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Sample records for plasma-mass spectrometry multi-elemental

  1. Determination of trace multi-elements in coal fly ash by inductively coupled plasma mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    XIE Hua-lin; TANG You-gen; LI Yu-jie; LI Li-bo

    2007-01-01

    The contents of Cr,Cu, Ni, As, Cd and Pb in coal fly ash were determined by a high resolution inductively coupled plasma mass spectrometry method.The sample digestions were performed in closed microwave vessels with HN03, HClO4 and HF.The optimum conditions for the determination were obtained.The applicability of the proposed method was validated by the analysis of coal fly ash reference material (NIST SRM 1633a). The results show that most of the spectral interferences can be avoided by measuring in the high resolution mode(maximum mass resolution R=9 000).The detection limit is from 0.05 to 0.21μg/g,and the precision is fine with relative standard deviation less than 4.3%.

  2. Multi-elemental analysis of brain tissue from healthy Wistar rats using sector field inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Mitchell C. [Molecular Structure and Detection Group, School of Environmental and Life Sciences, University of Newcastle, University Drive, Callaghan NSW 2308 (Australia); Parsons, Carl H. [School of Biomedical Science, University of Newcastle, Callaghan NSW 2308 (Australia); Calford, Mike B. [School of Biomedical Science, University of Newcastle, Callaghan NSW 2308 (Australia); Nagy-Felsobuki, Ellak I. von [Molecular Structure and Detection Group, School of Environmental and Life Sciences, University of Newcastle, University Drive, Callaghan NSW 2308 (Australia)]. E-mail: ellak@newcastle.edu.au

    2004-09-20

    The normal distribution of a range of elements in the brain tissue of healthy Wistar rats was established using sector field inductively coupled plasma mass spectrometry. A protocol was developed to determine concentrations of Ag, Cd, Hg, Pb, Bi, U, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As and Se in specific brain regions. The concentrations of these elements were determined in the range of 2{+-}1 (e.g. Cr in diencephalon) to 7558{+-}450 ng ml{sup -1} (e.g. Fe in olfactory bulb). The detection limits of the sixteen elements ranged between 5 and 300 pg ml{sup -1}, with U yielding the lowest and Fe the highest value. The validity of the protocol was assessed by the analysis of SRM 1577B Bovine Liver and brain tissue spike recoveries. A principal component analysis was used to reveal elemental patterns of the brain regions.

  3. Use of dried blood spots and inductively coupled plasma mass spectrometry for multi-element determination in blood.

    Science.gov (United States)

    Vacchina, Véronique; Huin, Vincent; Hulo, Sébastien; Cuny, Damien; Broly, Franck; Renom, Gilles; Perini, Jean-Marc

    2014-07-01

    The paper describes the development of an inductively coupled plasma mass spectrometry (ICP MS) method for multitrace element determination in dried blood spots (DBSs). The analytical conditions were optimized using Seronorm™ L-3 and L-1 Certified Reference Materials. The best results were obtained by sampling blood drops on a decontaminated PVDF filter membrane. After drying under metal-free conditions, the DBSs underwent acidic digestion and were analyzed with ICP MS. The method was then validated for As, Cd, Cu, Pb, Mo, Se and Zn. Using a matrix-matched calibration curve, the recovery levels ranged from 96% to 117%. The repeatability and reproducibility were generally below 15%. Limits of quantification ranging from 0.5 to 50 μg/L. In order to investigate the analytical procedure under real sampling conditions, the results obtained from DBSs and liquid blood aliquots (less subject to contamination) from two adult subjects were compared.

  4. A provenance study of iron archaeological artefacts by Inductively Coupled Plasma-Mass Spectrometry multi-elemental analysis

    Energy Technology Data Exchange (ETDEWEB)

    Desaulty, Anne-Marie [Laboratoire Pierre Suee CEA - CNRS/UMR 9956 Centre de Saclay, Bat. 637 91191 Gif sur Yvette, Cedex (France); Laboratoire Metallurgies et culture CNRS/UMR 5060 UTBM 90010 Belfort, Cedex (France); Mariet, Clarisse [Laboratoire Pierre Suee CEA - CNRS/UMR 9956 Centre de Saclay, Bat. 637 91191 Gif sur Yvette, Cedex (France)], E-mail: clarisse.mariet@cea.fr; Dillmann, Philippe [Laboratoire Pierre Suee CEA - CNRS/UMR 9956 Centre de Saclay, Bat. 637 91191 Gif sur Yvette, Cedex (France); Laboratoire Metallurgies et culture CNRS/UMR 5060 UTBM 90010 Belfort, Cedex (France); Joron, Jean Louis [Laboratoire Pierre Suee CEA - CNRS/UMR 9956 Centre de Saclay, Bat. 637 91191 Gif sur Yvette, Cedex (France); Institut de Physique du Globe de Paris, Paris VI et Paris VII, 4, place Jussieu 75252 Paris, Cedex 05 (France); Fluzin, Philippe [Laboratoire Metallurgies et culture CNRS/UMR 5060 UTBM 90010 Belfort, Cedex (France)

    2008-11-15

    Raw materials and wastes (i.e. ore, slag and laitier) from ironmaking archaeological sites have been analyzed in order to understand the behavior of the trace elements in the ancient ironmaking processes and to find the significant-most elements to characterize an iron making region. The ICP-MS (Inductively Coupled Plasma Mass Spectrometry) appears to be an excellent technique for this type of studies. The comparison between the ICP-MS results obtained with the Standard Addition method and the INAA (Instrumental Neutron Activation Analyses) results proved that Sc, Co, (Ni), Rb, Cs, Ba, La, Ce, Sm, Eu, Yb, Hf, Th, U contents in the ores, slag and laitiers, and Co and Ni contents in the cast iron can be successfully determined by ICP-MS after wet acid digestion (low detection limits, good sensitivity and precision). By using significant trace element pairs (Yb/Ce, Ce/Th, La/Sc, U/Th, Nb/Y) present in the ores, laitiers and slag, it is possible to discriminate different French ironmaking regions as the Pays de Bray, Lorraine and Pays d'Ouche. These results open the way to further studies on the provenance of iron objects. The comparison between the ICP-MS results obtained with the Standard Calibration Curves method and the INAA results shows that matrices rich in iron, affect the ICP-MS analyses by suppressing the analytes signal. Further studies are necessary to improve understanding matrix effects.

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

    Science.gov (United States)

    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.

  6. Multi-element analysis of urine using dynamic reaction cell inductively coupled plasma mass spectrometry (ICP-DRC-MS — A practical application

    Directory of Open Access Journals (Sweden)

    Renata Brodzka

    2013-04-01

    Full Text Available Objectives: The method for the determination of As, Al, Cd, Ni, Pb (toxic elements and Cr, Co, Cu, Fe, Mn, Zn (essential elements in human urine by the use of Inductively Coupled Plasma Mass Spectrometry (quadrupole ICP-MS DRCe Elan, Perkin Elmer with the dynamic reaction cell (DRC was developed. Materials and Methods: The method has been applied for multi-element analysis of the urine of 16 non-exposed healthy volunteers and 27 workers employed in a copper smelter. The analysis was conducted after initial 10-fold dilution of the urine samples with 0,1% nitric acid. Rhodium was used as an internal standard. The method validation parameters such as detection limit, sensitivity, precision were described for all elements. Accuracy of the method was checked by the regular use of certified reference materials ClinCheck®-Control Urine (Recipe as well as by participation of the laboratory in the German External Quality Assessment Scheme (G-EQUAS. Results: The detection limits (DL 3s of the applied method were 0.025, 0.007, 0.002, 0.004, 0.004, 0.086, 0.037, 0.009, 0.016, 0.008, 0.064 (μg/l for Al, As, Cd, Cr, Co, Cu, Fe, Mn, Ni, Pb, Zn in urine, respectively. For each element linearity with correlation coefficient of at least 0.999 was determined. Spectral interferences from some of the ions were removed using DRC-e with addition of alternative gas: methane for cobalt, copper, cadmium, chromium, iron, manganese, nickel and rhodium, and oxygen for arsenic. Conclusions: The developed method allows to determine simultaneously eleven elements in the urine with low detection limits, high sensitivity and good accuracy. Moreover, the method is appropriate for the assessment of both environmental and occupational exposure.

  7. Flow injection on-line dilution for multi-element determination in human urine with detection by inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Wang, J.H.; Hansen, E.H.; Gammelgaard, Bente

    2001-01-01

    A simple flow injection on-line dilution procedure with detection by inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of copper, zinc, arsenic, lead, selenium, nickel and molybdenum in human urine. Matrix effects were minimized by employing a dilution fact...... of 16.5 with on-line standard addition, and Rh-103 was used as internal standard to compensate for signal fluctuation. The procedure was validated by the analysis of two standard reference materials SRM 2670 (NIST) and Seronorm (TM) Trace Elements in Urine. Recovery experiments were pet...... human urine samples. No correlations between the concentrations of the elements were observed. (C) 2001 Elsevier Science B.V. All rights reserved...

  8. Multi-element quantification of ancient/historic glasses by laser ablation inductively coupled plasma mass spectrometry using sum normalization calibration

    Energy Technology Data Exchange (ETDEWEB)

    Elteren, Johannes T. van, E-mail: elteren@ki.si [National Institute of Chemistry, Hajdrihova 19, 1001 Ljubljana (Slovenia); Tennent, Norman H. [Fyne Conservation Services, St. Catherine' s, Argyll PA25 8BA, Scotland (United Kingdom); Faculty of Humanities, University of Amsterdam, Oude Turfmarkt 147, 1012GC Amsterdam (Netherlands); Selih, Vid S. [National Institute of Chemistry, Hajdrihova 19, 1001 Ljubljana (Slovenia)

    2009-06-30

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for quantitative analysis of ancient/historic glasses is subject to calibration issues which have been addressed in this work. Since ancient/historic glasses have widely ranging matrix compositions, a complementary analysis by an alternative method is generally employed to determine at least one major element which can be used as an internal standard. We demonstrate that such a complementary analysis is unnecessary using a so-called sum normalization calibration technique (mathematically formulated) by simultaneous measurement of 54 elements and normalizing them to 100% [w/w] based on their corresponding oxide concentrations. The crux of this approach is that by assuming a random internal standard concentration of a particular major oxide, e.g. SiO{sub 2}, the normalization algorithm varies the internal standard concentration until the cumulated concentrations of all 54 elemental oxides reach 100% [w/w]. The fact that 54 elements are measured simultaneously predetermines the laser ablation mode to rastering. Nine glass standards, some replicating historic compositions, were used for calibration. The linearity of the calibration graphs (forced through the origin) represented by the relative standard deviations in the slope were between 0.1 and 6.6% using SiO{sub 2} as an internal standard. This allows high-accuracy determination of elemental oxides as confirmed by good agreement between found and reported values for major and minor elemental oxides in some synthetic glasses with typical medieval composition (European Science Foundation 151 and 158). Also for trace elemental concentrations of lanthanides in a reference glass (P and H Developments Ltd. DLH7, a base glass composition with nominally 75 {mu}g g{sup -1} elements added) accurate data were obtained. Interferences from polyatomic species and doubly charged species on the masses of trace elements are possible, depending on the base

  9. Multi-elemental characterization of tunnel and road dusts in Houston, Texas using dynamic reaction cell-quadrupole-inductively coupled plasma-mass spectrometry: Evidence for the release of platinum group and anthropogenic metals from motor vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Spada, Nicholas; Bozlaker, Ayse [Department of Civil and Environmental Engineering, University of Houston, Houston, TX 77204-4003 (United States); Chellam, Shankararaman, E-mail: chellam@uh.edu [Department of Civil and Environmental Engineering, University of Houston, Houston, TX 77204-4003 (United States); Department of Chemical and Biomolecular Engineering, University of Houston, Houston, TX 77204-4004 (United States)

    2012-07-20

    Highlights: Black-Right-Pointing-Pointer Analytical method for PGEs, main group, transition and rare earth metals developed. Black-Right-Pointing-Pointer Comprehensive characterization of road and tunnel dust samples was accomplished. Black-Right-Pointing-Pointer PGEs in dusts arise from autocatalyst attrition. Black-Right-Pointing-Pointer Mobile sources also contributed to Cu, Zn, Ga, As, Mo, Cd, Sn, Sb, Ba, W and Pb. Black-Right-Pointing-Pointer All other elements, including rare earths arose from crustal sources. - Abstract: Platinum group elements (PGEs) including Rh, Pd, and Pt are important tracers for vehicular emissions, though their measurement is often challenging and difficult to replicate in environmental campaigns. These challenges arise from sample preparation steps required for PGE quantitation, which often cause severe isobaric interferences and spectral overlaps from polyatomic species of other anthropogenically emitted metals. Consequently, most previous road dust studies have either only quantified PGEs or included a small number of anthropogenic elements. Therefore a novel analytical method was developed to simultaneously measure PGEs, lanthanoids, transition and main group elements to comprehensively characterize the elemental composition of urban road and tunnel dusts. Dust samples collected from the vicinity of high-traffic roadways and a busy underwater tunnel restricted to single-axle (predominantly gasoline-driven) vehicles in Houston, TX were analyzed for 45 metals with the newly developed method using dynamic reaction cell-quadrupole-inductively coupled plasma-mass spectrometry (DRC-q-ICP-MS). Average Rh, Pd and Pt concentrations were 152 {+-} 52, 770 {+-} 208 and 529 {+-} 130 ng g{sup -1} respectively in tunnel dusts while they varied between 6 and 8 ng g{sup -1}, 10 and 88 ng g{sup -1} and 35 and 131 ng g{sup -1} in surface road dusts. Elemental ratios and enrichment factors demonstrated that PGEs in dusts originated from autocatalyst

  10. Quantitative aspects of inductively coupled plasma mass spectrometry

    Science.gov (United States)

    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'.

  11. Minimally-invasive Laser Ablation Inductively Coupled Plasma Mass Spectrometry analysis of model ancient copper alloys

    Energy Technology Data Exchange (ETDEWEB)

    Walaszek, Damian [University of Warsaw, Faculty of Chemistry, Biological and Chemical Research Centre, Żwirki i Wigury 101, 02-089 Warszawa (Poland); Laboratory for Analytical Chemistry, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf (Switzerland); Senn, Marianne; Wichser, Adrian [Laboratory for Analytical Chemistry, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf (Switzerland); Faller, Markus [Laboratory for Jointing Technology and Corrosion, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf (Switzerland); Wagner, Barbara; Bulska, Ewa [University of Warsaw, Faculty of Chemistry, Biological and Chemical Research Centre, Żwirki i Wigury 101, 02-089 Warszawa (Poland); Ulrich, Andrea [Laboratory for Analytical Chemistry, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf (Switzerland)

    2014-09-01

    This work describes an evaluation of a strategy for multi-elemental analysis of typical ancient bronzes (copper, lead bronze and tin bronze) by means of laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS).The samples originating from archeological experiments on ancient metal smelting processes using direct reduction in a ‘bloomery’ furnace as well as historical casting techniques were investigated with the use of the previously proposed analytical procedure, including metallurgical observation and preliminary visual estimation of the homogeneity of the samples. The results of LA-ICPMS analysis were compared to the results of bulk composition obtained by X-ray fluorescence spectrometry (XRF) and by inductively coupled plasma mass spectrometry (ICPMS) after acid digestion. These results were coherent for most of the elements confirming the usefulness of the proposed analytical procedure, however the reliability of the quantitative information about the content of the most heterogeneously distributed elements was also discussed in more detail. - Highlights: • The previously proposed procedure was evaluated by analysis of model copper alloys. • The LA-ICPMS results were comparable to the obtained by means of XRF and ICPMS. • LA-ICPMS results indicated the usefulness of the proposed analytical procedure.

  12. Ion sampling and transport in Inductively Coupled Plasma Mass Spectrometry

    Science.gov (United States)

    Farnsworth, Paul B.; Spencer, Ross L.

    2017-08-01

    Quantitative accuracy and high sensitivity in inductively coupled plasma mass spectrometry (ICP-MS) depend on consistent and efficient extraction and transport of analyte ions from an inductively coupled plasma to a mass analyzer, where they are sorted and detected. In this review we examine the fundamental physical processes that control ion sampling and transport in ICP-MS and compare the results of theory and computerized models with experimental efforts to characterize the flow of ions through plasma mass spectrometers' vacuum interfaces. We trace the flow of ions from their generation in the plasma, into the sampling cone, through the supersonic expansion in the first vacuum stage, through the skimmer, and into the ion optics that deliver the ions to the mass analyzer. At each stage we consider idealized behavior and departures from ideal behavior that affect the performance of ICP-MS as an analytical tool.

  13. Quantification of Multi Elements in Geological Samples by Inductively Coupled Plasma-Mass Spectrometry with Pressurized Decomposition-Hydrochloric Acid Extraction%封闭压力酸溶-盐酸提取-电感耦合等离子体质谱法测定地质样品中的多元素

    Institute of Scientific and Technical Information of China (English)

    张保科; 温宏利; 王蕾; 马生凤; 巩爱华

    2011-01-01

    Rock, soil, sediments and other geological samples can be effectively decomposed by acid under high temperature and pressure, and be measured by Inductively Coupled Plasma-Mass Spectrometry ( ICP-MS ). The recoveries of most elements were satisfactory, except for the results of Zr, Hf, REEs, Rb, Th, and U. In this paper, the traditional pressurized acid digestion method has been improved as the sample was extracted by hydrochloric acid instead of nitric acid. 46 elements in the National Standard Materials of rock, soil and sediments can be accurately determined by this improved method. Sample weight was increased from 25 mg to 100m and digestion time was extended from 12 h to 48 h,which effectively resolved the problems including the representation of the samples and inadequate results for Rb, Sr, REEs and other elements dissolved by HN03. The results of many experiments showed that the 44 elements measured were consistent with standard values except for As and V elements, according to Cl interference in ICP-MS. Detection limits of the improved method were 0. 01 -0. 85 μg/g, with a precision RSD( n = 10 ) of 0. 73% -13. 1% and an accuracy RE( n = 10 )of less than 10%. The improved method is accurate, reliable and suitable for avariety of different types of geological samples.%高温、高压封闭压力酸溶可有效分解岩石、土壤、沉积物等地质样品,采用电感耦合等离子体质谱法(ICP-MS)进行测定,大部分元素可得到满意的回收率;但Zr、Hf、REEs、Rb、Th、U等元素用硝酸复溶困难,测定结果不准确.本文对传统的封闭压力酸溶方法进行改进,用盐酸复溶提取代替硝酸复溶提取,ICP-MS法测定岩石、土壤、沉积物等国家一级标准物质中Li、Be、Cr、Mn、Co、Ni、Cu、Zn、Ga、Rb、Sr、Mo、Cd、In、Cs、Ba、Ti、Zr、Nb、Sn、Sb、W、Hf、Ta、Tl、Pb、Bi、Th、U以及稀土元素(REEs)等46个元素.将原方法中的称样量25 mg加大至100 mg,溶样时间由12 h

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Todorov, Todor; Ejnik, John W.; Guandalini, Gustavo S.; Xu, Hanna; Hoover, Dennis; Anderson, Larry W.; 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 2 g 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.

