flow-injection introduction of 50 μL of eluate obtained after desorption was used to avoid corrosion of the parts of the ICP-MS instrument due to high acidity of the eluate. The accuracy of the developed technique is checked by the analysis of the certified reference materials of rock samples. The REEs recoveries within 85-100% interval were attained for most REEs in tested reference materials.

  17. Comparison of digestion procedures and methods for quantification of trace lead in breast milk by isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Amarasiriwardena, Chitra J; Jayawardene, Innocent; Lupoli, Nicola; Barnes, Ramon M; Hernandez-Avila, Mauricio; Hu, Howard; Ettinger, Adrienne S

    2013-01-01

    Measurement of lead in breast milk is an important public health consideration and can be technically quite challenging. The reliable and accurate determination of trace lead in human breast milk is difficult for several reasons including: potential for contamination during sample collection, storage, and analysis; complexities related to the high fat content of human milk; and poor analytic sensitivity at low concentrations. Breast milk lead levels from previous published studies should therefore be reviewed with caution. Due to the difficulty in identifying a method that would successfully digest samples with 100% efficiency, we evaluated three different digestion procedures including: (1) dry ashing in a muffle furnace, (2) microwave oven digestion, and (3) digestion in high pressure asher. High temperature, high pressure asher digestion was selected as the procedure of choice for the breast milk samples. Trace lead analysis was performed using isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS). Measured lead concentrations in breast milk samples (n = 200) from Mexico ranged from 0.2 to 6.7 ng ml(-1). The precision for these measurements ranged from 0.27-7.8% RSD. Use of strict contamination control techniques and of a very powerful digestion procedure, along with an ID-ICP-MS method for lead determination, enables us to measure trace lead levels as low as 0.2 ng ml(-1) in milk (instrument detection limit = 0.01 ng ml(-1)). PMID:24808927

  18. Determination of toxic inorganic elements pollution in ground waters of Kahuta Industrial Triangle Islamabad, Pakistan using inductively coupled plasma mass spectrometry.

    PubMed

    Kausar, Rubina; Ahmad, Zulfiqar

    2009-10-01

    The present study deals with the ground water quality assessment in Kahuta Industrial Triangle Islamabad, Pakistan. The objective of the study was to assess ground water quality against the drinking water standards for various toxic inorganic elements. Representative groundwater samples were collected and analyzed in the Water Quality Laboratory of Pakistan Council of Research in Water Resources (PCRWR) at Islamabad, Pakistan. The samples were run on ICP-MS (Inductively coupled plasma mass spectrometry), which has the capability to separate and quantify 70 elements at a time. One of the finding of study is that ICP-MS is a very good tool to analyze broad range of toxic inorganic elements to the level of parts per billion (ppb). World Health Organization drinking water standards shows that these toxic inorganic elements such as heavy metals even at this concentration level (ppb) are injurious to human health. This analysis indicated pollution of various toxic elements including Selenium. Vertical leachate through industrial waste septic tanks is identified as major cause of groundwater pollution in the Industrial Triangle. Monitoring of the septic tanks and groundwater quality in study area is suggested along with remedial measures.

  19. Solid-phase extraction of Cu, Co and Pb on oxidized single-walled carbon nanotubes and their determination by inductively coupled plasma mass spectrometry.

    PubMed

    Chen, Shizhong; Liu, Cheng; Yang, Ming; Lu, Dengbo; Zhu, Li; Wang, Zhan

    2009-10-15

    A novel method using a microcolumn packed with single-walled carbon nanotubes (SWNTs) as a new adsorption material was developed for the preconcentration of trace Cu, Co and Pb in biological and environmental samples prior to their determination by inductively coupled plasma mass spectrometry (ICP-MS). SWNTs oxidized with concentrated nitric acid have been proved to possess an exceptional adsorption capability for the analytes due to their surface functionalization. The adsorption behaviors of the analytes on SWNTs under dynamic conditions were studied systematically. The main factors influencing the preconcentration and determination of the analytes (pH, sample flow rate and volume, eluent concentration and interfering ions) have been examined in detail. Under the optimum conditions, the detection limits for Cu, Co and Pb were 39, 1.2 and 5.4 pg mL(-1), respectively; the relative standard deviations (RSDs) were found to be less than 6.0% (n=9, c=1.0 ng mL(-1)). This method was validated using a certified reference material of mussel, and has been successfully applied for the determination of trace Cu, Co and Pb in real water sample with the recoveries of 96.0-109%. PMID:19473762

  20. Mass Spectrometric and Langmuir Probe Measurements in Inductively Coupled Plasmas in Ar, CHF3/Ar and CHF3/Ar/O2 Mixtures

    NASA Technical Reports Server (NTRS)

    Kim, J. S.; Rao, M. V. V. S.; Cappelli, M. A.; Sharma, S. P.; Meyyappan, M.; Arnold, Jim (Technical Monitor)

    2000-01-01

    Absolute fluxes and energy distributions of ions in inductively coupled plasmas of Ar, CHF3/Ar, and CHF3/Ar/O2 have been measured. These plasmas were generated in a Gaseous Electronics Conference (GEC) cell modified for inductive coupling at pressures 10-50 mTorr and 100-300 W of 13.56 MHz radio frequency (RF) power in various feedgas mixtures. In pure Ar plasmas, the Ar(+) flux increases linearly with pressure as well as RF-power. Total ion flux in CHF3 mixtures decreases with increase in pressure and also CHF3 concentration. Relative ion fluxes observed in the present studies are analyzed with the help of available cross sections for electron impact ionization and charge-exchange ion-molecule reactions. Measurements of plasma potential, electron and ion number densities, electron energy distribution function, and mean electron energy have also been made in the center of the plasma with a RF compensated Langmuir probe. Plasma potential values are compared with the mean ion energies determined from the measured ion energy distributions and are consistent. Electron temperature, plasma potential, and mean ion energy vary inversely with pressure, but increase with CHF3 content in the mixture.