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

    Science.gov (United States)

    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.

  17. Mapping of lead, magnesium and copper accumulation in plant tissues by laser-induced breakdown spectroscopy and laser-ablation inductively coupled plasma mass spectrometry

    Science.gov (United States)

    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.

  18. Mapping of lead, magnesium and copper accumulation in plant tissues by laser-induced breakdown spectroscopy and laser-ablation inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kaiser, J. [Institute of Physical Engineering, Faculty of Mechanical Engineering, Brno University of Technology, Technicka 2896/2, 616 69 Brno (Czech Republic)], E-mail: kaiser@fme.vutbr.cz; Galiova, M.; Novotny, K.; Cervenka, R. [Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic); Reale, L. [Faculty of Sciences, University of L' Aquila, Via Vetoio (Coppito 1), 67010 L' Aquila (Italy); Novotny, J.; Liska, M.; Samek, O. [Institute of Physical Engineering, Faculty of Mechanical Engineering, Brno University of Technology, Technicka 2896/2, 616 69 Brno (Czech Republic); Kanicky, V.; Hrdlicka, A. [Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic); Stejskal, K.; Adam, V.; Kizek, R. [Department of Chemistry and Biochemistry, Faculty of Agronomy, Mendel University of Agriculture and Forestry, Zemedelska 1, 613 00 Brno (Czech Republic)

    2009-01-15

    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 {mu}m in a up to cm x 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.

  19. Determination of platinum in human subcellular microsamples by inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Björn, Erik; Nygren, Yvonne; Nguyen, Tam T. T. N.

    2007-01-01

    A fast and robust method for the determination of platinum in human subcellular microsamples by inductively coupled plasma mass spectrometry was developed, characterized, and validated. Samples of isolated DNA and exosome fractions from human ovarian (2008) and melanoma (T289) cancer cell lines...

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

    Science.gov (United States)

    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

  1. [Selenium determination in plasma/serum by inductively coupled plasma mass spectrometry (ICP-MS): comparison with graphite furnace atomic absorption spectrometry (GF-AAS)].

    Science.gov (United States)

    Janasik, Beata; Trzcinka-Ochocka, Małgorzata; Brodzka, Renata

    2011-01-01

    The present study was aimed at comparing two techniques of selenium (Se) determination in serum/plasma samples: inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption (GF-AAS). Blood samples were collected by venipuncture, using Venosafe closed blood sampling system. The samples were centrifuged. The measurements were performed by Elan DRC-e mass spectrometry, Perkin Elmer, SCIEX, USA and Unicam Solar 989 QZ atomic absorption spectrometry. Reference material, Clincheck Serum Control Level 1 (Recipe, Germany), was used to verify the determinations. The Laboratory participates in external quality control (G-EQUAS). Analytical parameters for both techniques are respectively: ICP-MS--precision 5.9%, limit of detection 0.19 microg/l, repeatability 5.5%, trueness 2.4%, bias 97.6%, GF-AAS--precision 8%, limit of detection 3.4 microg/l, repeatability 7.2%, trueness 6.8%, bias 93.2%. The benefits of the ICP-MS technique are high accuracy, low detection limits and the possibility of multi-element analysis.

  2. Multi-elemental analysis of aqueous geological samples by inductively coupled plasma-optical emission spectrometry

    Science.gov (United States)

    Todorov, Todor I.; Wolf, Ruth E.; Adams, Monique

    2014-01-01

    Typically, 27 major, minor, and trace elements are determined in natural waters, acid mine drainage, extraction fluids, and leachates of geological and environmental samples by inductively coupled plasma-optical emission spectrometry (ICP-OES). At the discretion of the analyst, additional elements may be determined after suitable method modifications and performance data are established. Samples are preserved in 1–2 percent nitric acid (HNO3) at sample collection or as soon as possible after collection. The aqueous samples are aspirated into the ICP-OES discharge, where the elemental emission signals are measured simultaneously for 27 elements. Calibration is performed with a series of matrix-matched, multi-element solution standards.

  3. Imaging gold nanoparticles in mouse liver by laser ablation inductively coupled plasma mass spectrometry

    OpenAIRE

    Li, Qing; Wang, Zheng; Mo, Jiamei; Zhang, Guoxia; Chen, Yirui; Huang, Chuchu

    2017-01-01

    Imaging the size distribution of metal nanoparticles (NPs) in a tissue has important implications in terms of evaluating NP toxicity. Microscopy techniques used to image tissue NPs are limited by complicated sample preparation or poor resolution. In this study, we developed a laser ablation (LA) system coupled to single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS) for quantitative imaging of gold (G)NPs in tissue samples. In this system, GNPs were ablated but did not disi...

  4. New Applications of Inductively Coupled Plasma-Mass Spectrometry in the Nuclear Industry

    Energy Technology Data Exchange (ETDEWEB)

    Rob Henry; Dagmar Koller; Phil Marriott

    1998-12-31

    Inductively coupled plasma mass spectrometry (ICP-MS) complements the traditional methods of quantitation of radioactive isotopes. Because of the favorable ionization potential of most actinides and their daughter products, the argon plasma provides a rich, stable source of ions, which are introduced through a plasma-mass spectrometer interface into the mass spectrometer for isotopic separation. Samples are normally introduced in solution, although direct solids analysis has also been achieved using laser ablation of the sample into the argon plasma. Since 1983, improvements in ICP-MS sensitivity have resulted in correspondingly lower mass detection capability. This development has in turn expanded the number of isotopes accessible to measurement at the levels required in the nuclear industry.

  5. Low-resolution continuum source simultaneous multi-element electrothermal atomic absorption spectrometry: steps into practice

    Energy Technology Data Exchange (ETDEWEB)

    Katskov, Dmitri, E-mail: katskovda@tut.ac.za

    2015-03-01

    The theory and practical problems of continuum source simultaneous multi-element electrothermal atomic absorption spectrometry (SMET AAS) are discussed by the example of direct analysis of underground water. The experimental methodology is based on pulse vaporization of the sample in a fast heated graphite tube and measurement of transient absorption of continuum spectrum radiation from D{sub 2} and Xe lamps within 200–400 nm wavelengths range with a low resolution spectral instrument and linear charge-coupled device. The setup permits the acquisition of 200 spectra during 1 s atomization pulse. Respective data matrix absorbance vs wavelength/time is employed for the quantification of elements in the sample. The calculation algorithm developed includes broad band and continuum background correction, linearization of function absorbance vs. concentration of atomic vapor and integration of thus modified absorbance at the resonance lines of the elements to be determined. Practical application shows that the method can be employed for the direct simultaneous determination of about 20 elements above microgram per liter level within 3–5 orders of the magnitude concentration range. The investigated sources of measurement errors are mainly associated with the atomization and vapor transportation problems, which are aggravated for the simultaneous release of major and minor sample constituents. Respective corrections concerning the selection of analytical lines, optimal sampling volume, matrix modification and cleaning of the atomizer have been introduced in the SMET AAS analytical technology. Under the optimized experimental conditions the calibration curves in Log-Log coordinates for all the investigated analytes in the single or multi-element reference solutions are approximated by the first order equations. The use of these equations as permanent characteristics of the setup enables instant quantification of Al, Ca, Co, Cr, Cu, Fe, Mg, Mn and Ni in the underground

  6. Quantitative real-time monitoring of multi-elements in airborne particulates by direct introduction into an inductively coupled plasma mass spectrometer

    Science.gov (United States)

    Suzuki, Yoshinari; Sato, Hikaru; Hiyoshi, Katsuhiro; Furuta, Naoki

    2012-10-01

    A new calibration system for real-time determination of trace elements in airborne particulates was developed. Airborne particulates were directly introduced into an inductively coupled plasma mass spectrometer, and the concentrations of 15 trace elements were determined by means of an external calibration method. External standard solutions were nebulized by an ultrasonic nebulizer (USN) coupled with a desolvation system, and the resulting aerosol was introduced into the plasma. The efficiency of sample introduction via the USN was calculated by two methods: (1) the introduction of a Cr standard solution via the USN was compared with introduction of a Cr(CO)6 standard gas via a standard gas generator and (2) the aerosol generated by the USN was trapped on filters and then analyzed. The Cr introduction efficiencies obtained by the two methods were the same, and the introduction efficiencies of the other elements were equal to the introduction efficiency of Cr. Our results indicated that our calibration method for introduction efficiency worked well for the 15 elements (Ti, V, Cr, Mn, Co, Ni, Cu, Zn, As, Mo, Sn, Sb, Ba, Tl and Pb). The real-time data and the filter-collection data agreed well for elements with low-melting oxides (V, Co, As, Mo, Sb, Tl, and Pb). In contrast, the real-time data were smaller than the filter-collection data for elements with high-melting oxides (Ti, Cr, Mn, Ni, Cu, Zn, Sn, and Ba). This result implies that the oxides of these 8 elements were not completely fused, vaporized, atomized, and ionized in the initial radiation zone of the inductively coupled plasma. However, quantitative real-time monitoring can be realized after correction for the element recoveries which can be calculated from the ratio of real-time data/filter-collection data.

  7. Multiplex bio-assay with inductively coupled plasma mass spectrometry: Towards a massively multivariate single-cell technology

    Energy Technology Data Exchange (ETDEWEB)

    Tanner, Scott D. [Institute of Biomaterials and Biomedical Engineering, University of Toronto, Room 407, 164 College Street, Toronto, Ontario, M5S 3G9 (Canada)], E-mail: sd.tanner@utoronto.ca; Ornatsky, Olga; Bandura, Dmitry R.; Baranov, Vladimir I. [Institute of Biomaterials and Biomedical Engineering, University of Toronto, Room 407, 164 College Street, Toronto, Ontario, M5S 3G9 (Canada)

    2007-03-15

    Recent progress in the development of massively multiplexed bioanalytical assays using element tags with inductively coupled plasma mass spectrometry detection is reviewed. Feasibility results using commercially available secondary immunolabeling reagents for leukemic cell lines are presented. Multiplex analysis of higher order is shown with first generation tag reagents based on functionalized carriers that bind lanthanide ions. DNA quantification using metallointercalation allows for cell enumeration or mitotic state differentiation. In situ hybridization permits the determination of cellular RNA. The results provide a feasibility basis for the development of a multivariate assay tool for individual cell analysis based on inductively coupled plasma mass spectrometry in a cytometer configuration.

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

    Science.gov (United States)

    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.

  9. Filterless preconcentration, flow injection analysis and detection by inductively-coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thaulov

    The influence of interferences in the analysis of elements by inductively-coupled-plasma mass-spectrometry (ICP-MS) may be significantly diminished by utilising a protocol of flow-injection analysis (FIA). The method is based on filterless preconcentration of metallic elements at the walls...... of a knotted reactor that was made of nylon tubings. In the load mode, the preconcentration was accomplished by precipitation of metallic species in alkaline-buffered carriers onto the inner walls of the hydrofilic tube. After a preconcen-tration period of 40-120 seconds using sample volumes of 4-10 m......L, the analyte was transferred by a FIAS 400 system to the ICP-MS detector by dissolving the species in an acidic carrier. The magnitude of the enrichment factor largely depended on the time of preconcentration, on the pH-value of the preconcentration buffer and on the pH-value of the samples. Enrichment factors...

  10. Determination of Trace Elements in High Purity Gold by High Resolution Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    XIE Hualin; HUANG Kelong; NIE Xidu; FU Liang

    2009-01-01

    Trace elements were determined in high purity gold by high resolution inductively coupled plasma mass spectrometry(HR-ICP-MS).Sample were decomposed by aqua regia.To overcome some potentially problematic spectral interference,measurements were acquired in both medium and high resolution modes.The matrix effects due to the presence of excessive HCl and Au were evaluated.The optimum conditions for the determination was tested and discussed.The standard addition method was employed for quantitative analysis.The detection limits range from 0.01 μg/g to 0.28 μg/g depending on the elements.The method is accurate,quick and convenient.It has been applied to the determination of trace elements in high purity gold with satisfactory results.

  11. Development of analytical methods for multiplex bio-assay with inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Ornatsky, Olga I; Kinach, Robert; Bandura, Dmitry R; Lou, Xudong; Tanner, Scott D; Baranov, Vladimir I; Nitz, Mark; Winnik, Mitchell A

    2008-01-01

    Advances in the development of highly multiplexed bio-analytical assays with inductively coupled plasma mass spectrometry (ICP-MS) detection are discussed. Use of novel reagents specifically designed for immunological methods utilizing elemental analysis is presented. The major steps of method development, including selection of elements for tags, validation of tagged reagents, and examples of multiplexed assays, are considered in detail. The paper further describes experimental protocols for elemental tagging of antibodies, immunostaining of live and fixed human leukemia cells, and preparation of samples for ICP-MS analysis. Quantitative analysis of surface antigens on model cell lines using a cocktail of seven lanthanide labeled antibodies demonstrated high specificity and concordance with conventional immunophenotyping.

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

    Science.gov (United States)

    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.

  13. Inductively coupled plasma mass spectrometry (ICP-MS)and its application in life sciences

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    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 ICPMS 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.

  14. Determination of metals in composite diet samples by inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Melnyk, Lisa Jo; Morgan, Jeffrey N; Fernando, Reshan; Pellizzari, Edo D; Akinbo, Olujide

    2003-01-01

    A study was conducted to evaluate the applicability of inductively coupled plasma-mass spectrometry (ICP-MS) techniques for determination of metals in composite diets. Aluminum, cadmium, chromium, copper, lead, manganese, nickel, vanadium, and zinc were determined by this method. Atmospheric pressure microwave digestion was used to solubilize analytes in homogenized composite diet samples, and this procedure was followed by ICP-MS analysis. Recovery of certified elements from standard reference materials ranged from 92 to 119% with relative standard deviations (RSDs) of 0.4-1.9%. Recovery of elements from fortified composite diet samples ranged from 75 to 129% with RSDs of 0-11.3%. Limits of detection ranged from 1 to 1700 ng/g; high values were due to significant amounts of certain elements naturally present in composite diets. Results of this study demonstrate that low-resolution quadrupole-based ICP-MS provides precise and accurate measurements of the elements tested in composite diet samples.

  15. Multiplex DNA assay based on nanoparticle probes by single particle inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Zhang, Shixi; Han, Guojun; Xing, Zhi; Zhang, Sichun; Zhang, Xinrong

    2014-04-01

    A multiplex DNA assay based on nanoparticle (NP) tags detection utilizing single particle mode inductively coupled plasma mass spectrometry (SP-ICP-MS) as ultrasensitive readout has been demonstrated in the article. Three DNA targets associated with clinical diseases (HIV, HAV, and HBV) down to 1 pM were detected by DNA probes labeled with AuNPs, AgNPs, and PtNPs via DNA sandwich assay. Single nucleotide polymorphisms in genes can also be effectively discriminated. Since our method is unaffected by the sample matrix, it is well-suited for diagnostic applications. Moreover, with the high sensitivity of SP-ICP-MS and the variety of NPs detectable by SP-ICP-MS, high-throughput DNA assay could be achieved without signal amplification or chain reaction amplification.

  16. Multielement Analysis of Deep-Sea Sediments by Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    XIA Ning; WU Zhaohui; GUO Dongfa; YAO De

    2008-01-01

    Marine sediments were dissolved by HNO3-HF-HCIO4 in a sealed container at low pressure; I-IF was evaporated in an open container and salts were dissolved in HCl by heating, then transferred to 2% HNO3 solution. A total of 45 elements, including Li, Be, So, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, TI, Pb, Bi, Th and U, were measured by inductively coupled plasma mass spectrometry (ICP-MS). Condi-tions and sample experiments showed that this procedure defines a good experimental method which has the advantages of clear interference, easy operation and reliable results. The concentrations of the 45 elements could be used for resource exploration, envi-ronmental assessment and academic research.

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

    Science.gov (United States)

    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.

  18. Standard practice for alternate actinide calibration for inductively coupled plasma-mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2004-01-01

    1.1 This practice provides guidance for an alternate linear calibration for the determination of selected actinide isotopes in appropriately prepared aqueous solutions by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). This alternate calibration is mass bias adjusted using thorium-232 (232Th) and uranium-238 (238U) standards. One of the benefits of this standard practice is the ability to calibrate for the analysis of highly radioactive actinides using calibration standards at much lower specific activities. Environmental laboratories may find this standard practice useful if facilities are not available to handle the highly radioactive standards of the individual actinides of interest. 1.2 The instrument response for a series of determinations of known concentration of 232Th and 238U defines the mass versus response relationship. For each standard concentration, the slope of the line defined by 232Th and 238U is used to derive linear calibration curves for each mass of interest using interference equ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Baxter, Douglas C., E-mail: douglas.baxter@alsglobal.com [ALS Scandinavia AB, Aurorum 10, 977 75 Lulea (Sweden); Faarinen, Mikko [ALS Scandinavia AB, Aurorum 10, 977 75 Lulea (Sweden); Osterlund, Helene; Rodushkin, Ilia [ALS Scandinavia AB, Aurorum 10, 977 75 Lulea (Sweden); Division of Geosciences, Lulea University of Technology, 977 87 Lulea (Sweden); Christensen, Morten [ALS Scandinavia AB, Maskinvaegen 2, 183 53 Taeby (Sweden)

    2011-09-09

    Highlights: {center_dot} We determine methylmercury in serum and plasma using isotope dilution calibration. {center_dot} Separation by gas chromatography and detection by inductively coupled plasma mass spectrometry. {center_dot} Data for 50 specimens provides first reference range for methylmercury in serum. {center_dot} Serum samples shown to be stable for 11 months in refrigerator. - Abstract: A method for the determination of methylmercury in plasma and serum samples was developed. The method uses isotope dilution with {sup 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) {mu}g L{sup -1} could be performed with uncertainty amplification factors <2. A limit of quantification of 0.03 {mu}g L{sup -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 {mu}g L{sup -1}, 0.35 {mu}g L{sup -1} and 2.8 {mu}g L{sup -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) {mu}g L{sup -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.

  20. Authenticity of Benin metalworks evaluated by inductively coupled plasma mass spectrometry and lead isotope analyses

    Science.gov (United States)

    Fabbri, E.; Soffritti, C.; Merlin, M.; Vaccaro, C.; Garagnani, G. L.

    2017-05-01

    Two metal plaques and a cock statuette belonging to a private collection and stylistically consistent with the Royal Art of Benin (Nigeria) were investigated in order to verify their authenticity. The characterization of alloys and patinas were carried out by inductively coupled plasma mass spectrometry, optical microscopy, scanning electron microscopy and energy dispersion spectroscopy, and X-Ray diffraction spectrometry. Furthermore, thermal ionization mass spectrometry was used to assess the abundances of lead isotopes and to attempt a dating by the measurement of 210Pb/204Pb ratio. The results showed that all three artefacts were mainly composed of low lead-brass alloys, with relatively high concentrations of zinc, antimony, cadmium and aluminum in the solid copper solution. Microstructures were mostly dendritic, typical of as-cast brasses, and characterized by recrystallized non-homogeneous twinned grains in areas corresponding to surface decorations, probably due to multiple hammering steps followed by partial annealing treatments. The matrix was composed of a cored α-Cu solid solution together with non-metallic inclusions, lead globules and Sn-rich precipitates in interdendritic spaces. On the surface of all metalworks, both copper and zinc oxides, a non-continuous layer of sulphur-containing contaminants and chloride-containing compounds, were identified. The lead isotope results were consistent with brasses produced shortly before or after 1900 CE. Overall, the data obtained by different techniques supported the hypothesis that the three artefacts were not authentic.

  1. Measurement of the 135Cs half-life with accelerator mass spectrometry and inductively coupled plasma mass spectrometry

    Science.gov (United States)

    MacDonald, C. M.; Cornett, R. J.; Charles, C. R. J.; Zhao, X. L.; Kieser, W. E.

    2016-01-01

    The isotope 135Cs is quoted as having a half-life of 2.3 Myr. However, there are three published values ranging from 1.8 to 3 Myr. This research reviews previous measurements and reports a new measurement of the half-life using newly developed accelerator mass spectrometry (AMS) and inductively coupled plasma mass spectrometry (ICPMS) techniques along with β and γ radiometric analysis. The half-life was determined to be (1.6 ±0.6 ) ×106 yr by AMS and (1.3 ±0.2 ) ×106 yr by ICPMS with 95% confidence. The two values agree with each other but differ from the accepted value by ˜40 % .

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

    NARCIS (Netherlands)

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

    2015-01-01

    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

  3. Determination of selenoprotein P in human plasma by solid phase extraction and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Bendahl, L.; Sidenius, U.; Gammelgaard, Bente

    2000-01-01

    measured by inductively coupled plasma mass spectrometry (ICP-MS) monitoring the Se-82 isotope. Linear response was observed in the concentration range 0.3-70.8 mu g/l selenium as selenoprotein P with a correlation coefficient of 0.9994. The precision expressed as relative standard deviation was better...

  4. Determination of selenite and selenate in human urine by ion chromatography and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Jons, O.

    2000-01-01

    monitored in the inductively coupled plasma mass spectrometry (ICP-MS) detector. When the chromatographic system was applied to analysis of urine samples diluted 1 + 1, the selenomethionine signal appeared in the front together with other unresolved selenium species, while the selenite and selenate signals...

  5. [Determination of Heavy Metal Elements in Diatomite Filter Aid by Inductively Coupled Plasma Mass Spectrometry].

    Science.gov (United States)

    Nie, Xi-du; Fu, Liang

    2015-11-01

    This study established a method for determining Be, Cr, Ni, As, Cd, Sb, Sn, Tl, Hg and Pb, total 10 heavy metals in diatomite filter aid. The diatomite filter aid was digested by using the mixture acid of HNO₃ + HF+ H₃PO₄ in microwave system, 10 heavy metals elements were determined by inductively coupled plasma mass spectrometry (ICP-MS). The interferences of mass spectrometry caused by the high silicon substrate were optimized, first the equipment parameters and isotopes of test metals were selected to eliminate these interferences, the methane was selected as reactant gas, and the mass spectral interferences were eliminated by dynamic reaction cell (DRC). Li, Sc, Y, In and Bi were selected as the internal standard elements to correct the interferences caused by matrix and the drift of sensitivity. The results show that the detection limits for analyte is in the range of 3.29-15.68 ng · L⁻¹, relative standard deviations (RSD) is less than 4.62%, and the recovery is in the range of 90.71%-107.22%. The current method has some advantages such as, high sensitivity, accurate, and precision, which can be used in diatomite filter aid quality control and safety estimations.

  6. Bioimaging of metals by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    Science.gov (United States)

    Becker, J Sabine; Zoriy, Miroslav; Matusch, Andreas; Wu, Bei; Salber, Dagmar; Palm, Christoph; Becker, J Susanne

    2010-01-01

    The distribution analysis of (essential, beneficial, or toxic) metals (e.g., Cu, Fe, Zn, Pb, and others), metalloids, and non-metals in biological tissues is of key interest in life science. Over the past few years, the development and application of several imaging mass spectrometric techniques has been rapidly growing in biology and medicine. Especially, in brain research metalloproteins are in the focus of targeted therapy approaches of neurodegenerative diseases such as Alzheimer's and Parkinson's disease, or stroke, or tumor growth. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) using double-focusing sector field (LA-ICP-SFMS) or quadrupole-based mass spectrometers (LA-ICP-QMS) has been successfully applied as a powerful imaging (mapping) technique to produce quantitative images of detailed regionally specific element distributions in thin tissue sections of human or rodent brain. Imaging LA-ICP-QMS was also applied to investigate metal distributions in plant and animal sections to study, for example, the uptake and transport of nutrient and toxic elements or environmental contamination. The combination of imaging LA-ICP-MS of metals with proteomic studies using biomolecular mass spectrometry identifies metal-containing proteins and also phosphoproteins. Metal-containing proteins were imaged in a two-dimensional gel after electrophoretic separation of proteins (SDS or Blue Native PAGE). Recent progress in LA-ICP-MS imaging as a stand-alone technique and in combination with MALDI/ESI-MS for selected life science applications is summarized.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. Characterization of microconcentric nebulizer uptake rates for capillary electrophoresis inductively coupled plasma mass spectrometry

    Science.gov (United States)

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

    2003-05-01

    There is demonstrated interest in combining capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) for speciation determinations. When self-aspirating nebulizers are used for this application, it is important to offset the suction effect to avoid degradation of the separation. In this study, sample uptake rates for three microconcentric nebulizers of the same model, in combination with a cyclonic spray chamber, were characterized and compared for future utilization in CE-ICP-MS interfaces. The specific model studied was a MicroMist with a nominal uptake rate of 100 μl/min at 1 l/min argon gas flow rate per the manufacturer's specifications. Sample uptake rates at various nebulizer gas flows were measured by aspirating water from a weighed container and calculating the uptake rate in microliter per minute. The nebulizers studied provided good reproducibility from day to day, but a comparison of the different nebulizers reflected a significant difference in performance. A characteristic observed during the study was that uptake rates decreased with increasing nebulizer gas flow. This can be used for sample introduction for CE-ICP-MS. Interestingly, very different performance was observed when comparing the three different nebulizers of the same model. Uptake rates showed strong dependence on argon gas flow rates and the dimensions of the sample uptake tubing.

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

    Energy Technology Data Exchange (ETDEWEB)

    Veverková, Lenka [Regional Centre of Advanced Technologies and Materials, Department of Analytical Chemistry, Faculty of Science, Palacky University, 17.listopadu 12, CZ 771 46 Olomouc (Czech Republic); Hradilová, Šárka [Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University, 17.listopadu 12, CZ 771 46 Olomouc (Czech Republic); Milde, David, E-mail: david.mlde@upol.cz [Regional Centre of Advanced Technologies and Materials, Department of Analytical Chemistry, Faculty of Science, Palacky University, 17.listopadu 12, CZ 771 46 Olomouc (Czech Republic); Panáček, Aleš [Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University, 17.listopadu 12, CZ 771 46 Olomouc (Czech Republic); Skopalová, Jana [Regional Centre of Advanced Technologies and Materials, Department of Analytical Chemistry, Faculty of Science, Palacky University, 17.listopadu 12, CZ 771 46 Olomouc (Czech Republic); Kvítek, Libor [Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University, 17.listopadu 12, CZ 771 46 Olomouc (Czech Republic); Petrželová, Kamila [Regional Centre of Advanced Technologies and Materials, Department of Analytical Chemistry, Faculty of Science, Palacky University, 17.listopadu 12, CZ 771 46 Olomouc (Czech Republic); National Reference Laboratory for Chemical Elements, Department of Residues in Kroměříž, State Veterinary Institute Olomouc, Hulínská 2286, CZ 767 60 Kroměříž (Czech Republic); and others

    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 HNO{sub 3} 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 AgCl{sub 2}{sup −} and AgCl{sub 3}{sup 2−} 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. - Highlights: • We performed detailed optimization of microwave assisted digestion procedure of animal tissue used prior to Ag determination by ICP-MS. • We provide basic equilibrium calculations to give theoretical explanation of results from optimization of tested mineralization mixtures. • Results from method validation that was done by analysis of several matrix CRMs are presented.

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

    Science.gov (United States)

    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.

  14. Determination of impurity elements in MnZn ferrites by inductively coupled plasma mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    张萍; 符靓; 马俊才; 唐有根

    2015-01-01

    An inductively coupled plasma mass spectrometry (ICP-MS) method was developed for the determination of Na, Mg, Al, K, Ca, Ti, Cr, Co, Ni, Cu, Ga, As, Mo, Ag, Cd and Pb in MnZn ferrites. The sample was digested by HNO3+HCl with microwave digestion followed by dilution with ultrapure water, then the above 16 impurity elements in the solution were analyzed directly by ICP-MS. The impurity elements were introduced by the helium gas or hydrogen gas into the octopole reaction system (ORS) to eliminate the polyatomic interferences caused by the high salty matrixes. The matrix effect was minimized through matrix matching, and Be, Y and Rh were used as internal standard elements. The working parameters of the instrument were optimized. The results show that the method has good precision and high accuracy. The detection limits for the investigated elements are in the range of 0.9−37.5 ng/L, the relative standard deviation of each element is within 1.1%−4.8%, and the recovery of each element is 90%−108%.

  15. Determination of stable cesium and strontium in rice samples by inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Srinuttrakul, W.; Yoshida, S.

    2017-06-01

    For long-term radiation dose assessment models, food ingestion is one of the major exposure pathways to human. In general, the stable isotopes can serve as analogues of radioisotopes. In this study, rice samples were collected from 30 paddy fields in Si Sa Ket, Yasothon and Roi Et in the northeast of Thailand in November 2014. The concentrations of stable cesium (Cs-133) and strontium (Sr-88) in polished rice were determined by inductively coupled plasma mass spectrometry (ICP-MS). The standard reference material of rice flour (NIST 1568a) with spiked Cs and Sr was used to validate the analytical method. The concentration of Cs in polished rice from Si Sa Ket, Yasothon and Roi Et was 0.158 ± 0.167 mg kg-1, 0.090 ± 0.117 mg kg-1 and 0.054 ± 0.031 mg kg-1, respectively. The concentration of Sr in polished rice from Si Sa Ket, Yasothon and Roi Et was 0.351 ± 0.108 mg kg-1, 0.364 ± 0.215 mg kg-1 and 0.287 ± 0.102 mg kg-1, respectively. Comparison of the results with Japanese data before the Fukushima Di-ichi nuclear power plant accident showed that the concentrations of both Cs and Sr for Thai rice were higher than those for Japanese rice.

  16. Comparison of femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements

    Energy Technology Data Exchange (ETDEWEB)

    Havrilla, George Joseph [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); McIntosh, Kathryn Gallagher [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Judge, Elizabeth [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Dirmyer, Matthew R. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Campbell, Keri [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Gonzalez, Jhanis J. [Applied Spectra Inc., Fremont, CA (United States)

    2016-10-20

    Feasibility tests were conducted using femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for rapid uranium isotopic measurements. The samples used in this study consisted of a range of pg quantities of known 235/238 U solutions as dried spot residues of 300 pL drops on silicon substrates. The samples spanned the following enrichments of 235U: 0.5, 1.5, 2, 3, and 15.1%. In this direct comparison using these particular samples both pulse durations demonstrated near equivalent data can be produced on either system with respect to accuracy and precision. There is no question that either LA-ICP-MS method offers the potential for rapid, accurate and precise isotopic measurements of U10Mo materials whether DU, LEU or HEU. The LA-ICP-MS equipment used for this work is commercially available. The program is in the process of validating this work for large samples using center samples strips from Y-12 MP-1 LEU-Mo Casting #1.

  17. Profiling metals in Cordyceps sinensis by using inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Wei, Xin; Hu, Hankun; Zheng, Baogeng; Arslan, Zikri; Huang, Hung-Chung; Mao, Weidong; Liu, Yi-Ming

    2017-01-28

    Cordyceps sinensis (C. sinensis) is a natural product that has diverse nutritional and medicinal values. Since the availability of natural C. sinensis becomes limited its authentication and quality control is of high significance. Herein we report on profiling of metals in C. sinensis by using inductively coupled plasma mass spectrometry (ICP-MS). The analysis reveals that C. sinensis contains a wide array of essential elements, including P, Mg, Zn, Cu, Fe, etc. Toxic metals detected are Cd, Pb, and As. In all five samples analyzed Pb contents are below 2.0 ppm. Arsenic level in C. sinensis caterpillar is significantly higher than that in its mycelium and varies from 3.0 to 32 ppm likely due to soil contamination. It's for the first time demonstrated in this work that clustering analysis on the proposed metal profiles consisting of 24 elements is very useful to identify "abnormal" C. sinensis samples, thus adding another dimension to the effective means for authentication and quality assessment of this highly demanded previous natural product.

  18. Determination of cobalamins using capillary electrophoresis inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Baker, S. A.; Miller-Ihli, N. J.

    2000-12-01

    The determination of cobalamins using capillary electrophoresis inductively coupled plasma mass spectrometry (CE-ICP-MS) was investigated. Both capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography (MEKC) modes of operation were studied. The optimal separation of four cobalamin species (cyanocobalamin, hydroxocobalamin, methylcobalamin, and 5'-deoxyadenosylcobalamin) and a potentially harmful corrinoid analogue (cobinamide dicyanide) was obtained using CZE at a pH of 2.5. Both 20 mM phosphate and 20 mM formate buffers were used with success, although the formate buffer provided improved resolution. The CZE-ICP-MS method was used to quantify cyanocobalamin in a vitamin supplement and the analytical results were in good agreement (±5%) with values obtained by ICP-MS for total Co levels. The solution detection limits for cobalamins using CZE-ICP-MS were approximately 50 ng/ml. MEKC was found to be useful for the screening of vitamin preparations because it provided a rapid means of distinguishing cyanocobalamin (the form most commonly used in vitamin preparations) from free cobalt. The separation of free cobalt and cyanocobalamin using MEKC was achieved in less than 10 min.

  19. Thin-layer chromatography combined with diode laser thermal vaporization inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Bednařík, Antonín; Tomalová, Iva; Kanický, Viktor; Preisler, Jan

    2014-10-17

    Here we present a novel coupling of thin-layer chromatography (TLC) to diode laser thermal vaporization inductively coupled plasma mass spectrometry (DLTV ICP MS). DLTV is a new technique of aerosol generation which uses a diode laser to induce pyrolysis of a substrate. In this case the cellulose stationary phase on aluminum-backed TLC sheets overprinted with black ink to absorb laser light. The experimental arrangement relies on economic instrumentation: an 808-nm 1.2-W continuous-wave infrared diode laser attached to a syringe pump serving as the movable stage. Using a glass tubular cell, the entire length of a TLC separation channel is scanned. The 8-cm long lanes were scanned in ∼35 s. The TLC - DLTV ICP MS coupling is demonstrated on the separation of four cobalamins (hydroxo-; adenosyl-; cyano-; and methylcobalamin) with limits of detection ∼2 pg and repeatability ∼15% for each individual species. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Trace Elements Analysis of Geological Samples by Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    This paper describes recent work applying a taser ablation system (LSX-200) hyphenated with POEMS Ⅲ inductively coupled plasma mass spectrometry (LA-ICP-MS) for the in situ analysis of 22 trace elements of solid geological materials. It demonstrates the potential of LA-ICP-MS for the determination of geochemically important trace and ultra-trace elements following XRF routine sample preparation. Signal drift, difference in transport efficiency and sampling yield are well corrected with NIST SRM 612 as external calibration standard and Ca as internal standard. The obtained results agree to the recommended values with relative error better than 15 % and RSD less than 15 % for most determined trace elemems. LOD ranges from 0.021 × 10-6 to 0. 23 × 10-6 and less than 0.10 × 10-6 for majority trace elements determined. In addition, home-made macro functions including filter and calculator compiled by VBA language under Excel software greatly enhanced off-line data reduction efficiency.``

  1. Laser ablation - inductively coupled plasma mass spectrometry (LA-ICP-MS): Novel applications for coal research

    Energy Technology Data Exchange (ETDEWEB)

    Booth, C.A.; Spears, D.A.

    1999-07-01

    Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry (LA-ICP-MS) has enormous potential in coal research. Element concentrations are determined with limits of detection currently in the parts per billion range, whilst spatial resolution as low as 10 microns can be achieved using the CETAC Technologies LSX-100 laser ablation system. Calibration of the LA-ICP-MS systems is notoriously difficult but in this paper the authors review two different techniques used in Sheffield, which allow trace element concentrations of whole coals (bituminous) and minerals and macerals within the coal to be determined. The first technique involves calibrating the system with PF grade coal samples in order that trace element concentrations can directly be determined after ablation of a solid coal or pressed coal sample. Using this technique, potentially hazardous trace elements such as As, Cd, Pb and Hg can be detected and measured even in the low parts per billion concentration (mg/Kg) range. The second application utilizes the spatial resolution of the laser to measure element concentrations in individual coal components. In this paper the results from ablating pyrite framboids in polished sections of the coal are discussed. Elemental information is obtained throughout the ablation procedure and this is then calibrated against the Fe content in order to establish the concentration of an element per 1% pyritic iron.