  1. Laser ablation inductively coupled plasma mass spectrometry: A new technique for the determination of trace and ultra-trace elements in silicates

    SciTech Connect

    Perkins, W.T.; Pearce, N.J.G.; Jeffries, T.E. )

    1993-01-01

    This paper describes recent work applying a laser ablation system coupled to an inductively coupled plasma mass spectrometer (LA-ICP-MS) for the direct analysis of solid geological materials. This work demonstrates the potential of LA-ICP-MS for the determination of a wide range of petrogenetically important trace and ultra-trace elements (including for example REE, Hf, Ta, Nb, Th, U) following a routine method of sample preparation. Powdered geological materials have been prepared as both pressed powder disks and fused glasses; both common methods of sample preparation for X-ray fluorescence (XRF) analysis. The solid materials were sampled by ablation using a pulsed Nd:YAG laser operating at 1,064 nm. Analyses can be produced at approximately 10 samples per hour. This instrumental method has limits of detection at or close to those in chondritic meteorites and gives linear calibrations over four orders of magnitude. The accuracy of the technique has been evaluated using reference materials to calibrate the instrument and treating Geological Survey of Japan basalts JB-1a, JB-2, and JB-3 as unknowns.' Detection limits are better than routine XRF analysis and compare favorably with Instrumental Neutron Activation Analysis. Laser ablation overcomes the problems of sample dissolution employed in standard wet chemical techniques, whilst the fused glasses provide homogeneous solid samples. The fused glass technique has been applied to a wide range of reference materials from ultra-basic rocks through basalts and andesites to granites, as well as syenite, mica schist, and black shale. For all of the elements commonly used to generate multi-element discrimination diagrams the data obtained define straight line calibrations. This method is therefore capable of analyzing the complete range of silicate compositions normally encountered with a single calibration (i.e., there is no apparent matrix effect). 47 refs., 4 figs., 5 tabs.

  2. Determinations of rare earth element abundance and U-Pb age of zircons using multispot laser ablation-inductively coupled plasma mass spectrometry.

    PubMed

    Yokoyama, Takaomi D; Suzuki, Toshihiro; Kon, Yoshiaki; Hirata, Takafumi

    2011-12-01

    We have developed a new calibration technique for multielement determination and U-Pb dating of zircon samples using laser ablation-inductively coupled plasma mass spectrometry (ICPMS) coupled with galvanometric optics. With the galvanometric optics, laser ablation of two or more sample materials could be achieved in very short time intervals (~10 ms). The resulting sample aerosols released from different ablation pits or different solid samples were mixed and homogenized within the sample cell and then transported into the ICP ion source. Multiple spot laser ablation enables spiking of analytes or internal standard elements directly into the solid samples, and therefore the standard addition calibration method can be applied for the determination of trace elements in solid samples. In this study, we have measured the rare earth element (REE) abundances of two zircon samples (Nancy 91500 and Prešovice) based on the standard addition technique, using a direct spiking of analytes through a multispot laser ablation of the glass standard material (NIST SRM612). The resulting REE abundance data show good agreement with previously reported values within analytical uncertainties achieved in this study (10% for most elements). Our experiments demonstrated that nonspectroscopic interferences on 14 REEs could be significantly reduced by the standard addition technique employed here. Another advantage of galvanometric devices is the accumulation of sample aerosol released from multiple spots. In this study we have measured the U-Pb age of a zircon sample (LMR) using an accumulation of sample aerosols released from 10 separate ablation pits of low diameters (~8 μm). The resulting (238)U-(206)Pb age data for the LMR zircons was 369 ± 64 Ma, which is in good agreement with previously reported age data (367.6 ± 1.5 Ma). (1) The data obtained here clearly demonstrate that the multiple spot laser ablation-ICPMS technique can become a powerful approach for elemental and isotopic

  3. Simultaneous pressurized enzymatic hydrolysis extraction and clean up for arsenic speciation in seafood samples before high performance liquid chromatography-inductively coupled plasma-mass spectrometry determination.

    PubMed

    Moreda-Piñeiro, Jorge; Alonso-Rodríguez, Elia; Moreda-Piñeiro, Antonio; Moscoso-Pérez, Carmen; Muniategui-Lorenzo, Soledad; López-Mahía, Purificación; Prada-Rodríguez, Darío; Bermejo-Barrera, Pilar

    2010-10-29

    The feasibility of pressurized conditions to assist enzymatic hydrolysis of seafood tissues for arsenic speciation was novelty studied. A simultaneous in situ (in cell) clean-up procedure was also optimized, which speeds up the whole sample treatment. Arsenic species (As(III), MMA, DMA, As(V), AsB and AsC) were released from dried seafood tissues using pepsin as a protease, and the arsenic species were separated/quantified by anion exchange high performance liquid chromatography (HPLC) coupled to inductively coupled plasma-mass spectrometry (ICP-MS). Variables inherent to the enzymatic activity (pH, temperature and ionic strength), the amount of enzyme (pepsin), and factors affecting pressurization (pressure, static time, number of cycles and amount of dispersing agent, C-18) were fully evaluated. Pressurized assisted enzymatic hydrolysis (PAEH) with pepsin can be finished after few minutes (two cycles of 2 min each one plus 3 min to reach the hydrolysis temperature of 50 °C). A total sample solubilisation is not achieved after the procedure, however it is efficient enough for breaking down certain bonds of bio-molecules and for releasing arsenic species. The developed method has been found to be precise (RSDs lower than 6% for As(III), DMA and As(V); and 3% for AsB) and sensitive (LOQs of 18.1, 36.2, 35.7, 28.6, 20.6 and 22.5 ng/g for As(III), MMA, DMA, As(V), AsB and AsC, respectively). The optimized methodology was successfully applied to different certified reference materials (DORM-2 and BCR 627) which offer certified AsB and DMA contents, and also to different seafood products (mollusks, white fishes and cold water fishes).

  4. Physicochemical characterization of titanium dioxide pigments using various techniques for size determination and asymmetric flow field flow fractionation hyphenated with inductively coupled plasma mass spectrometry.