  2. Identification of organically associated trace elements in wood and coal by inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Richaud, R.; Lazaro, M.J.; Lachas, H.; Miller, B.B.; Herod, A.A.; Dugwell, D.R.; Kandiyoti, R. [Imperial College of Science, Technology and Medicine, London (United Kingdom). Dept. of Chemical Engineering and Chemical Technology

    2000-07-01

    1-Methyl-2-pyrrolidinone (NMP) was used to extract samples of wood (forest residue) and coal; the extracts were analysed by inductively coupled plasma mass spectrometry (ICP-MS) using two different sample preparation methods, in order to identify trace elements associated with the organic part of the samples. A sample of fly ash was similarly extracted and analysed. Size exclusion chromatograms of the extracts indicated the presence of significant amounts of large molecular mass materials ({gt} 1000 {mu}) in the biomass and coal extracts but not in the ash extract. Trace element analyses were carried out using ICP-MS on the acid digests prepared by 'wet ashing' and microwave extraction. Sixteen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, pH, Sb, Se, V and Zn) were quantified, in the samples before extraction, in the extracts and in the residues. Concentrations of trace elements in the original biomass samples were lower than in the coal sample while the concentrations in the ash sample were the highest. The major trace elements in the NMP extracts were Ba, Cu, Mn and Zn from the forest residue; Ba, Cu, Mn, Pb and Zn from the coal; Cu and Zn from the ash. These elements are believed to be associated with the organic extracts from the forest residue and coal, and also from the ash.

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

    Energy Technology Data Exchange (ETDEWEB)

    Giner Martínez-Sierra, J.; Galilea San Blas, O.; Marchante Gayón, J.M.; García Alonso, J.I., E-mail: jiga@uniovi.es

    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. - Highlights: • Emphasis placed on the sulfur-specific detection by chromatographic techniques coupled on-line to ICP-MS. • Different instrumental approaches available for sulfur measurements by ICP-MS. • Quantification of proteins and the analysis of metalloproteins via sulfur by LC-ICP-MS. • Labelling procedures for metabolic applications are also included. • The measurement of natural variations in S isotope composition with multicollector ICP-MS.

  4. Element fingerprinting of marine organisms by dynamic reaction cell inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Cubadda, Francesco; Raggi, Andrea; Coni, Ettore

    2006-02-01

    A method for the determination of sixteen elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Se, Sn, V, Zn) in seafood by dynamic reaction cell inductively coupled plasma mass spectrometry (ICP-DRC-MS) is presented. A preliminary study of polyatomic interferences was carried out in relation to the chemical composition of marine organisms belonging to different taxa. Acid effects and other matrix effects in marine organisms submitted to closed-vessel microwave digestion were investigated as well. Ammonia was the reactive gas used in the DRC to remove polyatomic ions interfering with 27Al, 52Cr, 56Fe and 51V. Optimal conditions for the simultaneous determination of analytes were identified in order to develop a fast multielement method. A suite of real samples (mussels and various fish species) were used during method development along with three certified reference materials: BCR CRM 278R (mussel tissue), BCR CRM 422 (cod muscle) and DORM-2 (dogfish muscle). The proposed analytical approach can be used in conjunction with suitable chemometric procedures to address quality and safety issues in aquaculture and fisheries. As an example, a case study is described in which mussels from three farming sites in the Venice Lagoon were distinguished by multivariate analysis of element fingerprints.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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 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; methylmercury has been directly measured in this kind of specimen, and is therefore the first estimate of a reference range.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Imaging gold nanoparticles in mouse liver by laser ablation inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Li, Qing; Wang, Zheng; Mo, Jiamei; Zhang, Guoxia; Chen, Yirui; Huang, Chuchu

    2017-06-07

    Imaging the size distribution of metal nanoparticles (NPs) in a tissue has important implications in terms of evaluating NP toxicity. Microscopy techniques used to image tissue NPs are limited by complicated sample preparation or poor resolution. In this study, we developed a laser ablation (LA) system coupled to single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS) for quantitative imaging of gold (G)NPs in tissue samples. In this system, GNPs were ablated but did not disintegrate and integrate under optimised operation conditions, which were verified by characterising LA particles by scanning electron microscopy. The feasibility of imaging size distributions in tissue was validated using reference GNPs 60 and 80 nm in size on matrix-matched kidney. A transport efficiency of 6.07% was obtained by LA-SP-ICP-MS under optimal conditions. We used this system to image 80-nm GNPs in mouse liver and the size distribution thus obtained was in accordance with that determined by nebuliser SP-ICP-MS. The images revealed that 80-nm GNPs mainly accumulate in the liver and did not obviously aggregate. Our results demonstrate that LA-SP-ICP-MS is an effective tool for evaluating the size distribution of metal NPs in tissue.

  9. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) Applications in Quantitative Proteomics.

    Science.gov (United States)

    Chahrour, Osama; Malone, John

    2017-01-01

    Recent advances in inductively coupled plasma mass spectrometry (ICP-MS) hyphenated to different separation techniques have promoted it as a valuable tool in protein/peptide quantification. These emerging ICP-MS applications allow absolute quantification by measuring specific elemental responses. One approach quantifies elements already present in the structure of the target peptide (e.g. phosphorus and sulphur) as natural tags. Quantification of these natural tags allows the elucidation of the degree of protein phosphorylation in addition to absolute protein quantification. A separate approach is based on utilising bi-functional labelling substances (those containing ICP-MS detectable elements), that form a covalent chemical bond with the protein thus creating analogs which are detectable by ICP-MS. Based on the previously established stoichiometries of the labelling reagents, quantification can be achieved. This technique is very useful for the design of precise multiplexed quantitation schemes to address the challenges of biomarker screening and discovery. This review discusses the capabilities and different strategies to implement ICP-MS in the field of quantitative proteomics. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

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

    Science.gov (United States)

    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.

  11. Unique applications of solvent removal in inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Minnich, M.

    1997-01-10

    Inductively coupled plasma mass spectrometry (ICP-MS) is the technique of choice for rapid, high precision, semiquantitative elemental and isotopic analysis for over 70 elements. Less than 20 years after the first mass spectrum was obtained by ICP-MS, this technique has applications in clinical chemistry, geochemistry, the semiconductor industry, the nuclear industry, environmental chemistry, and forensic chemistry. The determination of many elements, though, by ICP-MS is complicated by spectral interferences from background species, interelement spectral overlaps, and polyatomic ions of matrix elements. The emphasis of this thesis is the unique applications of solvent removal using cryogenic and membrane desolvation. Chapter 1 is a general introduction providing background information concerning the need for these methods and some information about the methods themselves. Chapter 5 discusses general conclusions and general observations pertaining to this work. Chapters 2, 3, and 4 have been processed separately for inclusion on the database. Chapter 2 describes a method to screen urine samples for vanadium using cryogenic desolvation. Chapter 3 compares solvent removal by cryogenic and membrane desolvation. Chapter 4 describes the use of cool plasma conditions for the determination of potassium in the presence of excess sodium by ICP-MS.

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

    Science.gov (United States)

    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.

  13. Thorium colloid analysis by single particle inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Degueldre, C; Favarger, P-Y

    2004-04-19

    Thorium colloid analysis in water has been carried out by a single particle mode using inductively coupled plasma mass spectrometry (ICP-MS). The flash of ions due to the ionisation of a thorium colloidal particle in the plasma torch can be detected and measured in a time scan for (232)Th (+ ) or (248)[ThO] (+ ) according to the sensitivity required by the mass spectrometer. The peaks of the recorded intensity of the MS signal can be analysed as a function of the particle size or fraction of the studied element in the colloid phase. The frequency of the flashes is directly proportional to the concentration of particles in the colloidal suspension. After discussing Th colloid detection, on the basis of the intensity of the ion flashes generated in the plasma torch, tests were performed on thorium dioxide colloidal particles. This feasibility study also describes the experimental conditions and the limitation of the plasma design to detect thorium colloids in a single particle analysis mode down to about 10fg.

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

    Energy Technology Data Exchange (ETDEWEB)

    Luong, Elise [Iowa State Univ., Ames, IA (United States)

    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 β-cyclodextrin are chosen for the study, initial observation of spectral interference of 13C+ with 12C 1H+ comes from the incomplete dissociation of myoglobin and/or β-cyclodextrin.

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

    Energy Technology Data Exchange (ETDEWEB)

    Resano, M. [Laboratory of Analytical Chemistry, Ghent University, Institute for Nuclear Sciences, Proeftuinstraat 86, B-9000 Ghent (Belgium)]. E-mail: mresano@unizar.es; Garcia-Ruiz, E. [Laboratory of Analytical Chemistry, Ghent University, Institute for Nuclear Sciences, Proeftuinstraat 86, B-9000 Ghent (Belgium); Vanhaecke, F. [Laboratory of Analytical Chemistry, Ghent University, Institute for Nuclear Sciences, Proeftuinstraat 86, B-9000 Ghent (Belgium)

    2005-11-15

    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 {mu}g g{sup -1} level in this kind of materials, due to the interference of ArC{sup +} 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 {mu}g g{sup -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-{mu}g g{sup -1} level to tens of thousands of {mu}g g{sup -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 {mu}g g{sup -1} level or higher, while this value could deteriorate to 20% for analytes found at the sub-{mu}g g{sup -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

  16. Analysis of Cu, Co, V and Zn in coastal waters of the East China Sea by inductively coupled plasma mass spectrometry (ICP-MS)

    Science.gov (United States)

    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.

  17. Trace Element Analysis of Minerals in Magmatic-Hydrothermal Ores by Laser Ablation Inductively-Coupled Plasma Mass Spectrometry: Approaches and Opportunities

    Directory of Open Access Journals (Sweden)

    Nigel Cook

    2016-10-01

    Full Text Available Laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS has rapidly established itself as the method of choice for generation of multi-element datasets for specific minerals, with broad applications in Earth science. Variation in absolute concentrations of different trace elements within common, widely distributed phases, such as pyrite, iron-oxides (magnetite and hematite, and key accessory minerals, such as apatite and titanite, can be particularly valuable for understanding processes of ore formation, and when trace element distributions vary systematically within a mineral system, for a vector approach in mineral exploration. LA-ICP-MS trace element data can assist in element deportment and geometallurgical studies, providing proof of which minerals host key elements of economic relevance, or elements that are deleterious to various metallurgical processes. This contribution reviews recent advances in LA-ICP-MS methodology, reference standards, the application of the method to new mineral matrices, outstanding analytical uncertainties that impact on the quality and usefulness of trace element data, and future applications of the technique. We illustrate how data interpretation is highly dependent on an adequate understanding of prevailing mineral textures, geological history, and in some cases, crystal structure.

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

    Science.gov (United States)

    Erdemir, Umran Seven; Gucer, Seref

    2014-11-05

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    OpenAIRE

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

    2011-01-01

    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 (spICP-MS) is an emerging technique that can both size and count metal-containing nanoparticles. A major benefit of the spICP-MS method is its ability to characterize nanoparticles at concentrations relevant to the environment. This paper...

  2. Improved Cd determination in glasses by laser ablation inductively coupled plasma mass spectrometry using nitrogen as a matrix modifier

    Institute of Scientific and Technical Information of China (English)

    Qian Ni; Zhao Chu Hu; Zheng Yu Bao; Ya Feng Zhang

    2009-01-01

    The addition of 5-10 mL min-1 nitrogen to the central channel of plasma in Laser ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) increases the sensitivities of Cd by a factor of 3 and decreases oxide interferences by one order of magnitude, which allows the direct analysis of trace levels of Cd in glass samples. This simple method shows a great potential for the direct determination of Cd in various kinds of samples.

  3. Delta34S measurements of sulfur by multicollector inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Clough, Robert; Evans, Peter; Catterick, Tim; Evans, E Hywel

    2006-09-01

    An accurate and precise method for the determination of delta34S measurements by multicollector inductively coupled plasma mass spectrometry has been developed. Full uncertainty budgets, taking into consideration all the uncertainties of the measurement process, have been calculated. The technique was evaluated by comparing measured values with a range of isotopically enriched sulfur solutions prepared by gravimetric addition of a 34S spike. The gravimetric and measured results exhibited a correlation of R2 >0.999. Repeat measurements were also made after adding Na (up to 420 microg g(-1)) and Ca (up to 400 microg g(-1)) salts to the sulfur standard. No significant deviations in the delta34S values were observed. The Russell correction expression (Ingle, C.; Sharp, B.; Horstwood, M.; Parrish, R.; Lewis, D. J. J. Anal. At. Spectrom. 2003, 18, 219) was used to correct for mass bias on the 34S/32S isotope amount ratio from the mass bias observed for the 30Si/28Si isotope amount ratio. Consistent compensation for instrumental mass bias was achieved. Resolution of the measured delta34S values was better than 1 per thousand after consideration of all uncertainty components. The technique was evaluated for practical applications by measurement of delta34S for a range of mineral waters by pneumatic nebulization sample introduction and the analysis of genuine and counterfeit pharmaceuticals using both laser ablation sample introduction and liquid chromatography. For the former two cases polyatomic interferences were resolved by operating the MC-ICPMS in medium resolution, while for the chromatographic analyses polyatomic interferences were minimized by the use of a membrane desolvator, allowing the instrument to be operated at a resolution of 400.

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

    Science.gov (United States)

    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.

  5. Detecting nanoparticulate silver using single-particle inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Mitrano, Denise M; Lesher, Emily K; Bednar, Anthony; Monserud, Jon; Higgins, Christopher P; Ranville, James F

    2012-01-01

    The environmental prevalence of engineered nanomaterials, particularly nanoparticulate silver (AgNP), is expected to increase substantially. The ubiquitous use of commercial products containing AgNP may result in their release to the environment, and the potential for ecological effects is unknown. Detecting engineered nanomaterials is one of the greatest challenges in quantifying their risks. Thus, it is imperative to develop techniques capable of measuring and characterizing exposures, while dealing with the innate difficulties of nanomaterial detection in environmental samples, such as low-engineered nanomaterial concentrations, aggregation, and complex matrices. Here the authors demonstrate the use of inductively coupled plasma-mass spectrometry, operated in a single-particle counting mode (SP-ICP-MS), to detect and quantify AgNP. In the present study, two AgNP products were measured by SP-ICP-MS, including one of precisely manufactured size and shape, as well as a commercial AgNP-containing health food product. Serial dilutions, filtration, and acidification were applied to confirm that the method detected particles. Differentiation of dissolved and particulate silver (Ag) is a feature of the technique. Analysis of two wastewater samples demonstrated the applicability of SP-ICP-MS at nanograms per liter Ag concentrations. In this pilot study, AgNP was found at 100 to 200 ng/L in the presence of 50 to 500 ng/L dissolved Ag. The method provides the analytical capability to monitor Ag and other metal and metal oxide nanoparticles in fate, transport, stability, and toxicity studies using a commonly available laboratory instrument. Rapid throughput and element specificity are additional benefits of SP-ICP-MS as a measurement tool for metal and metal oxide engineered nanoparticles. Copyright © 2011 SETAC.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-08-15

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  9. High spatial resolution analysis of Pb and U isotopes for geochronology by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS)

    National Research Council Canada - National Science Library

    Bühn, Bernhard; Pimentel, Márcio M; Matteini, Massimo; Dantas, Elton L

    2009-01-01

    ...), are widely used to decipher geological processes. A new method developed in the last couple of years, the laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS...

  10. Developments in and applications of capillary electrophoresis inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, K.A

    1999-08-01

    This project has set out to design and optimise a robust and efficient interface for capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) and to investigate the application of the technique in elemental speciation studies. An interface was constructed using a commercial microconcentric nebuliser (MCN) and a cyclonic spray chamber. The cyclonic spray chamber was designed specifically to provide rapid sample response and washout and to minimise sample dispersion. Isoforms of the heavy metal binding protein, metallothionein, were separated and the bound metals detected to characterise the interface. Suction from the self-aspirating nebuliser was identified as the principal factor controlling electrophoretic resolution. To maintain resolution, two methods for counterbalancing the nebuliser suction were investigated. In the first method an optimised make-up flow was employed, and in the second a negative pressure was applied to the buffer vial during the separation. The negative pressure method was preferred because it did not significantly compromise sensitivity. The MCN was found to be prone to regular blocking which compromised the analytical precision of the system. A second interface was constructed using a glass MicroMist nebuliser. The MicroMist nebuliser was found to be less prone to blocking than the MCN and significantly improved the precision of the system to less than 4.3% RSD. The MicroMist nebuliser did, however, provide a lower sensitivity. The advantage of employing an electroosmotic flow marker to correct for migration time drifts was demonstrated. A CE-ICP-MS method was developed for the speciation of selenium in selenium enriched yeasts and nutritional supplements. Selenoamino acids and inorganic selenium species were separated, as anions, under strong electroosmotic flow conditions. Methods to enhance the selenium sensitivity were investigated. A proteolytic enzyme extraction method was employed and the effect of the

  11. Identification of organically associated trace elements in wood and coal by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Richaud, R; Lazaro, M J; Lachas, H; Miller, B B; Herod, A A; Dugwell, D R; Kandiyoti, R

    2000-01-01

    1-Methyl-2-pyrrolidinone (NMP) was used to extract samples of wood (forest residue) and coal; the extracts were analysed by inductively coupled plasma mass spectrometry (ICP-MS) using two different sample preparation methods, in order to identify trace elements associated with the organic part of the samples. A sample of fly ash was similarly extracted and analysed in order to assess the behaviour of the mineral matter contained within the wood and coal samples. 32% of the biomass was extracted at the higher temperature and 12% at room temperature while only 12% of the coal was extracted at the higher temperature and 3% at room temperature. Less than 2% of the ash dissolved at the higher temperature. Size exclusion chromatograms of the extracts indicated the presence of significant amounts of large molecular mass materials (>1000 mu) in the biomass and coal extracts but not in the ash extract. Trace element analyses were carried out using ICP-MS on the acid digests prepared by 'wet ashing' and microwave extraction. Sixteen elements (As, Ba, Be, Cd, Co, Cr, Cu, Ga, Mn, Mo, Ni, Pb, Sb, Se, V and Zn) were quantified, in the samples before extraction, in the extracts and in the residues. Concentrations of trace elements in the original biomass sample were lower than in the coal sample while the concentrations in the ash sample were the highest. The major trace elements in the NMP extracts were Ba, Cu, Mn and Zn from the forest residue; Ba, Cu, Mn, Pb and Zn from the coal; Cu and Zn from the ash. These elements are believed to be associated with the organic extracts from the forest residue and coal, and also from the ash. Be and Sb were not quantified in the extracts because they were present at too low concentrations; up to 40% of Mn was extracted from the biomass sample at 202 degrees C, while Se was totally extracted from the ash sample. For the forest residue, approximately 7% (at room temperature) and 45% (at 202 degrees C) of the total trace elements studied were

  12. Investigation of lanthanum-strontium-cobalt ferrites using laser ablation inductively coupled plasma-mass spectrometry

    Science.gov (United States)

    Óvári, Mihály; Tarsoly, Gergely; Németh, Zoltán; Mihucz, Victor G.; Záray, Gyula

    2017-01-01

    In the present study, suitability of laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for characterization of the purity and homogeneity of lanthanum-strontium-cobalt ferrite (LSCF) ceramic microsamples with general formula La1 - xSrxFe0.025Co0.975O3 (0.00 ≤ x ≤ 0.50) was studied through determination of their Sr:La ratios as well as Sr content either in depth or line profiling mode. The Sr content of the LSCF samples expressed as weight percent ranged between 5.8% and 9.7% in the case of wet chemical ICP-MS analysis, while theoretical values varied from 5.5% to 9.4%. In the case of LA-ICP-MS, relative standard deviation of the La-normalized Sr intensities was sufficient to characterize the homogeneity of the studied samples. Major and trace element (Mn, Ni, Cu, Mg, Al, Ba) concentrations could be detected at medium resolution of the applied sector field ICP-MS instrument after microwave-assisted acid digestion. For depth and line profiling, a successful approach consisted of the normalization of intensities of Sr, Fe and Co with the corresponding La counts. For the determination of the elemental ratios of La and Sr, the methods involving LA were in good agreement with theoretical values by standardization to an in-house standard corresponding to the LSCF sample having the highest x value (i.e., 0.50) checked by wet chemical ICP-MS measurements. Thus, assessment of fine scale doping of synthesized perovskite type of microsamples could be achieved by the proposed LA-ICP-MS based on a novel calibration approach applying an in-house perovskite standard. Therefore, LA-ICP-MS can be recommended for quality control of perovskite-based products. In memoriam Attila Vértes (1934-2011), full professor of the Institute of Chemistry, Eötvös Loránd University, Budapest, Hungary.

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

    Science.gov (United States)

    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

  14. 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.

    Science.gov (United States)

    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.

  15. 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

    Energy Technology Data Exchange (ETDEWEB)

    Perdian, David C. [Iowa State Univ., Ames, IA (United States)

    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.

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

    Science.gov (United States)

    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. Implementation of suitable flow injection/sequential-sample separation/preconcentration schemes for determination of trace metal concentrations using detection by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Hansen, Elo Harald; Wang, Jianhua

    2002-01-01

    Various preconditioning procedures encomprising appropriate separation/preconcentration schemes in order to obtain optimal sensitivity and selectivity characteristics when using electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICPMS) are pres...

  18. Implementation of suitable flow injection/sequential-sample separation/preconcentration schemes for determination of trace metal concentrations using detection by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Hansen, Elo Harald; Wang, Jianhua

    2002-01-01

    Various preconditioning procedures encomprising appropriate separation/preconcentration schemes in order to obtain optimal sensitivity and selectivity characteristics when using electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICPMS) are pres......Various preconditioning procedures encomprising appropriate separation/preconcentration schemes in order to obtain optimal sensitivity and selectivity characteristics when using electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICPMS...... prior to detection are effected in a microconduit placed on top of an SI selection valve....

  19. Femtosecond laser ablation: Experimental study of the repetition rate influence on inductively coupled plasma mass spectrometry performance

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez, Jhanis J. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Fernandez, Alberto [Centro de Fisicoquimica. Escuela de Quimica, Universidad Central de Venezuela, Caracas 1020-A (Venezuela); Oropeza, Dayana; Mao Xianglei [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Russo, Richard E. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)], E-mail: RERusso@lbl.gov

    2008-02-15

    This paper demonstrates the feasibility of performing bulk chemical analysis based on laser ablation for good lateral resolution with only nominal mass ablated per pulse. The influence of repetition rate (1-1000 Hz) and scan speed (1-200 {mu}m/s) using a low energy (30 {mu}J) and a small spot size ({approx} 10 {mu}m) UV-femtosecond laser beam was evaluated for chemical analysis of silica glass samples, based on laser ablation sampling and inductively coupled plasma mass spectrometry (ICP-MS). Accuracy to approximately 14% and precision of 6% relative standard deviation (RSD) were measured.

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

    Energy Technology Data Exchange (ETDEWEB)

    Arnquist, Isaac J.; Holcombe, James A., E-mail: holcombe@mail.utexas.edu

    2012-10-15

    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 (K{sub app}) and intrinsic (K{sub int}) binding affinities of the metal-protein association for a model protein. In particular, the affinity of Cu{sup 2+} for the high affinity binding site in bovine serum albumin (BSA) is determined. Once equilibrium is established between Cu{sup 2+} 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 Cu{sup 2+} 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 Cu{sup 2+} ion, which is identical to the equilibrium concentration prior to ultracentrifugation. From these data K{sub app} and K{sub int} were determined at two different conditions, 100 mM Tris(hydroxymethyl)aminomethane (Tris) at pH 9.53 and pH 7.93. log K{sub app} values of 17.6 and 14.6 were determined at pH 9.53 and pH 7.93, respectively. Furthermore, pH-independent log K{sub int} values of - 1.43 and - 1.04 were determined at pH 9.53 and 7.93, respectively. While the log K{sub int} at pH 9.53 was in good agreement with literature values obtained from alternative methods, K{sub int} at pH 7.93 was about 2.5 Multiplication-Sign 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 p

  1. 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.

    Science.gov (United States)

    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.

  2. Application of dot matrix LCD in multi-element portable X-ray fluorescence spectrometry The LCD is stated for Liquid Crystal Display

    CERN Document Server

    Lin Yan Chang; Lai Wan Chang; Zhou Si Chun

    2002-01-01

    Dot matrix LCD based on T6963C is a low power supply module. It needs no complex interface circuits connecting with MCU. Application in text and graphics is easy. Application of this LCD in multi-element portable XRF spectrometry is show. How to use it in Chinese, pull-down menu, spectrum and how to design the interface circuits with embedded computer are shown as well

  3. Continuous ice-core chemical analyses using inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    McConnell, Joseph R; Lamorey, Gregg W; Lambert, Steven W; Taylor, Kendrick C

    2002-01-01

    Impurities trapped in ice sheets and glaciers have the potential to provide detailed, high temporal resolution proxy information on paleo-environments, atmospheric circulation, and environmental pollution through the use of chemical, isotopic, and elemental tracers. We present a novel approach to ice-core chemical analyses in which an ice-core melter is coupled directly with both an inductively coupled plasma mass spectrometer and a traditional continuous flow analysis system. We demonstrate this new approach using replicated measurements of ice-core samples from Summit, Greenland. With this method, it is possible to readily obtain continuous, exactly coregistered concentration records for a large number of elements and chemical species at ppb and ppt levels and at unprecedented depth resolution. Such very-high depth resolution, multiparameter measurements will significantly expand the use of ice-core records for environmental proxies.

  4. Cobalamin speciation using reversed-phase micro-high-performance liquid chromatography interfaced to inductively coupled plasma mass spectrometry

    Science.gov (United States)

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

    2004-06-01

    Micro-high-performance liquid chromatography interfaced to inductively coupled plasma mass spectrometry was optimized for the determination and separation of a mixture of cobalt containing species. Four cobalamin species (cyanocobalamin, hydroxocobalamin, methylcobalamin, and 5'-deoxyadenosylcobalamin) representing the various forms of vitamin B12 as well as the harmful corrinoid analogue cobinamide dicyanide were separated using reversed-phase microcapillary chromatography with columns containing C18 packing material with a 2-μm particle size. Selection of organic solvents for the separation took into consideration compatibility with the inductively coupled plasma mass spectrometer being used for element specific detection. Optimized method conditions included use of a methanol gradient and make-up solution for the nebulizer. Some issues associated with dead volume were overcome by the extension of the gradient program. The total analysis time was 52 min. The column-to-column variability was evaluated and was found to be very reasonable (9% RSD on average), confirming that this method is rugged and that the technology should be easily transferred to other laboratories.

  5. Cobalamin speciation using reversed-phase micro-high-performance liquid chromatography interfaced to inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Yanes, Enrique G. E-mail: yanes@bhnrc.usda.gov; Miller-Ihli, Nancy J. E-mail: miller-ihli@bhnrc.usda.gov

    2004-06-18

    Micro-high-performance liquid chromatography interfaced to inductively coupled plasma mass spectrometry was optimized for the determination and separation of a mixture of cobalt containing species. Four cobalamin species (cyanocobalamin, hydroxocobalamin, methylcobalamin, and 5'-deoxyadenosylcobalamin) representing the various forms of vitamin B12 as well as the harmful corrinoid analogue cobinamide dicyanide were separated using reversed-phase microcapillary chromatography with columns containing C18 packing material with a 2-{mu}m particle size. Selection of organic solvents for the separation took into consideration compatibility with the inductively coupled plasma mass spectrometer being used for element specific detection. Optimized method conditions included use of a methanol gradient and make-up solution for the nebulizer. Some issues associated with dead volume were overcome by the extension of the gradient program. The total analysis time was 52 min. The column-to-column variability was evaluated and was found to be very reasonable (9% RSD on average), confirming that this method is rugged and that the technology should be easily transferred to other laboratories.

  6. Hyphenation of ultra performance liquid chromatography (UPLC) with inductively coupled plasma mass spectrometry (ICP-MS) for fast analysis of bromine containing preservatives

    DEFF Research Database (Denmark)

    Bendahl, Lars; Hansen, Steen Honoré; Gammelgaard, Bente

    2006-01-01

    Ultra performance liquid chromatography (UPLC) was coupled to inductively coupled plasma mass spectrometry (ICP-MS) for fast analysis of three bromine-containing preservatives, monitoring the 79Br and 81Br isotopes simultaneously. Due to the efficiency of the 1.7 microm column packing material, t...... analysis of bromine-containing preservatives in commercially available cosmetic products.......Ultra performance liquid chromatography (UPLC) was coupled to inductively coupled plasma mass spectrometry (ICP-MS) for fast analysis of three bromine-containing preservatives, monitoring the 79Br and 81Br isotopes simultaneously. Due to the efficiency of the 1.7 microm column packing material...

  7. Direct Determination of Trace Impurities in High Purity Zinc Oxide by High Resolution Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    XIE Hualin; NIE Xidu; LI Libo; SONG Chuhua

    2006-01-01

    The determination of trace impurities in high purity zinc oxide by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was investigated. To overcome some potentially problematic spectral interference, measurements were acquired in both middle and high resolution modes. The matrix effects due to the presence of excess HCl and zinc were evaluated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits ranged from 0.02 μg/g to 6 μg/g depending on the elements.The experimental results for the determination of Na, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Mo, Cd, Sb and Pb in several high purity zinc oxide powders were presented.

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

    Science.gov (United States)

    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.

  9. Determination of cadmium, mercury and lead in coal fly ash by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Liao, H.C.; Jiang, S.J. [National Sun Yat Sen University, Kaohsiung (Taiwan). Dept. of Chemistry

    1999-08-09

    Ultrasonic slurry sampling electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry (USS-ETV-ID-ICP-MS) was used to the determine Cd, Hg and Pb in coal fly ash samples. Thioacetamide (TAC) was the modifier. Since the sensitivities of the elements studied in coal fly ash slurry and aqueous solution were quite different, isotope dilution method was used for the determination of Cd, Hg and Pb in the coal fly ash samples. The isotope ratios of each element were calculated from the peak areas of each injection peak. This method was applied to the determination of Cd, Hg and Pb in NIST SRM 1633a coal fly ash reference material and a coal fly ash sample collected from Kaohsiung area. Detection limits estimated from standard addition curves were in the range of 24-58, 6-28 and 108-110 ng g{sup -1} for Cd, Hg and Pb, respectively.

  10. Comparison of serum zinc levels measured by inductively coupled plasma mass spectrometry in preschool children with febrile and afebrile seizures.

    Science.gov (United States)

    Lee, Jun-Hwa; Kim, Jeong Hyun

    2012-05-01

    Changes in levels of trace elements have been proposed to underlie febrile seizures. Particularly, low zinc levels have been proposed as related factor of febrile seizure. In this study, we investigated whether mean serum zinc levels differed between children with febrile seizure and afebrile seizure. Using inductively coupled plasma mass spectrometry, serum zinc levels were measured in 288 children who had been diagnosed with febrile seizures (N=248) and afebrile seizures (N=40). Mean serum zinc levels were compared between the 2 groups. Mean serum zinc level was 60.5±12.7 µg/dL in the febrile seizure group and 68.9 ±14.5 µg/dL in the afebrile seizure group. A significant difference in serum zinc levels was observed between the febrile and afebrile seizure groups (Pfebrile seizure were significantly lower than those in children with afebrile seizure.

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

    Science.gov (United States)

    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.

  12. Comparison of ultraviolet femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry analysis in glass, monazite, and zircon.

    Science.gov (United States)

    Poitrasson, Franck; Mao, Xianglei; Mao, Samuel S; Freydier, Rémi; Russo, Richard E

    2003-11-15

    We compared the analytical performance of ultraviolet femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). The benefit of ultrafast lasers was evaluated regarding thermal-induced chemical fractionation, that is otherwise well known to limit LA-ICPMS. Both lasers had a Gaussian beam energy profile and were tested using the same ablation system and ICPMS analyzer. Resulting crater morphologies and analytical signals showed more straightforward femtosecond laser ablation processes, with minimal thermal effects. Despite a less stable energy output, the ultrafast laser yielded elemental (Pb/U, Pb/Th) and Pb isotopic ratios that were more precise, repeatable, and accurate, even when compared to the best analytical conditions for the nanosecond laser. Measurements on NIST glasses, monazites, and zircon also showed that femtosecond LA-ICPMS calibration was less matrix-matched dependent and therefore more versatile.

  13. Gas and liquid chromatography with inductively coupled plasma mass spectrometry detection for environmental speciation analysis — advances and limitations

    Science.gov (United States)

    Szpunar, Joanna; McSheehy, Shona; Połeć, Kasia; Vacchina, Véronique; Mounicou, Sandra; Rodriguez, Isaac; Łobiński, Ryszard

    2000-07-01

    Recent advances in the coupling of gas chromatography (GC) and high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP MS) and their role in trace element speciation analysis of environmental materials are presented. The discussion is illustrated with three research examples concerning the following topics: (i) development and coupling of multicapillary microcolumn GC with ICP MS for speciation of organotin in sediment and biological tissue samples; (ii) speciation of arsenic in marine algae by size-exclusion-anion-exchange HPLC-ICP MS; and (iii) speciation of cadmium in plant cell cultures by size-exclusion HPLC-ICP MS. Particular attention is paid to the problem of signal identification in ICP MS chromatograms; the potential of electrospray MS/MS for this purpose is highlighted.

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

    Science.gov (United States)

    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.

  15. Intelligent Analysis of Samples by Semiquantitative Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) Technique: A Review.

    Science.gov (United States)

    Krzciuk, Karina

    2016-07-03

    Inductively coupled plasma-mass spectrometry (ICP-MS) is a popular and routine analytical method that has been used for determination of trace elements since the 1980s. It provides fast quantitative analysis and allows the determination of more than 70 elements with good accuracy and very low detection limits, but requires an intricate calibration procedure. In analyses of samples for which very low detection limits are not required a semiquantitative ICP-MS analysis mode can be used. This approach is more time- and cost-effective, and it uses a simple calibration procedure. This article presents a critical review of the semiquantitative (SQ) mode of ICP-MS and describes current and future applications of SQ analysis.

  16. The determination of low level trace elements in coals by laser ablation-inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Booth, C.A.; Spears, D.A.; Krause, P.; Cox, A.G. [University of Sheffield, Sheffield (United Kingdom). Dept. of Earth Sciences

    1999-11-01

    The rapid determination of elements present in low level concentrations in bituminous coals is possible using laser abalation-inductively coupled plasma-mass spectrometry (l.a.-i.c.p.-m.s.). A wide range of trace elements can routinely be determined using this technique but it is for environmentally sensitive elements, such as As, Cd, Mo, Sb, Se and Hg, that it is of most use due to the low levels of detection. Calibration of the i.c.p.-m.s. was achieved using a series of uncertified coals and the method evaluated using the South African certified coals, Sarm 18, 19 and 20. A critical evaluation of the data obtained shows that for many of the elements studied the results obtained are both accurate and precise, even at very low concentrations, with the limits of detection for all of the elements being in the {mu}g/kg (parts per billion) range. 6 refs., 3 figs., 9 tabs.

  17. Ultra-sensitive quantification of lysozyme based on element chelate labeling and capillary electrophoresis–inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Yang, MingWei [Key Laboratory of Analysis and Detection for Food Safety of Ministry of Education, Fujian Provincial Key Lab of Analysis and Detection for Food Safety, Department of Chemistry, Fuzhou University, Fuzhou 350108, Fujian (China); Department of Chemistry, Florida International University, Miami, FL 33199 (United States); Wu, WeiHua; Ruan, YaJuan; Huang, LiMei [Key Laboratory of Analysis and Detection for Food Safety of Ministry of Education, Fujian Provincial Key Lab of Analysis and Detection for Food Safety, Department of Chemistry, Fuzhou University, Fuzhou 350108, Fujian (China); Wu, Zujian [Department of Plant Protection, Fujian Agriculture and Forest University, Fuzhou 350002, Fujian (China); Cai, Yong [Department of Chemistry, Florida International University, Miami, FL 33199 (United States); Fu, FengFu, E-mail: fengfu@fzu.edu.cn [Key Laboratory of Analysis and Detection for Food Safety of Ministry of Education, Fujian Provincial Key Lab of Analysis and Detection for Food Safety, Department of Chemistry, Fuzhou University, Fuzhou 350108, Fujian (China); Department of Plant Protection, Fujian Agriculture and Forest University, Fuzhou 350002, Fujian (China)

    2014-02-17

    Graphical abstract: An ultra-sensitive method for the determination of lysozyme was developed based on the Gd{sup 3+} chelate labeling and CE–ICP–MS. The proposed method has an extremely low detection limit of 3.89 attomole and has been successfully used to detect lysozyme in saliva sample, showing excellent reliability. The success of the present method provides a new possibility for biological assays and clinical diagnoses. -- Highlights: •An ultra-sensitive method for detecting lysozyme based on CE–ICP–MS was described. •The proposed method has an extremely low detection limit of 3.89 attomole. •It can be used to detect trace lysozyme in saliva sample with a satisfied recovery. •The method provides a new potential for sensitive detection of low-abundant proteins. -- Abstract: In this study, an ultra-sensitive method for the quantification of lysozyme based on the Gd{sup 3+} diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid labeling and capillary electrophoresis–inductively coupled plasma mass spectrometry (CE–ICP–MS) was described. The Gd{sup 3+}-tagged lysozyme was effectively separated by capillary electrophoresis (CE) and sensitively determined by inductively coupled plasma mass spectrometry (ICP–MS). Based on the gadolinium-tagging and CE–ICP–MS, the lysozyme was determined within 12 min with an extremely low detection limit of 3.89 attomole (3.89 × 10{sup −11} mol L{sup −1} for 100 nL of sample injection) and a RSD < 6% (n = 5). The proposed method has been successfully used to detect lysozyme in saliva samples with a recovery of 91–106%, suggesting that our method is sensitive and reliable. The success of the present method provides a new potential for the biological assays and sensitive detection of low-abundant proteins.