    PubMed

    Helsper, Johannes P F G; Peters, Ruud J B; van Bemmel, Margaretha E M; Rivera, Zahira E Herrera; Wagner, Stephan; von der Kammer, Frank; Tromp, Peter C; Hofmann, Thilo; Weigel, Stefan

    2016-09-01

    Seven commercial titanium dioxide pigments and two other well-defined TiO2 materials (TiMs) were physicochemically characterised using asymmetric flow field flow fractionation (aF4) for separation, various techniques to determine size distribution and inductively coupled plasma mass spectrometry (ICPMS) for chemical characterization. The aF4-ICPMS conditions were optimised and validated for linearity, limit of detection, recovery, repeatability and reproducibility, all indicating good performance. Multi-element detection with aF4-ICPMS showed that some commercial pigments contained zirconium co-eluting with titanium in aF4. The other two TiMs, NM103 and NM104, contained aluminium as integral part of the titanium peak eluting in aF4. The materials were characterised using various size determination techniques: retention time in aF4, aF4 hyphenated with multi-angle laser light spectrometry (MALS), single particle ICPMS (spICPMS), scanning electron microscopy (SEM) and particle tracking analysis (PTA). PTA appeared inappropriate. For the other techniques, size distribution patterns were quite similar, i.e. high polydispersity with diameters from 20 to >700 nm, a modal peak between 200 and 500 nm and a shoulder at 600 nm. Number-based size distribution techniques as spICPMS and SEM showed smaller modal diameters than aF4-UV, from which mass-based diameters are calculated. With aF4-MALS calculated, light-scattering-based "diameters of gyration" (Øg) are similar to hydrodynamic diameters (Øh) from aF4-UV analyses and diameters observed with SEM, but much larger than with spICPMS. A Øg/Øh ratio of about 1 indicates that the TiMs are oblate spheres or fractal aggregates. SEM observations confirm the latter structure. The rationale for differences in modal peak diameter is discussed. PMID:27469116

  5. Ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry for the determination of Cr, Fe, Cu, Zn and Se in cereals

    NASA Astrophysics Data System (ADS)

    Huang, Shih-Yi; Jiang, Shiuh-Jen; Sahayam, A. C.

    2014-11-01

    Ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) has been applied to determine Cr, Fe, Cu, Zn and Se in several cereal samples. Thioacetamide was used as the modifier to enhance the ion signals. The background ions at the masses of interest were reduced in intensity significantly by using 1.0 mL min- 1 methane (CH4) as reaction cell gas in the dynamic reaction cell (DRC). Since the sensitivities of Cr, Fe, Cu, Zn and Se in different matrices were quite different, standard addition and isotope dilution methods were used for the determination of Cr, Fe, Cu, Zn and Se in these cereal samples. The method detection limits estimated from standard addition curves were about 1, 10, 4, 12 and 2 ng g- 1 for Cr, Fe, Cu, Zn and Se, respectively, in original cereal samples. This procedure has been applied to the determination of Cr, Fe, Cu, Zn and Se whose concentrations are in μg g- 1 (except Cr and Se) in standard reference materials (SRM) of National institute of standards and technology (NIST), NIST SRM 1568a Rice Flour and NIST SRM 1567a Wheat Flour and two cereal samples purchased from a local market. The analysis results of reference materials agreed with certified values at 95% confidence level according to Student's T-test. The results for the real world cereal samples were also found to be in good agreement with the pneumatic nebulization DRC ICP-MS results of the sample solutions.

  6. Method development for the redox speciation analysis of iron by ion chromatography-inductively coupled plasma mass spectrometry and carryover assessment using isotopically labeled analyte analogues.

    PubMed

    Wolle, Mesay Mulugeta; Fahrenholz, Timothy; Rahman, G M Mizanur; Pamuku, Matt; Kingston, H M 'Skip'; Browne, Damien

    2014-06-20

    An ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS) method was developed for the redox speciation analysis of iron (Fe) based on in-column complexation of Fe(2+) and Fe(3+) by dipicolinic acid (DPA). The effects of column type, mobile phase composition and molecular ion interference were studied in the method optimization. The carryover of the target species in the IC-ICP-MS method was uniquely and effectively evaluated using isotopically enriched analogues of the analytes ((54)Fe(2+) and (57)Fe(3+)). Standard solutions of the enriched standards were injected into the system following analysis of a sample, and the ratios of the isotopes of iron in the enriched standards were calculated based on the chromatographic peak areas. The concentrations of the analytes carried over from the sample to the enriched standards were determined using the quantitative relationship in isotope dilution mass spectrometry (IDMS). In contrast to the routine way of evaluating carryover effect by injecting a blank solution after sample analysis, the use of isotopically enriched standards identified significant analyte carryover in the present method. Extensive experiments were carried out to systematically identify the source of the carryover and to eliminate the problem; the separation column was found to be the exclusive source. More than 95% of the analyte carryover was eliminated by reducing the length of the column. The detection limit of the IC-ICP-MS method (MDL) for the iron species was 2ngg(-1). The method was used to determine Fe(2+) and Fe(3+) in synthetic aqueous standard solutions and a beverage sample.

  7. Speciation analysis of arsenic in prenatal and children's dietary supplements using microwave-enhanced extraction and ion chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Wolle, Mesay M; Rahman, G M Mizanur; Kingston, H M Skip; Pamuku, Matt

    2014-03-25

    A study was conducted to develop a microwave-enhanced extraction method for the determination of arsenic species in prenatal and children's dietary supplements prepared from plant materials. The method was optimized by evaluating the efficiency of various solutions previously used to extract arsenic from the types of plant materials used in the dietary supplement formulations. A multivitamin standard reference material (NIST SRM 3280) and a prenatal supplement sample were analyzed in the method optimization. The identified optimum conditions were 0.25 g of sample, 5 mL of 0.3 mol L(-1) orthophosphoric acid (H3PO4) and microwave heating at 90 °C for 30 min. The extracted arsenic was speciated by cation exchange ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS). The method detection limit (MDL) for the arsenic species was in the range 2-8 ng g(-1). Ten widely consumed prenatal and children's dietary supplements were analyzed using the optimized protocol. The supplements were found to have total arsenic in the concentration range 59-531 ng g(-1). The extraction procedure recovered 61-92% of the arsenic from the supplements. All the supplementary products were found to contain arsenite (As(3+)) and dimethylarsinic acid (DMA). Arsenate (As(5+)) was found in two of the supplements, and an unknown specie of arsenic was detected in one product. The results of the analysis were validated using mass balance by comparing the sum of the extracted and non-extracted arsenic with the total concentration of the element in the corresponding samples.

  8. High-performance liquid chromatography of selenium compounds utilizing perfluorinated carboxylic acid ion-pairing agents and inductively coupled plasma and electrospray ionization mass spectrometric detection.