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

    Science.gov (United States)

    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. Copyright © 2014 by The American Association of Immunologists, Inc.

  19. Establishing human heart chromium, cobalt and vanadium concentrations by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Day, Patrick L; Eckdahl, Steven J; Maleszewski, Joseph J; Wright, Thomas C; Murray, David L

    2017-05-01

    Chromium, cobalt, and vanadium are used in metallic joint prosthesis. Case studies have associated elevated heart tissue cobalt concentrations with myocardial injury. To document the long term heart metal ion concentrations, a validated inductively coupled plasma mass spectroscopy (ICP-MS) method was needed. The method utilized a closed-vessel microwave digestion system to digest the samples. An ICP-MS method utilizing Universal Cell Technology was used to determine our target analyte concentrations. Accuracy was verified using reference materials. Precision, sensitivity, recovery and linearity studies were performed. This method was used to establish a reference range for a non-implant containing cohort of 80 autopsy human heart tissues RESULTS: This method demonstrated an analytic measurement range of 0.5-100ng/mL for each element. Accuracy was within ±10% of target value for each element. Within-run precision for each element was below 20% CV. The chromium, vanadium and cobalt concentrations (mean±SD) were 0.1523±0.2157μg/g, 0.0094±0.0211μg/g and 0.1039±0.1305μg/g respectively in 80 non-implant containing human heart tissue samples. This method provides acceptable recovery of the chromium, cobalt and vanadium in heart tissue; allowing assessment of the effects of metallic joint prosthesis on myocardial health. Copyright © 2017 Elsevier GmbH. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  1. 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

    NARCIS (Netherlands)

    Helsper, J.P.F.G.; Peters, R.J.B.; Bemmel, M.E.M. van; Rivera, Z.E.H.; Wagner, S.; Kammer, F. von der; Tromp, P.C.; Hofmann, T.; Weigel, S.

    2016-01-01

    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 (IC

  2. Quantitative Characterization of Gold Nanoparticles by Field-Flow Fractionation Coupled Online with Light Scattering Detection and Inductively Coupled Plasma Mass Spectrometry

    DEFF Research Database (Denmark)

    Schmidt, Bjørn; Löschner, Katrin; Hadrup, Niels

    2011-01-01

    An analytical platform coupling asymmetric flow field-flow fractionation (AF4) with multiangle light scattering (MALS), dynamic light scattering (DLS), and inductively coupled plasma mass spectrometry (ICPMS) was established and used for separation and quantitative determination of size and mass ...

  3. Determination of Total Arsenic and Speciation in Apple Juice by Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry: An Experiment for the Analytical Chemistry Laboratory

    Science.gov (United States)

    He, Ping; Colon, Luis A.; Aga, Diana S.

    2016-01-01

    A two-part laboratory experiment was designed for upper-level analytical chemistry students to provide hands-on experience in the use of high performance liquid chromatography (HPLC) for separation and inductively coupled plasma mass spectrometry (ICP-MS) for detection. In the first part of the experiment, the students analyze total arsenic in…

  4. High-resolution line-scan analysis of resin-embedded sediments using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

    NARCIS (Netherlands)

    Hennekam, Rick|info:eu-repo/dai/nl/357286081; Jilbert, Tom|info:eu-repo/dai/nl/304835714; Mason, Paul R D|info:eu-repo/dai/nl/304829331; de Lange, Gert J.|info:eu-repo/dai/nl/073930962; Reichart, Gert Jan|info:eu-repo/dai/nl/165599081

    2015-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) line-scanning is a promising technique for producing high-resolution (μm-scale) geochemical records on resin-embedded sediments. However, this approach has not yet been thoroughly tested on sediment samples of known elemental

  5. High-resolution line-scan analysis of resin-embedded sediments using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

    NARCIS (Netherlands)

    Hennekam, R.; Jilbert, T.; de Lange, G.J.; Reichart, G.J.

    2015-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) line-scanning is a promising technique for producing high-resolution (µm-scale) geochemical records on resin-embedded sediments. However, this approach has not yet been thoroughly tested on sediment samples of known elemental

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

    Science.gov (United States)

    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...

  7. Comparison of an ultrasonic nebulizer with a cross-flow nebulizer for selenium speciation by ion-chromatography and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Jons, O.

    2000-01-01

    The purpose of this work was to compare an ultrasonic nebulizer (USN) with a cross-flow nebulizer (CFN) for selenium speciation with inductively coupled plasma mass spectrometry (ICP-MS) detection. The influence of instrumental parameters as well as composition of the solvent on the selenium...

  8. Evaluation of the analytical capability of NIR femtosecond laser ablation-inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Hirata, Takafumi; Kon, Yoshiaki

    2008-03-01

    A laser ablation-inductively coupled plasma-mass spectrometric (LA-ICPMS) technique utilizing a titanium-sapphire (TiS) femtosecond laser (fs-laser) has been developed for elemental and isotopic analysis. The signal intensity profile, depth of the ablation pit and level of elemental fractionation were investigated in order to evaluate the analytical capability of the present fs-laser ablation-ICPMS technique. The signal intensity profile of (57)Fe, obtained from iron sulfide (FeS(2)), demonstrated that the resulting signal intensity of (57)Fe achieved by the fs-laser ablation was almost 4-times higher than that obtained by ArF excimer laser ablation under a similar energy fluence (5 J/cm(2)). In fs-laser ablation, there is no significant difference in a depth of the ablation pit between glass and zircon material, while in ArF laser ablation, the resulting crater depth on the zircon crystal was almost half the level than that obtained for glass material. Both the thermal-induced and particle size-related elemental fractionations, which have been thought to be main sources of analytical error in the LA-ICPMS analysis, were measured on a Harvard 91500 zircon crystal. The resulting fractionation indexes on the (206)Pb/(238)U (f(Pb/U)) and (238)U/(232)Th (f(U/Th)) ratios obtained by the present fs-laser ablation system were significantly smaller than those obtained by a conventional ArF excimer laser ablation system, demonstrative of smaller elemental fractionation. Using the present fs-laser ablation technique, the time profile of the signal intensity of (56)Fe and the isotopic ratios ((57)Fe/(54)Fe and (56)Fe/(54)Fe) have been measured on a natural pyrite (FeS(2)) sample. Repeatability in signal intensity of (56)Fe achieved by the fs-laser ablation system was significantly better than that obtained by ArF excimer laser ablation. Moreover, the resulting precision in (57)Fe/(54)Fe and (56)Fe/(54)Fe ratio measurements could be improved by the fs-laser ablation system

  9. Speciation of four selenium compounds using high performance liquid chromatography with on-line detection by inductively coupled plasma mass spectrometry or flame atomic absorption spectrometry

    DEFF Research Database (Denmark)

    Pedersen, Gitte Alsing; Larsen, Erik Huusfeldt

    1997-01-01

    An analytical method for the speciation of selenomethionine, selenocystine, selenite and selenate by high performance liquid chromatography (HPLC) with atomic spectrometric detection is presented. An organic polymeric strong anion exchange column was used as the stationary phase in combination...... with an aqueous solution of 6 mmol L-1 of salicylate ion at pH 8.5 as the mobile phase which allowed the isocratic separation of the four selenium analytes within 8 minutes. The separated selenium species were detected on-line by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma mass...... spectrometry (ICP-MS). The signal-to-noise ratio of the FAAS detector was optimized using a hydrogen-argon entrained-air flame and a slotted-tube atom trap (STAT) in the flame. The limit of detection (3 sigma) achieved by the HPLC-FAAS system was 1 mg L-1 of selenium (100 mu L injections) for each of the four...

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

    Energy Technology Data Exchange (ETDEWEB)

    McIntyre, Sally M. [Iowa State Univ., Ames, IA (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    McIntyre, Sally M. [Iowa State Univ., Ames, IA (United States)

    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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2016-01-01

    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 (AsIII), arsino-glutathione (As(GS)3), arsenate (AsV), monomethylarsonous acid (MMAIII), monomethylarsino-glutathione (MMAIII(GS)2), monomethylarsonic acid (MMAV), dimethylarsinous acid (DMAIII (from DMAIIII)), S-(dimethylarsinic)cysteine (DMAIII(Cys)), dimethylarsino-glutathione (DMAIII(GS)), dimethylarsinic acid (DMAV), dimethylmonothioarsinic acid (DMMTAV), dimethyldithioarsinic acid (DMDTAV), dimethylarsinothioyl glutathione (DMMTAV(GS)). The developed method was applied for the analysis of cancer cells that were incubated with Darinaparsin (DMAIII(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. PMID:26708625

  14. Speciation of vanadium in oilsand coke and bacterial culture by high performance liquid chromatography inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Li, X. Sherry [Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada); Le, X. Chris [Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada); Analytical and Environmental Toxicology, Department of Laboratory Medicine and Pathology, University of Alberta, Edmonton, Alberta T6G 2G3 (Canada)], E-mail: xc.le@ualberta.ca

    2007-10-17

    A simple and sensitive method for the speciation of vanadium(III), (IV), and (V) was developed by using high performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICPMS). The EDTA-complexed vanadium species were separated on a strong anion exchange column with an eluent containing 2 mM EDTA, 3% acetonitrile, and 80 mM ammonium bicarbonate at pH 6. Each analysis was complete in 5 min. The detection limits were 0.6, 0.7 and 1.0 {mu}g L{sup -1} for V(III), V(IV), and V(V), respectively. The method was applied to coke pore water samples from an oilsand processing/upgrading site in Fort McMurray, Alberta, Canada and to Shewanella putrefaciens CN32 bacterial cultures incubated with V(V). In the coke pore water samples, V(IV) and V(V) were found to be the major species. For the first time, V(III) was detected in the bacterial cultures incubated with V(V)

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

    Energy Technology Data Exchange (ETDEWEB)

    Duyck, Christiane Beatrice, E-mail: cbduyck@vm.uff.br [Pontificia Universidade Catolica do Rio de Janeiro (PUC-Rio), R. Marques de Sao Vicente, 225, Gavea, Rio de Janeiro, RJ, 22451-900 (Brazil); Universidade Federal Fluminense (UFF), Campus do Valonguinho, Outeiro de Sao Joao Batista, s/no, 24020-150, Niteroi, RJ (Brazil); Saint' Pierre, Tatiana Dillenburg; Miekeley, Norbert [Pontificia Universidade Catolica do Rio de Janeiro (PUC-Rio), R. Marques de Sao Vicente, 225, Gavea, Rio de Janeiro, RJ, 22451-900 (Brazil); Oliveira da Fonseca, Teresa Cristina; Szatmari, Peter [Centro de Pesquisas Leopoldo A. Miguez de Mello da Petrobras (CENPES), Av. Horacio Macedo, 950, Cidade Universitaria, Rio de Janeiro, RJ, 21941-915 (Brazil)

    2011-05-15

    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 {mu}g L{sup -1} and 8 {mu}g L{sup -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.

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

    Science.gov (United States)

    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.

  17. Analysis of four toxic metals in a single rice seed by matrix solid phase dispersion -inductively coupled plasma mass spectrometry

    Science.gov (United States)

    He, Xiufen; Chen, Lixia; Chen, Xin; Yu, Huamei; Peng, Lixu; Han, Bingjun

    2016-12-01

    Toxic metals in rice pose great risks to human health. Metal bioaccumulation in rice grains is a criterion of breeding. Rice breeding requires a sensitive method to determine metal content in single rice grains to assist the variety selection. In the present study, four toxic metals of arsenic (As), cadmium (Cd), chromium (Cr) and lead (Pb) in a single rice grain were determined by a simple and rapid method. The developed method is based on matrix solid phase dispersion using multi-wall carbon nanotubes (MWCNTs) as dispersing agent and analyzed by inductively coupled plasma mass spectrometry. The experimental parameters were systematically investigated. The limits of detection (LOD) were 5.0, 0.6, 10 and 2.1 ng g‑1 for As, Cd, Cr, and Pb, respectively, with relative standard deviations (n = 6) of microwave digestion. The amount of sample required was reduced approximately 100 fold in comparison with the microwave digestion. The method has a high application potential for other sample matrices and elements with high sensitivity and sample throughput.

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

    Science.gov (United States)

    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.

  19. Direct determination of mercury in cosmetic samples by isotope dilution inductively coupled plasma mass spectrometry after dissolution with formic acid

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Ying; Shi, Zeming; Zong, Qinxia; Wu, Peng; Su, Jing [Sichuan Provincial Key Laboratory of Nuclear Technology in Geology, College of Nuclear Technology and Automation Engineering, Chengdu University of Technology, Chengdu 610059 (China); Liu, Rui, E-mail: liur.ray@gmail.com [Mineral Resources Chemistry Key Laboratory of Sichuan Higher Education Institutions, College of Materials and Chemistry and Chemical Engineering, Chengdu University of Technology, Chengdu 610059 (China)

    2014-02-17

    Graphical abstract: -- Highlights: •Simple, sensitive, and accurate method is established for mercury determination in cosmetics. •The sample preparation procedure is highly simplified. •Isotope dilution efficiently eliminates matrix effect. •First report of using formic acid based method in combination with PVG-ID-ICP MS for mercury quantitation in cosmetics. -- Abstract: A new method was proposed for the accurate determination of mercury in cosmetic samples based on isotopic dilution (ID)-photochemical vapor generation (PVG)-inductively coupled plasma mass spectrometry (ICP MS) measurement. Cosmetic samples were directly dissolved in formic acid solution and subsequently subjected to PVG for the reduction of mercury into vapor species following by ICP MS detection. Therefore, the risks of analyte contamination and loss were avoided. Highly enriched {sup 201}Hg isotopic spike is added to cosmetics and the isotope ratios of {sup 201}Hg/{sup 202}Hg were measured for the quantitation of mercury. With ID calibration, the influences originating from sample matrixes for the determination of mercury in cosmetic samples have been efficiently eliminated. The effects of several experimental parameters, such as the concentration of the formic acid, and the flow rates of carrier gas and sample were investigated. The method provided good reproducibility and the detection limits were found to be 0.6 pg mL{sup −1}. Finally, the developed method was successfully applied for the determination of mercury in six cosmetic samples and a spike test was performed to verify the accuracy of the method.

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

    Science.gov (United States)

    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.

  1. Determination of selenomethionine, selenocysteine, and inorganic selenium in eggs by HPLC-inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lipiec, Elzbieta; Siara, Grzegorz [CNRS/UPPA, Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, Pau (France); Warsaw University of Technology, Warsaw (Poland); Bierla, Katarzyna; Ouerdane, Laurent; Szpunar, Joanna [CNRS/UPPA, Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, Pau (France)

    2010-05-15

    A method for the simultaneous determination of selenomethionine (SeMet), selenocysteine (SeCys), and selenite [Se(IV)] in chicken eggs was developed. A sample preparation protocol including defatting, protein denaturation, and carbamidomethylation was optimized in order to achieve complete protein digestion and to avoid SeCys losses. Quantification was carried out by reversed-phase HPLC-inductively coupled plasma mass spectrometry (ICP MS) after quantitative isolation of the selenium-containing fraction by size-exclusion liquid chromatography. The detection limits were 0.06, 0.003, and 0.01 {mu}g g{sup -1} (dry weight) for SeCys, Se(IV) and SeMet, respectively, and the precision was 5-10%. The end products of carbamidomethylation of the different selenium species were identified for the first time by electrospray QTOF MS after custom-designed 2D HPLC purification. Differences in selenium speciation in egg yolk and white were highlighted, the yolk containing more SeCys and the white more SeMet. An insight into selenium bioaccessibility in eggs was obtained by digestion with simulated gastric and gastrointestinal juices and size-exclusion HPLC-ICP MS. (orig.)

  2. Quantification of Trace Amounts of Impurities in High Purity Cobalt by High Resolution Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    Hua Lin XIE; Xi Du NIE; You Gen TANG

    2006-01-01

    An analytical method using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for rapid simultaneous determination of Be, Mg, Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn, Sb, Ba, Pt, Au and Pb in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCl. The matrix effects due to thc presence of excess HCl and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination was tested and discussed. Correction for matrix effects, Sc, Rh and Bi were used as internal standards. The detection limits is 0.003-0.57 μg/g, the recovery ratio is 92.2%- 111.2%, and the RSD is less than 3.6%. The method is accurate, quick and convenient. It has been applied to the determination of trace impurities in high purity cobalt with satisfactory results.

  3. Quantification of trace amounts of impurities in high purity cobalt by high resolution inductively coupled plasma mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    XIE Hualin; HUANG Kelong; NIE Xidu; TANG Yougen

    2007-01-01

    An analytical method using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for rapid simultaneous determination of 24 elements (Be, Mg, Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Mo, Ag, Cd, Sn,Sb, Ba, Pt, Au, and Pb) in high purity cobalt was described. Sample digestions were performed in closed microwave vessels using HNO3 and HCl. The matrix effects because of the presence of excess HCl and Co were evaluated. The usefulness of high mass resolution for overcoming some spectral interference was demonstrated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits were 0.016-1.50 μg.g-1, the recovery ratios were 92.2%-111.2%, and the RSD was less than 3.6%. The method was accurate, quick, and convenient. It was applied to the determination of trace impurities in high purity cobalt with satisfactory results.

  4. Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

    2017-04-01

    In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

  5. [Discussion on diagenesis of Xilingang pluton-constrained by X-ray Fluorescence spectroscopy, plasma mass spectrometry and Raman spectroscopy].

    Science.gov (United States)

    Tang, Yu-Kun; Chen, Guo-Neng; Zhang, Ke; Huang, Hai-Hua

    2013-05-01

    The results on Xilingang pluton, mainly consisting of red beds, granites containing numerous debris of red beds and granites, obtained by X-ray fluorescence spectroscopy, plasma mass spectrometry and Raman spectroscopy show: (1) Xilingang pluton from red beds, granites containing numerous debris of red beds to granites has obvious characteristics of decreasing silicon and alkali content, and rising ignition loss, dark mineral content and oxidation index; (2) Chondrite-normalized REE distribution curves and primitive mantle-normalized spider diagram for trace elements of redbed, granites containing numerous debris of red beds and granites have a good consistency, the distribution characteristics of elements are similar to Nanling transformation-type granite; (3) The value of Raman spectrogram characteristic peak of quartz crystal in Xilingang granite decreased from the center of quartz crystal, and FWHM is steady. According to the above, the authors believe that Xilingang granite formed was related to in-situ melting of red beds and underlying strata and magma consolidation. Volatile components were discharged continuously, and oxidation index decreased gradually in the melting process. In the process of diagenesis, the top of pluton tend to be an ongoing silicon and alkali increase, while TFeO and MgO continue to migrate to bottom, and crystallization environment is a relatively closed and steady system.

  6. Green and Fast Laser Fusion Technique for Bulk Silicate Rock Analysis by Laser Ablation-Inductively Coupled Plasma Mass Spectrometry.

    Science.gov (United States)

    Zhang, Chenxi; Hu, Zhaochu; Zhang, Wen; Liu, Yongsheng; Zong, Keqing; Li, Ming; Chen, Haihong; Hu, Shenghong

    2016-10-18

    Sample preparation of whole-rock powders is the major limitation for their accurate and precise elemental analysis by laser ablation inductively-coupled plasma mass spectrometry (ICPMS). In this study, a green, efficient, and simplified fusion technique using a high energy infrared laser was developed for major and trace elemental analysis. Fusion takes only tens of milliseconds for each sample. Compared to the pressed pellet sample preparation, the analytical precision of the developed laser fusion technique is higher by an order of magnitude for most elements in granodiorite GSP-2. Analytical results obtained for five USGS reference materials (ranging from mafic to intermediate to felsic) using the laser fusion technique generally agree with recommended values with discrepancies of less than 10% for most elements. However, high losses (20-70%) of highly volatile elements (Zn and Pb) and the transition metal Cu are observed. The achieved precision is within 5% for major elements and within 15% for most trace elements. Direct laser fusion of rock powders is a green and notably simple method to obtain homogeneous samples, which will significantly accelerate the application of laser ablation ICPMS for whole-rock sample analysis.

  7. Roxarsone and transformation products in chicken manure: determination by capillary electrophoresis-inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Rosal, Charlita G; Momplaisir, Georges-Marie; Heithmar, Edward M

    2005-04-01

    The determination of the animal feed additive roxarsone (3-nitro-4-hydroxyphenylarsonic acid) and six of its possible transformation products (arsenite, arsenate, monomethylarsonate, dimethylarsinate, 3-amino-4-hydroxyphenylarsonic acid, and 4-hydroxyphenylarsonic acid) in chicken manure was investigated using capillary electrophoresis-inductively coupled plasma-mass spectrometry (CE-ICP-MS). Initial method development was conducted using ultraviolet (UV) detection for ruggedness and time efficiency. Separation of these seven arsenic species was effected using a 20 mM phosphate buffer at pH 5.7. The CE-ICP-MS limits of detection in terms of As for each of the species was in the low microg.L(-1) range, corresponding to absolute detection limits in the range 20-70 fg As (based on a 23 nL injection). Overall, the method developed in this study provides high selectivity and low limits of detection (1-3 microg.L(-1) or low-ppb, based on As), uses small sample volume (low nL), and produces minimal wastes.

  8. The quick and ultrasensitive determination of K in NaI using inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Arnquist, Isaac J.; Hoppe, Eric W.

    2017-04-01

    A highly sensitive, novel and quick assay method utilizing inductively coupled plasma mass spectrometry was developed for the determination of K in NaI powders and NaI(Tl) scintillator crystals for use in ultralow background applications. The determination of K (viz. 40K), as well as Th and U and their daughters, is important in ultralow background detector materials to ensure incorporation of materials of sufficiently high radiopurity. Through the use of improved instrumentation, cool plasma operating conditions, and meticulously clean sample preparations, detection limits of 11 fg natK∙g-1 (or 341 pBq 40K∙kg-1) was attained for K in pure water. Detection limits in the sample matrix (i.e., NaI) were 0.529 ng natK∙g NaI-1 (or 16.4 Bq 40K∙kg NaI -1). A number of different precursor NaI powder samples and NaI(Tl) scintillator crystals were assayed for their K content. Determinations ranged from 0.757 – 31.4 ng natK∙g NaI-1. This method allows for the screening of materials to unprecedented levels in a fraction of the time compared to gamma counting techniques, providing a useful method for a more effective screening tool of K in ultralow background detector materials.

  9. Determination of cadmium, mercury and lead in coal fly ash by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Liao, Hsien-Chung; Jiang, Shiuh-Jen

    1999-08-01

    Ultrasonic slurry sampling electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry (USS-ETV-ID-ICP-MS) has been applied to the determination of Cd, Hg and Pb in coal fly ash samples. Thioacetamide (TAC) was used as the modifier. Since the sensitivities of the elements studied in coal fly ash slurry and aqueous solution were quite different, isotope dilution method was used for the determination of Cd, Hg and Pb in these coal fly ash samples. The isotope ratios of each element were calculated from the peak areas of each injection peak. This method has been applied to the determination of Cd, Hg and Pb in NIST SRM 1633a coal fly ash reference material and a coal fly ash sample collected from Kaohsiung area. Analysis results of reference sample NIST SRM 1633a coal fly ash agreed satisfactorily with the certified values. The other sample determined by isotope dilution and method of standard additions was agreed satisfactorily. Precision was better than 6% for most of the determinations and accuracy was better than 4% with the USS-ETV-ID-ICP-MS method. Detection limits estimated from standard addition curves were in the range of 24-58, 6-28 and 108-110 ng g-1 for Cd, Hg and Pb, respectively.

  10. Determination of As, Mn, Pb and Se in coal by slurry electrothermal vaporization inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Maia, S.M. da; Silva, J.B.B. Da; Curtius, A.J.; Weiz, B.

    2000-07-01

    A method for the determination of trace elements in coal by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS), introducing the sample as a slurry, is proposed. The slurry was prepared by mixing the powdered coal ({lt} 45 {mu}m) with aqueous 5% v/v nitric acid solution in an ultrasonic bath. An ultrasonic probe was used to homogenize the slurry in the autosampler cup just before its introduction into the graphite tube. By introducing 10{mu}L of 4.0 mg mL{sup -1} coal slurry, using 3{mu}g of Pd as a modifier, and a pyrolysis temperature of 600{degree}C, most of the obtained values for four coal reference materials were well within the certified range, using external calibration with aqueous solutions. No carrier had to be added in addition to the palladium modifier. Using a lower slurry concentration of 1.3 mg mL{sup -1} and 2{mu}g of Pd as the modifier, the values obtained for lead were significantly lower than the certified ones. This problem could be solved in part by adding NaCl as a physical carrier, in addition to the palladium, showing that this carrier reduces the differences in the analyte transport from the sample and from the calibration solutions. However, results for most elements, except for arsenic, tended to be a little low even under these conditions, hence, preference was given to the higher slurry concentration.

  11. Arsenic and selenium speciation in coal fly ash extracts by ion chromatography-inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jackson, B.P.; Miller, W.P. [University of Georgia, Aiken, SC (United States). Savannah River Ecology Lab.

    1998-10-01

    Ion chromatography (IC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) was used to determine As(III), As(V), Se(IV), and Se(VI) in aqueous extracts of coal fly ash. Because all species were fully resolved, the resulting chromatograms were obtained by summing signal intensities for m/z 75 + m/z 82. Absolute detection limits of 7.2, 87, 117 and 28 pg for As(III), Se(IV), Se(VI), and As(V) respectively, were obtained corresponding to 0.072, 0.868, 1.174, and 0.284 {mu} gl{sup -1} for 100 {mu} l injection volume. The technique was used to determine the speciation of As and Se in aqueous extracts of 24 coal fly ash samples including NIST SRM 1633 b. The predominant species were As(V) and Se(IV), with As(III) detected in two low pH fly ashes. Extraction of fly ashes at pH 5 altered the concentrations of total soluble As and Se but did not affect the predominant As and Se speciation.

  12. Laser ablation inductively coupled plasma mass spectrometry: a new tool for trace element analysis in ice cores.

    Science.gov (United States)

    Reinhardt, H; Kriews, M; Miller, H; Schrems, O; Lüdke, C; Hoffmann, E; Skole, J

    2001-07-01

    A new method for the detection of trace elements in polar ice cores using laser ablation with subsequent inductively coupled plasma mass spectrometry analysis is described. To enable direct analysis of frozen ice samples a special laser ablation chamber was constructed. Direct analysis reduces the risk of contamination. The defined removal of material from the ice surface by means of a laser beam leads to higher spatial resolution (300-1000 microm) in comparison to investigations with molten ice samples. This is helpful for the detection of element signatures in annual layers of ice cores. The method was applied to the successful determination of traces for the elements Mg, Al, Fe, Zn, Cd, Pb, some rare-earth elements (REE) and minor constituents such as Ca and Na in ice cores. These selected elements serve as tracer elements for certain sources and their element signatures detected in polar ice cores can give hints to climate changes in the past. We report results from measurements of frozen ice samples, the achievable signal intensities, standard deviations and calibration graphs as well as the first signal progression of 205Pb in an 8,000-year-old ice core sample from Greenland. In addition, the first picture of a crater on an ice surface burnt by an IR laser made by cryogenic scanning electron microscopy is presented.

  13. Direct determination of arsenic in fresh and saline waters by electrothermal vaporization inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Conrad Grégoire, D.; de Lourdes Ballinas, Maria

    1997-01-01

    A method is described for the direct determination of arsenic in fresh and saline waters by electrothermal vaporization inductively coupled plasma mass spectrometry. Arsenic could be determined directly in waters containing up to 10 000 μg ml -1 NaCl without interference from the formation of 75ArCl +. For non-saline waters, arsenic was determined directly with the addition to both aqueous calibration standards and samples of 0.1 μg each of Pd and Mg to act as physical carriers. For the analysis of highly saline waters, the use of Pd and Mg chemical modifier served to thermally stabilize arsenic up to a temperature of 1000°C, while the separate addition of 8 mg of ammonium nitrate was used to remove chloride from the sample. This eliminated serious spectral interference on 75As + from 75ArCl +. Although the ArCl + spectral interference was completely eliminated, residual Na co-volatilized with As caused signal suppression, requiring the use of the method of standard additions for calibration. An absolute limit of detection limit for As of 0.069 pg was obtained corresponding to 6.9 pg ml -1 in a 10 μl sample.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  16. Sequential cloud point extraction of trace elements from biological samples and determination by inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Gine, Maria Fernanda; Patreze, Aparecida F.; Silva, Edson L. [Centro de Energia Nuclear na Agricultura (CENA-USP), Piracicaba, SP (Brazil)]. E-mail: mfgine@cena.usp.br; Sarkis, Jorge E.S.; Kakazu, Mauricio H. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2008-07-01

    A two-step sequential cloud point extraction (CPE) of trace elements from small sample volumes of human serum, animal blood, and food diet is proposed to gain analytical information in the analysis by inductively coupled plasma mass spectrometry. The first CPE was attained by adding O,O-diethyldithiophosphate, the non ionic surfactant Triton{sup R} X-114 followed by heating at 40 deg C, centrifugation and cooling at 0 deg C. The resulting surfactant-rich phase was separated to determine Cd, Pb and Cu by isotope dilution. Isotope ratio measurements presented RSD < 0.7%. The residual surfactant-poor phase solution had the pH adjusted in the range 4 to 5 before the chelating reagent, 4-(2-pyridylazo) resorcinol plus surfactant Triton{sup R} X-114 were added followed by the sequence to attain the CPE. Co and Ni were quantified in the second extracted surfactant-rich phases by standard additions method with RSD < 2%. Recoveries from 85 to 96% were obtained for all elements. Analyzing reference materials with certified and recommended values assessed accuracy. (author)

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

    Science.gov (United States)

    Kautenburger, Ralf; Beck, Horst Philipp

    2007-08-03

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2012-03-06

    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.

  20. Imaging Metals in Brain Tissue by Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry (LA-ICP-MS).

    Science.gov (United States)

    Hare, Dominic J; Kysenius, Kai; Paul, Bence; Knauer, Beate; Hutchinson, Robert W; O'Connor, Ciaran; Fryer, Fred; Hennessey, Tom P; Bush, Ashley I; Crouch, Peter J; Doble, Philip A

    2017-01-22

    Metals are found ubiquitously throughout an organism, with their biological role dictated by both their chemical reactivity and abundance within a specific anatomical region. Within the brain, metals have a highly compartmentalized distribution, depending on the primary function they play within the central nervous system. Imaging the spatial distribution of metals has provided unique insight into the biochemical architecture of the brain, allowing direct correlation between neuroanatomical regions and their known function with regard to metal-dependent processes. In addition, several age-related neurological disorders feature disrupted metal homeostasis, which is often confined to small regions of the brain that are otherwise difficult to analyze. Here, we describe a comprehensive method for quantitatively imaging metals in the mouse brain, using laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS) and specially designed image processing software. Focusing on iron, copper and zinc, which are three of the most abundant and disease-relevant metals within the brain, we describe the essential steps in sample preparation, analysis, quantitative measurements and image processing to produce maps of metal distribution within the low micrometer resolution range. This technique, applicable to any cut tissue section, is capable of demonstrating the highly variable distribution of metals within an organ or system, and can be used to identify changes in metal homeostasis and absolute levels within fine anatomical structures.

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

    Science.gov (United States)

    Giussani, Barbara; Monticelli, Damiano; Rampazzi, Laura

    2009-03-02

    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.

  2. High-resolution laser ablation-inductively coupled plasma-mass spectrometry imaging of cisplatin-induced nephrotoxic side effects.

    Science.gov (United States)

    Van Acker, Thibaut; Van Malderen, Stijn J M; Van Heerden, Marjolein; McDuffie, James Eric; Cuyckens, Filip; Vanhaecke, Frank

    2016-11-16

    Two-dimensional elemental mapping (bioimaging) via laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on 5 μm thick formalin-fixed, paraffin-embedded kidney tissue sections from Cynomolgus monkeys administered with increasing pharmacological doses of cisplatin. Laterally resolved pixels of 1 μm were achieved, enabling elemental analysis on a (sub-)cellular level. Zones of high Pt response were observed in the renal cortex, where proximal tubules are present, the epithelium of which is responsible for partial reabsorption of cisplatin. Histopathological evaluation, of hematoxylin and eosin-stained serial sections, adjacent to the sections probed via LA-ICP-MS, revealed minimal to mild cisplatin-related lesions (<100 μm) in the renal cortex. Necrotic proximal tubules with sloughed epithelial cells in their lumen could be linked directly to the areas with the highest accumulation of cisplatin, indicating a direct link between cellular concentration and toxicity, thereby providing more insight into the mechanisms through which renal damage occurs.

  3. Standard test method for determination of impurities in nuclear grade uranium compounds by inductively coupled plasma mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2010-01-01

    1.1 This test method covers the determination of 67 elements in uranium dioxide samples and nuclear grade uranium compounds and solutions without matrix separation by inductively coupled plasma mass spectrometry (ICP-MS). The elements are listed in Table 1. These elements can also be determined in uranyl nitrate hexahydrate (UNH), uranium hexafluoride (UF6), triuranium octoxide (U3O8) and uranium trioxide (UO3) if these compounds are treated and converted to the same uranium concentration solution. 1.2 The elements boron, sodium, silicon, phosphorus, potassium, calcium and iron can be determined using different techniques. The analyst's instrumentation will determine which procedure is chosen for the analysis. 1.3 The test method for technetium-99 is given in Annex A1. 1.4 The values stated in SI units are to be regarded as standard. 1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish ...

  4. Dry ashing of organic rich matrices with palladium for the determination of arsenic using inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Sahayam, A C; Chaurasia, S C; Venkateswarlu, G

    2010-02-19

    A dry ashing procedure is developed for the determination of As in organic rich matrices such as wheat flour, lichen and tobacco leaves. The volatility of As during dry ashing is avoided by the addition of palladium nitrate [Pd(NO(3))(2)]. The recovery of both As(III) and As(V) is found to be near quantitative. The residue after dry ashing is dissolved in nitric acid (HNO(3)) and analysed by inductively coupled plasma-mass spectrometry (ICP-MS). The process blank and limit of detection (LOD) are 11 and 6.6 ng g(-1), respectively. The procedure is applied for the determination of As in certified reference materials namely wheat flour NIST SRM 1567a (National Institute of Standards and Technology Standard Reference Material), lichen BCR CRM 482 (Institute for Reference Materials, European Commission) and Virginia tobacco leaves CTA-VTL-2 (Poland Academy of Sciences). The results obtained by the present procedure are in good agreement with the certified values and also determined after complete dissolution of samples using closed microwave digestion.

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

    Science.gov (United States)

    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 (behaviour of sphalerite serves to characterise ore types and help detect technologically important trace elements.

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

    Directory of Open Access Journals (Sweden)

    Adriana Dehelean

    2013-01-01

    Full Text Available 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.

  7. Determination of rare earth elements in dust deposited on tree leaves from Greater Cairo using inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Shaltout, Abdallah A; Khoder, M I; El-Abssawy, A A; Hassan, S K; Borges, Daniel L G

    2013-07-01

    This work aims at monitoring the rare earth elements (REEs) and Th in dust deposited on tree leaves collected inside and outside Greater Cairo (GC), Egypt. Inductively coupled plasma mass spectrometry (ICP-MS) was employed. The concentration of REEs in the collected dust samples was found to be in the range from 1 to 60 μg g(-1). The highest concentration of REEs was found in dust samples collected outside GC, in the middle of the Nile Delta. This would refer to the availability of black sands, due to desert wind occurrence during the sample collection, and anthropogenic activities. The limits of detection of the REEs ranged from 0.02 ng g(-1) for Tm to 3 ng g(-1) for Yb. There was an obvious variation in the concentration of REEs inside and outside GC due to variations of natural and anthropogenic sources. Strong correlations among all the REEs were found.