    PubMed

    Kotrebai, M; Tyson, J F; Block, E; Uden, P C

    2000-01-01

    Increasing speciation demands in clinical chemistry, toxicology and nutrition have made the determination of the total elements in a sample inadequate; the amount of an element and the chemical forms in which it is present need to be known. Inductively coupled plasma mass spectrometry (ICP-MS) was used after high-performance liquid chromatographic (HPLC) separation, as was electrospray ionization mass spectrometry (ESI-MS). The effect of variation of the number of carbon atoms in perfluorinated carboxylic acids used as ion-pairing agents for the separation of selenium compounds was examined. Trifluoroacetic acid (0.1%), pentafluoropropanoic acid (0.1%) or heptafluorobutanoic acid (0.1%; HFBA) were alternatively used as additives to methanol-water (1:99, v/v) solutions as mobile phases. Reversed-phase HPLC-ICP-MS with 0.1% HFBA in the mobile phase allowed more than 20 selenium compounds to be separated in 70 min in an isocratic elution mode; the separation of natural selenium-enriched sample extracts was examined and explained. The pH of the 0.1% HFBA solution was modified with hydrochloric acid or ammonia and the pH of the sample extracts before injection was modified in order to overcome unwanted double peak formation in the chromatograms of sample extracts. Oxidations of standard gamma-glutamyl-Se-methylselenocysteine and Se-methylselenocysteine were carried out using 30% H2O2 solution and identifications of selenium-containing oxidation products were made using HPLC-ICP-MS and HPLC-ESI-MS. The principal organic oxidation product in both cases was methaneseleninic acid (MeSeO2H).

  9. Fit for purpose validated method for the determination of the strontium isotopic signature in mineral water samples by multi-collector inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Brach-Papa, Christophe; Van Bocxstaele, Marleen; Ponzevera, Emmanuel; Quétel, Christophe R.

    2009-03-01

    A robust method allowing the routine determination of n( 87Sr)/ n( 86Sr) with at least five significant decimal digits for large sets of mineral water samples is described. It is based on 2 consecutive chromatographic separations of Sr associated to multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) measurements. Separations are performed using commercial pre-packed columns filled with "Sr resin" to overcome isobaric interferences affecting the determination of strontium isotope ratios. The careful method validation scheme applied is described. It included investigations on all parameters influencing both chromatographic separations and MC-ICPMS measurements, and also the test on a synthetic sample made of an aliquot of the NIST SRM 987 certified reference material dispersed in a saline matrix to mimic complex samples. Correction for mass discrimination was done internally using the n( 88Sr)/ n( 86Sr) ratio. For comparing mineral waters originating from different geological backgrounds or identifying counterfeits, calculations involved the well known consensus value (1/0.1194) ± 0 as reference. The typical uncertainty budget estimated for these results was 40 'ppm' relative ( k = 2). It increased to 150 'ppm' ( k = 2) for the establishment of stand alone results, taking into account a relative difference of about 126 'ppm' systematically observed between measured and certified values of the NIST SRM 987. In case there was suspicion of a deviation of the n( 88Sr)/ n( 86Sr) ratio (worst case scenario) our proposal was to use the NIST SRM 987 value 8.37861 ± 0.00325 ( k = 2) as reference, and assign a typical relative uncertainty budget of 300 'ppm' ( k = 2). This method is thus fit for purpose and was applied to eleven French samples.

  10. Microwave-assisted extraction and ion chromatography dynamic reaction cell inductively coupled plasma mass spectrometry for the speciation analysis of arsenic and selenium in cereals.

    PubMed

    Tsai, Chia-Ying; Jiang, Shiuh-Jen

    2011-01-01

    An ion chromatography dynamic reaction cell inductively coupled plasma mass spectrometric (IC-DRC-ICP-MS) method for the speciation of arsenic and selenium compounds is described. Chromatographic separation was performed in a gradient elution mode using 0.5 mmol L(-1) ammonium citrate in 1% methanol (pH 4.5) and 15 mmol L(-1) ammonium citrate in 1% methanol (pH 8.0). The potentially interfering (38)Ar(40)Ar(+) and (40)Ar(40)Ar(+) at selenium masses of m/z 78 and 80 were reduced in intensity by approximately 3 orders of magnitude by using 1.0 mL min(-1) CH(4) as a reactive cell gas in the DRC. Arsenic was determined as the adduct ion (75)As(12)CH(2)(+) at m/z 89. The detection limits of the procedure were in the ranges of 0.006-0.009 ng As mL(-1) and 0.009-0.03 ng Se mL(-1), respectively. This method has been applied to determine various arsenic and selenium compounds in cereal samples. The accuracy of the method has been verified by comparing the sum of the concentrations of individual species obtained by the present procedure with the total concentration of elements. The arsenic and selenium compounds were quantitatively extracted with a Protease XIV and α-amylase solution in a microwave field at 70°C during a period of 30 min. The spike recoveries were in the range of 94-105% for all determinations.

  11. Evaluation of the multi-element capabilities of collision/reaction cell inductively coupled plasma-mass spectrometry in wine analysis.

    PubMed

    Grindlay, Guillermo; Mora, Juan; de Loos-Vollebregt, Margaretha T C; Vanhaecke, Frank

    2014-10-01

    This work explores the multi-element capabilities of inductively coupled plasma-mass spectrometry with collision/reaction cell technology (CCT-ICP-MS) for the simultaneous determination of both spectrally interfered and non-interfered nuclides in wine samples using a single set of experimental conditions. The influence of the cell gas type (i.e. He, He+H2 and He+NH3), cell gas flow rate and sample pre-treatment (i.e. water dilution or acid digestion) on the background-equivalent concentration (BEC) of several nuclides covering the mass range from 7 to 238u has been studied. Results obtained in this work show that, operating the collision/reaction cell with a compromise cell gas flow rate (i.e. 4 mL min(-1)) improves BEC values for interfered nuclides without a significant effect on the BECs for non-interfered nuclides, with the exception of the light elements Li and Be. Among the different cell gas mixtures tested, the use of He or He+H2 is preferred over He+NH3 because NH3 generates new spectral interferences. No significant influence of the sample pre-treatment methodology (i.e. dilution or digestion) on the multi-element capabilities of CCT-ICP-MS in the context of simultaneous analysis of interfered and non-interfered nuclides was observed. Nonetheless, sample dilution should be kept at minimum to ensure that light nuclides could be quantified in wine. Finally, a direct 5-fold aqueous dilution is recommended for the simultaneous trace and ultra-trace determination of spectrally interfered and non-interfered elements in wine by means of CCT-ICP-MS. The use of the CCT is mandatory for interference-free ultra-trace determination of Ti and Cr. Only Be could not be determined when using the CCT due to a deteriorated limit of detection when compared to conventional ICP-MS.

  12. Physicochemical characterization of titanium dioxide pigments using various techniques for size determination and asymmetric flow field flow fractionation hyphenated with inductively coupled plasma mass spectrometry.

    PubMed

    Helsper, Johannes P F G; Peters, Ruud J B; van Bemmel, Margaretha E M; Rivera, Zahira E Herrera; Wagner, Stephan; von der Kammer, Frank; Tromp, Peter C; Hofmann, Thilo; Weigel, Stefan

    2016-09-01

    Seven commercial titanium dioxide pigments and two other well-defined TiO2 materials (TiMs) were physicochemically characterised using asymmetric flow field flow fractionation (aF4) for separation, various techniques to determine size distribution and inductively coupled plasma mass spectrometry (ICPMS) for chemical characterization. The aF4-ICPMS conditions were optimised and validated for linearity, limit of detection, recovery, repeatability and reproducibility, all indicating good performance. Multi-element detection with aF4-ICPMS showed that some commercial pigments contained zirconium co-eluting with titanium in aF4. The other two TiMs, NM103 and NM104, contained aluminium as integral part of the titanium peak eluting in aF4. The materials were characterised using various size determination techniques: retention time in aF4, aF4 hyphenated with multi-angle laser light spectrometry (MALS), single particle ICPMS (spICPMS), scanning electron microscopy (SEM) and particle tracking analysis (PTA). PTA appeared inappropriate. For the other techniques, size distribution patterns were quite similar, i.e. high polydispersity with diameters from 20 to >700 nm, a modal peak between 200 and 500 nm and a shoulder at 600 nm. Number-based size distribution techniques as spICPMS and SEM showed smaller modal diameters than aF4-UV, from which mass-based diameters are calculated. With aF4-MALS calculated, light-scattering-based "diameters of gyration" (Øg) are similar to hydrodynamic diameters (Øh) from aF4-UV analyses and diameters observed with SEM, but much larger than with spICPMS. A Øg/Øh ratio of about 1 indicates that the TiMs are oblate spheres or fractal aggregates. SEM observations confirm the latter structure. The rationale for differences in modal peak diameter is discussed.

  13. Certification of Total Arsenic in Blood and Urine Standard Reference Materials by Radiochemical Neutron Activation Analysis and Inductively Coupled Plasma - Mass Spectrometry

    PubMed Central

    Paul, Rick L.; Davis, W. Clay; Yu, Lee; Murphy, Karen E.; Guthrie, William F.; Leber, Dennis D.; Bryan, Colleen E.; Vetter, Thomas W.; Shakirova, Gulchekhra; Mitchell, Graylin; Kyle, David J.; Jarrett, Jeffery M.; Caldwell, Kathleen L.; Jones, Robert L.; Eckdahl, Steven; Wermers, Michelle; Maras, Melissa; Palmer, C. D.; Verostek, M.F.; Geraghty, C. M.; Steuerwald, Amy J.; Parsons, Patrick J.

    2015-01-01

    A newly developed procedure for determination of arsenic by radiochemical neutron activation analysis (RNAA) was used to measure arsenic at four levels in SRM 955c Toxic Elements in Caprine Blood and at two levels in SRM 2668 Toxic Elements in Frozen Human Urine for the purpose of providing mass concentration values for certification. Samples were freeze-dried prior to analysis followed by neutron irradiation for 3 h at a fluence rate of 1×1014cm−2s−1. After sample dissolution in perchloric and nitric acids, arsenic was separated from the matrix by extraction into zinc diethyldithiocarbamate in chloroform, and 76As quantified by gamma-ray spectroscopy. Differences in chemical yield and counting geometry between samples and standards were monitored by measuring the count rate of a 77As tracer added before sample dissolution. RNAA results were combined with inductively coupled plasmamass spectrometry (ICP-MS) values from NIST and collaborating laboratories to provide certified values of (10.81 ± 0.54) μg/kg and (213.1 ± 0.73) μg/kg for SRM 2668 Levels I and II, and certified values of (21.66 ± 0.73) μg/kg, (52.7 ± 1.1) μg/kg, and (78.8 ± 4.9) μg/kg for SRM 955c Levels 2, 3, and 4 respectively. Because of discrepancies between values obtained by different methods for SRM 955c Level 1, an information value of < 5 μg/kg was assigned for this material. PMID:26300575

  14. Pharmacokinetics and tissue distribution of novel platinum containing anticancer agent BP‐C1 studied in rabbits using sector field inductively coupled plasma mass spectrometry

    PubMed Central

    Navolotskii, Denis V.; Ivanenko, Natalya B.; Fedoros, Elena I.; Panchenko, Andrey V.

    2015-01-01

    A method of platinum quantification in whole blood samples after microwave digestion using sector field inductively coupled plasma mass spectrometry has been developed. The following analytical figures of merit have been established: limit of detection 1.1 µg/L for blood samples, dynamic range 3.6–200 µg/L, intra‐day precision (relative standard deviation, n = 9) did not exceed 5%. Spiked samples were analyzed for method validation. The method was used for pharmacokinetics studies of a novel anti‐cancer drug BP‐С1, a complex of cis‐configured platinum and benzene‐poly‐carboxylic acids. Main pharmacokinetic parameters (area under curve, maximum concentration, clearance, half‐life times for α‐ and β‐phase) were estimated for two dosage forms of BP‐C1 0.05 and 0.125 mass %. Pharmacokinetic curves were assessed for single and course administration. Studies were performed using rabbits (n = 6) as a model. BP‐C1 was injected intramuscularly. The study established dose proportionality of the tested dosage forms and suggested clinical dosing schedule: 5 days of injections followed by 2 days’ break. Platinum tissue distribution was studied in tissue samples collected 20 days after the last injection. Predominant platinum accumulation was observed in kidneys, liver, and muscles near injection site. ‘Slow’ phase of platinum excretion kinetics may be related to the muscles at the injection site. © 2015 The Authors. Drug Testing and Analysis published by John Wiley & Sons Ltd. PMID:26061351

  15. Determination of As, Cd, Pb, and Hg in urine using inductively coupled plasma mass spectrometry with the direct injection high efficiency nebulizer

    NASA Astrophysics Data System (ADS)

    Minnich, Michael G.; Miller, Derek C.; Parsons, Patrick J.

    2008-03-01

    The application of the large-bore direct injection high efficiency nebulizer (LB-DIHEN) for the determination of arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg) in urine by inductively coupled plasma mass spectrometry (ICP-MS) is described. The LB-DIHEN is compared with the standard method using a concentric pneumatic nebulizer and cyclonic spray chamber. In addition to the toxicological significance of As, Cd, Pb, and Hg, these elements represent a cross-section of analytical issues including spectral interferences (e.g., 40Ar 35Cl + on 75As + and 98Mo 16O + on 114Cd +) and memory effects (Hg). In this study, the low sample consumption of the LB-DIHEN is used to reduce the volume of urine needed for analysis, and to reduce the volume of final diluted sample required for analysis. Eliminating the spray chamber and reducing the dead volume of the nebulizer reduces memory effects, especially for analytes such as Hg. The Dynamic Reaction Cell (DRC) is used in this study to attenuate the background level of ArCl + in spite of the increase in the solvent load and, in turn, the urine matrix (chloride) delivered to the plasma by the LB-DIHEN. This is the first report on coupling the LB-DIHEN to a standard autosampler for unattended sample analysis. The robustness of direct injection nebulization for routine analysis and the issues associated with automation of the sample introduction process are discussed. Although the figures of merit (sensitivity, limit of detection, and precision) determined for both nebulizers are slightly poorer for the LB-DIHEN than for the concentric pneumatic nebulizer, there is not a clinically significant difference between the results for both sample introduction systems. The accuracy of results is assessed using archived urine materials that are circulated by several different proficiency testing (PT) programs and external quality assessment schemes (EQAS). Results obtained using the LB-DIHEN were within the acceptable range

  16. Biomonitoring of 20 trace elements in blood and urine of occupationally exposed workers by sector field inductively coupled plasma mass spectrometry.

    PubMed

    Ivanenko, N B; Ivanenko, A A; Solovyev, N D; Zeimal', A E; Navolotskii, D V; Drobyshev, E J

    2013-11-15

    A sector field inductively coupled plasma mass spectrometry method for the determination of Ag, Al, As, Ba, Be, Cd, Co, Cr, Cs, Cu, Fe, Mn, Ni, Pb, Se, Sr, Tl, U, V and Zn in whole blood and urine was designed. Microwave-assisted digestion with concentrated nitric acid was used for blood samples. Urine samples were analyzed after 1/50 (v/v) dilution with 5% (v/v) nitric acid. For beryllium the necessity of medium resolution mode (R=4000) was shown. Method validation was performed using blood and urine reference materials and by analyzing of spiked samples. For the designed method relative standard deviation (RSD) for the concentration range 0.01-1.0 μg/L was 5-10%. RSD did not exceed 3% when trace elements concentrations were above 1.0 μg/L. Method detection limits (3σ): Ag 0.7 ng/L, Al 16 ng/L, As 3.4 ng/L, Ba 0.02 ng/L, Be 1.5 ng/L, Cd 7.7 ng/L, Co 1.0 ng/L, Cr 2.8 ng/L, Cs 9.8 ng/L, Cu 27 ng/L, Fe 1.1 ng/L, Mn 1.8 ng/L, Ni 17 ng/L, Pb 13 ng/L, Se 0.07 ng/L, Sr 5.7 ng/L, Tl 0.2 ng/L, U 0.1 ng/L, V 0.7 ng/L and Zn 1.2 ng/L. A developed method was applied for trace element biomonitoring of occupationally exposed workers of a beryllium processing enterprise. For preliminary risk assessment technological surface dust had been analyzed by inductively coupled plasma optical emission spectrometry. Based upon results of 50 blood and 40 urine samples analyses occupational exposure evaluation was performed. Exposure risks were found not to exceed acceptable ranges. Possible health hazards were found for Be and also Al, Cr, Mn. Occupational health and safety recommendations for the biomonitored enterprise medical care unit were issued as a result of the current investigation.

  17. 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

    NASA Astrophysics Data System (ADS)

    Cheng, Heyong; Liu, Jinhua; Xu, Zigang; Yin, Xuefeng

    2012-07-01

    A microfluidic sub-microliter sample introducing system was developed for direct analysis of Chinese rice wine by inductively coupled plasma mass spectrometry (ICP-MS). It consisted of a microfluidic chip integrating variable-volume sampling channels (0.1-0.8 μL), an eight-way multi-functional valve used in flow injection analysis (FIA), a syringe pump and a peristaltic pump of the Ar ICP-MS instrument. Three solutions, i.e., 15, 40 and 100 g L- 1 glucose in 20% ethanol were used to simulate Chinese rice wine of the dry type, the semidry type and the semisweet type, each. The effects of their volume introduced into ICP-MS on the plasma stability and ICP-MS intensities were studied. The experimental results showed that neither alteration of plasma stability nor carbon deposition was observed when the sampling volume of 20% ethanol containing 100 g L- 1 glucose was downscaled to 0.8 μL. Further reducing the sampling volume to 0.4 μL, no significant difference between the intensities of multi-element standard prepared in three simulated Chinese rice wine matrices and those in aqueous solution was observed. It indicated no negative effect of Chinese rice wine matrix on the ICP-MS intensities. A sampling volume of 0.4 μL was considered to be a good compromise between sensitivity and matrix effect. The flow rate of the carrier was chosen as 20 μL min- 1 for obtaining peaks with the highest peak height within the shortest time. Based on these observations, a microflow injection (μFI) method for the direct determination of cadmium and lead in Chinese rice wine by ICP-MS using an external aqueous calibration was developed. The sample throughput was 45 h- 1 with the detection limit of 19.8 and 10.4 ng L- 1 for Cd and Pb, respectively. The contents of Cd and Pb in 10 Chinese rice wine samples were measured. The results agreed well with those determined by ICP-MS with the conventional sampling system after microwave assisted digestion. The recoveries of three Chinese

  18. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

    2016-09-28

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous

  19. Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lazarov, Marina; Horn, Ingo

    2015-09-01

    Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ65Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as (32S33S)+ and (32S-16O17O)+ do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn-H or doubly-charged Sn2 + that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ65Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm2 for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm2 which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible to measure Cu isotopic ratios in native copper and Cu-bearing sulfides

  20. Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Frick, Daniel A; Schuessler, Jan A; von Blanckenburg, Friedhelm

    2016-09-28

    Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous

  1. Speciation of metallothionein-like proteins of the mussel Mytilus edulis by orthogonal separation mechanisms with inductively coupled plasma-mass spectrometry detection: effect of selenium administration

    NASA Astrophysics Data System (ADS)

    Ferrarello, Claudio N.; del Rosario Fernández de la Campa, María.; Francisco Carrasco, José; Sanz-Medel, Alfredo

    2002-03-01

    Several complementary separation mechanisms (size-exclusion chromatography, SEC; fast protein liquid chromatography, FPLC; reverse-phase chromatography, RPC) have been coupled to inductively coupled plasma mass spectrometry (ICP-MS) detection to investigate the speciation of Cd, Se, Cu and Zn in mussel hepatopancreas. SEC with double-focusing (DF) ICP-MS detection was used first for speciation analysis of those four trace elements, both in uncontaminated mussels and in mussels exposed to Cd (500 μg l -1) or to Cd+Se (500 μg l -1 of each element). Observed SEC results indicated that Se does not seem to significantly bind to metallothionein-like proteins (MLPs) 'in vivo'. Total cytosolic Cd and MLPs content were lower in Cd+Se exposed mussels than those exposed to Cd only. For each treatment, 50 μl of the SEC peak fraction containing the MLPs was used to perform fast protein liquid chromatography coupled 'on-line' with a quadrupole (Q) ICP-MS. 82Se and 114Cd isotopes were simultaneously monitored. Four and five Cd/MLPs isoforms were then detected in mussels exposed to only Cd and Cd+Se, respectively. In contrast, no signs of Se/MLP isoforms were found for both treatments. Subsequently, the bulk of MLPs eluting from the FPLC system were isolated and lyophilizated. A 50-μl aliquot of such reconstituted lyophilisate was then injected into a Vydac C 8 Reverse-Phase column directly connected to the Q-ICP-MS. Results confirmed the presence of one more Cd/MLP peak in those mussels exposed to Cd+Se. However, the number of Cd/MLP peaks detected decreased to three and four in only Cd and Cd+Se exposed animals, respectively. These results tend to indicate that Se, which does not trigger the biosynthesis of MLPs, could probably orient such synthesis towards the generation of a new Cd/MLP isoform in mussels submitted to both elements. The possible interrelation/complementation between Se and MLP against Cd toxicity is discussed.

  2. Determination of compound-specific Hg isotope ratios from transient signals using gas chromatography coupled to multicollector inductively coupled plasma mass spectrometry (MC-ICP/MS).

    PubMed

    Dzurko, Mark; Foucher, Delphine; Hintelmann, Holger

    2009-01-01

    MeHg and inorganic Hg compounds were measured in aqueous media for isotope ratio analysis using aqueous phase derivatization, followed by purge-and-trap preconcentration. Compound-specific isotope ratio measurements were performed by gas chromatography interfaced to MC-ICP/MS. Several methods of calculating isotope ratios were evaluated for their precision and accuracy and compared with conventional continuous flow cold vapor measurements. An apparent fractionation of Hg isotopes was observed during the GC elution process for all isotope pairs, which necessitated integration of signals prior to the isotope ratio calculation. A newly developed average peak ratio method yielded the most accurate isotope ratio in relation to values obtained by a continuous flow technique and the best reproducibility. Compound-specific isotope ratios obtained after GC separation were statistically not different from ratios measured by continuous flow cold vapor measurements. Typical external uncertainties were 0.16 per thousand RSD (n = 8) for the (202)Hg(/198)Hg ratio of MeHg and 0.18 per thousand RSD for the same ratio in inorganic Hg using the optimized operating conditions. Using a newly developed reference standard addition method, the isotopic composition of inorganic Hg and MeHg synthesized from this inorganic Hg was measured in the same run, obtaining a value of delta (202)Hg = -1.49 +/- 0.47 (2SD; n = 10). For optimum performance a minimum mass of 2 ng per Hg species should be introduced onto the column. PMID:18488203

  3. Determination of plutonium and other transuranic elements by inductively coupled plasma mass spectrometry: A historical perspective and new frontiers in the environmental sciences

    NASA Astrophysics Data System (ADS)

    Ketterer, Michael E.; Szechenyi, Scott C.

    2008-07-01

    Inductively coupled plasma mass spectrometry (ICPMS), particularly with sector field mass analyzers (SF-ICPMS), has emerged in the past several years as an excellent analytical technique for rapid, highly sensitive determination of transuranic elements (TRU) in environmental samples. SF-ICPMS has advantages of simplicity of sample preparation, high sample throughput, widespread availability in laboratories worldwide, and relatively straightforward operation when compared to other competing mass spectrometric techniques. Arguably, SF-ICPMS is the preferred technique for routine, high-throughput determination of 237Np and the Pu isotopes, excepting 238Pu, at fg-pg levels in environmental samples. Many research groups have now demonstrated the SF-ICPMS determination of 239 + 240 Pu activities, 240Pu/ 239Pu and other Pu atom ratios in several different application areas. Many studies have examined the relative contribution of global fallout vs. local/regional Pu sources in the environment through measurement of 240Pu/ 239Pu and, in some cases, 241Pu/ 239Pu and 242Pu/ 239Pu. "Stratospheric fallout", which was deposited from thermonuclear tests, conducted largely during the 1952-1964 time period, is characterized by a well-defined 240Pu/ 239Pu of ~ 0.18, while most other sources have different ratios. Examples of local/regional Pu sources are the Nevada Test Site, the Chernobyl plume, and accidents at Palomares, Spain and Thule, Greenland. The determination of Pu activities and atom ratios has stimulated much interest in the use of Pu as a marine tracer; several studies have shown that Pu is transported over long distances by ocean currents. 240Pu/ 239Pu ratios > 0.20 in sediments and seawater of the North Pacific are ascribed to ocean current transport of fallout from the Pacific Proving Ground. In nuclear forensics, much effort is focused on detection and fingerprinting of small amounts of TRU in environmental samples consisting of bulk material or individual isolated

  4. IgY14 and SuperMix immunoaffinity separations coupled with liquid chromatography-mass spectrometry for human plasma proteomic biomarker discovery

    SciTech Connect

    Shi, Tujin; Zhou, Jianying; Gritsenko, Marina A.; Hossain, Mahmud; Camp, David G.; Smith, Richard D.; Qian, Weijun

    2012-02-01

    Interest in the application of advanced proteomics technologies to human blood plasma- or serum-based clinical samples for the purpose of discovering disease biomarkers continues to grow; however, the enormous dynamic range of protein concentrations in these types of samples (often >10 orders of magnitude) represents a significant analytical challenge, particularly for detecting low-abundance candidate biomarkers. In response, immunoaffinity separation methods for depleting multiple high- and moderate-abundance proteins have become key tools for enriching low-abundance proteins and enhancing detection of these proteins in plasma proteomics. Herein, we describe IgY14 and tandem IgY14-Supermix separation methods for removing 14 high-abundance and up to 60 moderate-abundance proteins, respectively, from human blood plasma and highlight their utility when combined with liquid chromatography-tandem mass spectrometry for interrogating the human plasma proteome.

  5. A dipole-assisted solid-phase extraction microchip combined with inductively coupled plasma-mass spectrometry for online determination of trace heavy metals in natural water.

    PubMed

    Shih, Tsung-Ting; Hsu, I-Hsiang; Chen, Shun-Niang; Chen, Ping-Hung; Deng, Ming-Jay; Chen, Yu; Lin, Yang-Wei; Sun, Yuh-Chang

    2015-01-21

    We employed a polymeric material, poly(methyl methacrylate) (PMMA), for fabricating a microdevice and then implanted the chlorine (Cl)-containing solid-phase extraction (SPE) functionality into the PMMA chip to develop an innovative on-chip dipole-assisted SPE technique. Instead of the ion-ion interactions utilized in on-chip SPE techniques, the dipole-ion interactions between the highly electronegative C-Cl moieties in the channel interior and the positively charged metal ions were employed to facilitate the on-chip SPE procedures. Furthermore, to avoid labor-intensive manual manipulation, a programmable valve manifold was designed as an interface combining the dipole-assisted SPE microchip and inductively coupled plasma-mass spectrometry (ICP-MS) to achieve the fully automated operation. Under the optimized operation conditions for the established system, the detection limits for each analyte ion were obtained based on three times the standard deviation of seven measurements of the blank eluent solution. The limits ranged from 3.48 to 20.68 ng L(-1), suggesting that this technique appears uniquely suited for determining the levels of heavy metal ions in natural water. Indeed, a series of validation procedures demonstrated that the developed method could be satisfactorily applied to the determination of trace heavy metals in natural water. Remarkably, the developed device was durable enough to be reused more than 160 times without any loss in its analytical performance. To the best of our knowledge, this is the first study reporting on the combination of a dipole-assisted SPE microchip and elemental analysis instrument for the online determination of trace heavy metal ions.

  6. Determination of total lead in lipstick: development and validation of a microwave-assisted digestion, inductively coupled plasma-mass spectrometric method.

    PubMed

    Hepp, Nancy M; Mindak, William R; Cheng, John

    2009-01-01

    Recent reports describing the presence of lead (Pb) in lipsticks have suggested that, under ordinary use, the potential amount of Pb exposure is harmful. To permit independent assessment of the Pb contamination, a method for determining total Pb in lipstick using microwave-assisted digestion and analysis employing inductively coupled plasma-mass spectrometry (ICP-MS) was developed and validated. Since lipsticks may contain fats, oils, pigments, dyes, and minerals, several reference materials (RM) were analyzed, including coal, wear metals in oil, organic Pb in oil, milk powder, and estuarine sediment. With the exception of the RM with mineral content (estuarine sediment), complete recovery of Pb from the RMs was obtained by simple nitric acid (HNO(3)) digestion. Complete recovery of Pb from estuarine sediment was achieved only when hydrofluoric acid (HF) was added to the digestion mix, followed by treatment with excess boric acid (H(3)BO(3)) to neutralize the HF and to dissolve insoluble fluorides. Commercial lipsticks were tested for total Pb by the validated method. The detection limit was estimated to be 0.04 microg Pb/g. The average value obtained for the lipsticks was 1.07 microg/g. Undigested material was present in some lipstick digests when only HNO(3) was used, and generally lower Pb values were obtained. All of the Pb levels found by the U.S. Food and Drug Administration (FDA) were within the range the agency would expect to find in lipsticks formulated with permitted color additives and other ingredients prepared under good manufacturing practice (GMP) conditions. This method will be useful for the FDA and industry in helping to ensure the safety of cosmetic products.

  7. Rapid determination of plutonium isotopes in environmental samples using sequential injection extraction chromatography and detection by inductively coupled plasma mass spectrometry.

    PubMed

    Qiao, Jixin; Hou, Xiaolin; Roos, Per; Miró, Manuel

    2009-10-01

    This article presents an automated method for the rapid determination of 239Pu and 240Pu in various environmental samples. The analytical method involves the in-line separation of Pu isotopes using extraction chromatography (TEVA) implemented in a sequential injection (SI) network followed by detection of isolated analytes with inductively coupled plasma mass spectrometry (ICP-MS). The method has been devised for the determination of Pu isotopes at environmentally relevant concentrations, whereby it has been successfully applied to the analyses of large volumes/amounts of samples, for example, 100-200 g of soil and sediment, 20 g of seaweed, and 200 L of seawater following analyte preconcentration. The investigation of the separation capability of the assembled SI system revealed that up to 200 g of soil or sediment can be treated using a column containing about 0.70 g of TEVA resin. The analytical results of Pu isotopes in the reference materials showed good agreement with the certified or reference values at the 0.05 significance level. Chemical yields of Pu ranged from 80 to 105%, and the decontamination factors for uranium, thorium, mercury and lead were all above 10(4). The duration of the in-line extraction chromatographic run was <1.5 h, and the proposed setup was able to handle up to 20 samples (14 mL each) in a fully automated mode using a single chromatographic column. The SI manifold is thus suitable for rapid and automated determination of Pu isotopes in environmental risk assessment and emergency preparedness scenarios. PMID:19722516

  8. Evaluation of Nickel and Chromium Ion Release During Fixed Orthodontic Treatment Using Inductively Coupled Plasma-Mass Spectrometer: An In Vivo Study

    PubMed Central

    Nayak, Rabindra S; Khanna, Bharti; Pasha, Azam;