  8. Comparison of selenium determination in liver samples by atomic absorption spectroscopy and inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Miksa, Irina Rudik; Buckley, Carol L; Carpenter, Nancy P; Poppenga, Robert H

    2005-07-01

    Selenium (Se) is an essential trace element that is often deficient in the natural diets of domestic animal species. The measurement of Se in whole blood or liver is the most accurate way to assess Se status for diagnostic purposes. This study was conducted to compare hydride generation atomic absorption spectroscopy (HG-AAS) with inductively coupled plasma-mass spectrometry (ICP-MS) for the detection and quantification of Se in liver samples. Sample digestion was accomplished with magnesium nitrate and nitric acid for HG-AAS and ICP-MS, respectively. The ICP-MS detection was optimized for 82Se with yttrium used as the internal standard and resulted in a method detection limit of 0.12 microg/g. Selenium was quantified by both methods in 310 samples from a variety of species that were submitted to the Toxicology Laboratory at New Bolton Center (Kennett Square, PA) for routine diagnostic testing. Paired measurements for each sample were evaluated by a mean difference plot method. Limits of agreement were used to describe the maximum differences likely to occur between the 2 methods. Results suggest that under the specified conditions ICP-MS can be reliably used in place of AAS for quantitation of tissue Se at or below 2 microg/g to differentiate between adequate and deficient liver Se concentrations.

  9. Comparison of laser ablation and dried solution aerosol as sampling systems in inductively coupled plasma mass spectrometry.

    Science.gov (United States)

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

    2004-12-01

    This paper describes a study designed to determine the possibility of using a dried aerosol solution for calibration in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The relative sensitivities of tested materials mobilized by laser ablation and by aqueous nebulization were established, and the experimentally determined relative sensitivity factors (RSFs) were used in conjunction with aqueous calibration for the analysis of solid steel samples. To such a purpose a set of CRM carbon steel samples (SS-451/1 to SS-460/1) were sampled into an ICP-MS instrument by solution nebulization using a microconcentric nebulizer with membrane desolvating (D-MCN) and by laser ablation (LA). Both systems were applied with the same ICP-MS operating parameters and the analyte signals were compared. The RSF (desolvated aerosol response/ablated solid response) values were close to 1 for the analytes Cr, Ni, Co, V, and W, about 1.3 for Mo, and 1.7 for As, P, and Mn. Complementary tests were carried out using CRM SS-455/1 as a solid standard for one-point calibration, applying LAMTRACE software for data reduction and quantification. The analytical results are in good agreement with the certified values in all cases, showing that the applicability of dried aerosol solutions is a good alternative calibration system for laser ablation sampling.

  10. Flow injection on-line dilution for multi-element determination in human urine with detection by inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Wang, Jianhua; Hansen, Elo Harald; Gammelgaard, Bente

    2001-01-01

    of 16.5 with on-line standard addition, and sup/ 103/Rh was used as internal standard to compensate for signal fluctuation. The procedure was validated by the analysis of two standard reference materials SRM 2670 (NIST) and Seronorm(TM) Trace Elements in Urine. Recovery experiments were performed...... urine samples. No correlations between the concentrations of the elements were observed....

  11. Molecularly imprinted polymers as selective adsorbents for ambient plasma mass spectrometry.

    Science.gov (United States)

    Cegłowski, Michał; Smoluch, Marek; Reszke, Edward; Silberring, Jerzy; Schroeder, Grzegorz

    2017-05-01

    The application of molecularly imprinted polymers (MIPs) as molecular scavengers for ambient plasma ionization mass spectrometry has been reported for the first time. MIPs were synthesized using methacrylic acid as functional monomer; nicotine, propyphenazone, or methylparaben as templates; ethylene glycol dimethacrylate as a cross-linker; and 2,2'-azobisisobutyronitrile as polymerization initiator. To perform ambient plasma ionization experiments, a setup consisting of the heated crucible, a flowing atmospheric-pressure afterglow (FAPA) plasma ion source, and a quadrupole ion trap mass spectrometer has been used. The heated crucible with programmable temperature allows for desorption of the analytes from MIPs structure which results in their direct introduction into the ion stream. Limits of detection, linearity of the proposed analytical procedure, and selectivities have been determined for three analytes: nicotine, propyphenazone, and methylparaben. The analytes used were chosen from various classes of organic compounds to show the feasibility of the analytical procedure. The limits of detections (LODs) were 10 nM, 10, and 0.5 μM for nicotine, propyphenazone, and methylparaben, respectively. In comparison with the measurements performed for the non-imprinted polymers, the values of LODs were improved for at least one order of magnitude due to preconcentration of the sample and reduction of background noise, contributing to signal suppression. The described procedure has shown linearity in a broad range of concentrations. The overall time of single analysis is short and requires ca. 5 min. The developed technique was applied for the determination of nicotine, propyphenazone, and methylparaben in spiked real-life samples, with recovery of 94.6-98.4%. The proposed method is rapid, sensitive, and accurate which provides a new option for the detection of small organic compounds in various samples. Graphical abstract The experimental setup used for analysis.

  12. Trace element biomonitoring in hair of school children from a polluted area by sector field inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Drobyshev, Evgenii J; Solovyev, Nikolay D; Ivanenko, Natalya B; Kombarova, Maria Yu; Ganeev, Alexander A

    2017-01-01

    In the current study, a biomonitoring of 18 hair trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, Se, V, Zn, Ca, Na and P) in school children from Leningradskaya Oblast' is reported. A case group, residing in a proximity to the toxic waste disposal grounds (Krasniy Bor), has been assessed vs. controls from a non-urban settlement Seltso. In total, 166 hair samples were analysed using double focusing sector field inductively coupled plasma mass spectrometry after microwave-assisted sample digestion with nitric acid. For the determination of Ca, Na and P inductively coupled plasma optical emission spectrometry was employed. For the validation, a reference material and spiked hair samples were analysed. The data obtained was processed using parametric statistics and factor analysis. Determined concentrations of trace elements were in agreement with the previously published results on chemically polluted areas. In the case group, linear correlations between Al, Cr, Cu, Fe, Ni and V were observed. Also, these metals correlated to selenium hair content in the case group. Additionally, a correlation between hair Se and P was observed in the case subjects. Several gender differences in trace content were observed within each group. However, no age- or body index-related difference was found. The obtained results show that closely located waste disposal grounds intensifies trace element exposure in school children of Krasniy Bor. However, judging from rather high values for the controls, total environmental status of the region seems to be unstable, so additional monitoring and chemical safety measures are required. Copyright © 2016 Elsevier GmbH. All rights reserved.

  13. Determination of uranium from nuclear fuel in environmental samples using inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, S.F. [Forschungszentrum Juelich GmbH (Germany). Zentralabteilung fuer Chemische Analysen]|[Radiation Physics and Chemistry Problems Inst., Minsk (Belarus); Becker, J.S. [Forschungszentrum Juelich GmbH (Germany). Zentralabteilung fuer Chemische Analysen

    2000-11-01

    As a result of the accident at the Chernobyl nuclear power plant (NPP) the environment was contaminated with spent nuclear fuel. The {sup 236}U isotope was used in this study to monitor the spent uranium from nuclear fallout in soil samples collected in the vicinity of the Chernobyl NPP. A rapid and sensitive analytical procedure was developed for uranium isotopic ratio measurement in environmental samples based on inductively coupled plasma quadrupole mass spectrometry with a hexapole collision cell (HEX-ICP-QMS). The figures of merit of the HEX-ICP-QMS were studied with a plasma-shielded torch using different nebulizers (such as an ultrasonic nebulizer (USN) and Meinhard nebulizer) for solution introduction. A {sup 238}U{sup +} ion intensity of up to 27000 MHz/ppm in HEX-ICP-QMS with USN was observed by introducing helium into the hexapole collision cell as the collision gas at a flow rate of 10 ml min{sup -1}. The formation rate of uranium hydride ions UH{sup +}/U{sup +} of 2 x 10{sup -6} was obtained by using USN with a membrane desolvator. The limit of {sup 236}U/{sup 238}U ratio determination in 10 {mu}g 1{sup -1} uranium solution was 3 x 10{sup -7} corresponding to the detection limit for {sup 236}U of 3 pg 1{sup -1}. The precision of uranium isotopic ratio measurements in 10 {mu}g 1{sup -1} laboratory uranium isotopic standard solution was 0.13% ({sup 235}U/{sup 238}U) and 0.33% ({sup 236}U/{sup 238}U) using a Meinhard nebulizer and 0.45% ({sup 235}U/{sup 238}U) and 0.88% ({sup 236}U/{sup 238}U) using a USN. The isotopic composition of all investigated Chernobyl soil samples differed from those of natural uranium; i.e. in these samples the {sup 236}U/{sup 238}U ratio ranged from 10{sup -5} to 10{sup -3}. (orig.)

  14. 碰撞/反应池技术在等离子体质谱仪上的应用和发展%Development and Application on the Collision/Reaction Cell Technology for Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    陆文伟

    2005-01-01

    Over the past 8 years, the commercial collision/reaction cell with inductively coupled plasma mass spectrometry (ICP-MS) has been developed and improved continuously. The commercial cell devices benefit from the original fundamental framework on the collision cell. Now the processes and principle of the collision or reaction are clearer than before. There are two approaches for collision/reaction cell technology to overcome spectral interference problem in ICP-MS: a) remove isobaric interference; b) shift the analyt to less interference mass. The kinetic energy discrimination effect and bandpass has been applied respectively on different multipole cell for ejecting the undesirable interferences species produced within cell. The cell gas selection is depend on which interference species want to be compressed and the working characteristics of the cell. To meet most routine task for a wide range of multi-element measurement, a new approach is developed and work on two mixed gas mode switching. An additional important characteristic with the cell (collision focusing) has been noticed and applied to get excellent precision in isotope ratio measurement.

  15. Determination of sup 238 U in marine organisms by inductively coupled plasma mass spectrometry. Yudo ketsugo plasma shitsuryo bunsekiho ni yoru kaiyo seibutsuchu no sup 238 U no teiryo

    Energy Technology Data Exchange (ETDEWEB)

    Ishii, T.; Nakahara, M; Matsuda, M.; Ishikawa, M. (National Institute of Radiological Sciences, Ibaraki (Japan))

    1991-05-25

    Since the {sup 238} U concentration in seawater is about 3ng/ml at the element level and the activity concentration is 40 {mu} Bq/ml which are considerably higher that those of other {alpha} radioactive materials, it is necessary to study the concentration levels of many marine organisms. After confirming that the inductively coupled plasma mass spectrometry as a new high sensitive analysis for multi-elements is effective to analyze heavy elements such as rare earth elements or uranium, etc., this method was applied to determine {sup 238} U in 55 species of marine organism. The {sup 238} U concentration in soft tissues of marine animal ranged from 0.076 to 5000ng/g wet weight and large difference of concentration was observed depending on the kind of animal and the tissue. Especially, the branchial heart of cephalopod molluscs showed the specific accumulation of {sup 238} U. The concentration factor of branchial heart of Octopus vulgaris which showed the highest value was calculated to be about 10 {sup 3} by comparing it with the concentration of {sup 238} U in Japanese coastal waterseas. The concentration of {sup 238} U in 20 species of algae ranged from 10 to 3700ng/g dry weight. 11 refs., 2 figs., 9 tabs.

  16. Dynamic etching of soluble surface layers with on-line inductively coupled plasma mass spectrometry detection - a novel approach for determination of complex metal oxide surface cation stoichiometry

    OpenAIRE

    Limbeck, A; Rupp, GM; M. Kubicek; Tellez, H.; Druce, J; Ishihara, T.; Kilner, JA; Fleig, J.

    2016-01-01

    In this work, an innovative approach for determining the surface stoichiometry of complex metal oxide (CMO) thin films is presented. The procedure is based on treatment of the sample surface with different etching solutions, followed by on-line analysis of the derived eluates using inductively coupled plasma ? mass spectrometry (ICP-MS). Via consecutive treatment of the sample surface with water and diluted HCl, a differentiation between water soluble and acid soluble parts of near surface re...

  17. Determination of picomolar beryllium levels in seawater with inductively coupled plasma mass spectrometry following silica-gel preconcentration

    Energy Technology Data Exchange (ETDEWEB)

    Tazoe, Hirofumi, E-mail: tazoe@cc.hirosaki-u.ac.jp [Department of Radiation Chemistry, Institute of Radiation Emergency Mediation, Hirosaki University, 66-1 Hon-cho, Hirosaki, Aomori 036-8564 (Japan); College of Humanities and Sciences, Nihon University, 3-25-40, Sakurajosui, Setagaya-ku, Tokyo 156-8550 (Japan); Yamagata, Takeyasu [College of Humanities and Sciences, Nihon University, 3-25-40, Sakurajosui, Setagaya-ku, Tokyo 156-8550 (Japan); Obata, Hajime [Atmosphere and Ocean Research Institute, The Tokyo University, 5-1-5 Kashiwanoha, Kashiwa-shi, Chiba 277-8564 (Japan); Nagai, Hisao [College of Humanities and Sciences, Nihon University, 3-25-40, Sakurajosui, Setagaya-ku, Tokyo 156-8550 (Japan)

    2014-12-10

    Highlights: • We developesd the simplest and robust SPE method for ultra low picomolar level beryllium in seawater. • Just silica gel column can quantitatively adsorb beryllium in neutral pH condition containing natural seawater. • EDTA solution can eliminate seawater matrixes retaining Be in the column, which optimize to ICP-MS detemination. • Accurate and precise Be data have been obtained for natural seawater from North Pacific Ocean. - Abstract: A robust and rapid method for the determination of natural levels of beryllium (Be) in seawater was developed to facilitate mapping Be concentrations in the ocean. A solid-phase extraction method using a silica gel column was applied for preconcentration and purification of Be in seawater prior to determination of Be concentrations with inductively coupled plasma mass spectrometry (ICP-MS). Be was quantitatively adsorbed onto silica gel from solutions with pH values ranging from 6.3 to 9, including natural seawater. The chelating agent ethylenediamine tetraacetic acid was used to remove other ions in the seawater matrix (Na, Mg, and Ca) that interfere with the ICP-MS analysis. The reproducibility of the method was 3% based on triplicate analyses of natural seawater samples, and the detection limit was 0.4 pmol kg{sup −1} for 250 mL of seawater, which is sufficient for the analysis of seawater in the open ocean. The method was then used to determine the vertical profile of Be in the eastern North Pacific Ocean, which was found to be a recycled-type profile in which the Be concentration increased with depth from the surface (7.2 pmol kg{sup −1} at <200 m) to deep water (29.2 pmol kg{sup −1} from 3500 m to the bottom)

  18. A rapid method for simultaneous determination of arsenic, cadmium and lead in drinking water by inductively coupled plasma mass spectrometry

    Directory of Open Access Journals (Sweden)

    Joshua Rey P. Torres

    Full Text Available The raw water source of drinking water in most areas in the Philippines is typically river water and in some cases groundwater. These sources are prone to elevated levels of metals and metalloids that may cause exposure of the general population when the treatment of the water is inadequate. This work presents a simple method based on EPA Method 200.8 for the determination of total concentrations of arsenic (As, cadmium (Cd and lead (Pb in drinking water using inductively coupled plasma-mass spectrometry (ICP-MS as the element-selective detector. This was applied in the determination of these elements in the water supply in Metro Manila, Philippines. The method detection limits were 0.095 μg L-1, 0.043 μg L-1, and 0.114 μg L-1 for total As, Cd and Pb, respectively.The method was validated using National Institute of Standards and Technology (NIST 1643e certified reference material for trace elements in water and determined values were 60.4 ± 0.5 μg L-1, 6.7 ± 0.1 μg L-1, and 19.6 ± 0.5 μg L-1 for As, Cd and Pb, respectively. These determined values were in good agreement with the certified values in the reference material. Analysis of actual drinking water samples showed that most samples did not exceed the limit of the Philippine drinking water standard for the elements.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  1. Determination of mercury in coal by isotope dilution cold-vapor generation inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Long, Stephen E; Kelly, W Robert

    2002-04-01

    A method based on isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICPMS) has been developed for high-accuracy determinations of mercury in bituminous and sub-bituminous coals. A closed-system digestion process employing a Carius tube is used to completely oxidize the coal matrix and chemically equilibrate the mercury in the sample with a 201Hg isotopic spike. The digestates are diluted with high-purity quartz-distilled water, and the mercury is released as a vapor by reduction with tin(II) chloride. Measurements of 201Hg/202Hg isotope ratios are made using a quadrupole ICPMS system in time-resolved analysis mode. The new method has some significant advantages over existing methods. The instrument detection limit is less than 1 pg/mL. The average blank (n = 17) is 30 pg, which is roughly 1 order of magnitude lower than the equivalent microwave digestion procedure. The detection limit in coal is blank limited and is approximately 40 pg/g. Memory effects are very low. The relative reproducibility of the analytical measurements is approximately 0.5% for mercury concentrations in the range 10-150 ng/g. The method has been used to measure mercury concentrations in six coal reference materials, SRM 1632b (77.4 ng/g), SRM 1632c (94.3 ng/g), BCR 40 (433.2 ng/g), BCR 180 (125.0 ng/g), BCR 181 (135.8 ng/g), and SARM 20 (252.6 ng/g), as well as a coal fly ash, SRM 1633b (143.1 ng/g). The method is equally applicable to other types of fossil fuels including both crude and refined oils.

  2. Determination of mercury in coal by isotope dilution cold-vapor generation inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Long, S.E.; Kelly, W.R.

    2002-04-01

    A method based on isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICPMS) has been developed for high-accuracy determinations of mercury in bituminous and sub-bituminous coals. A closed-system digestion process employing a Carius tube is used to completely oxidize the coal matrix and chemically equilibrate the mercury in the sample with a Hg-201 isotopic spike. The digestates are diluted with high-purity quartz-distilled water, and the mercury is released as a vapor by reduction with tin chloride. Measurements of Hg-201/Hg-202 isotope ratios are made using a quadrupole ICPMS system in time-resolved analysis mode. The new method has some significant advantages over existing methods. The instrument detection limit is less than 1 pg/mL. The average blank (n = 17) is 30 pg, which is roughly 1 order of magnitude lower than the equivalent microwave digestion procedure. The detection limit in coal is blank limited and is similar to 40 pg/g. Memory effects are very low. The relative reproducibility of the analytical measurements is similar to 0.5% for mercury concentrations in the range 10-150 ng/g. The method has been used to measure mercury concentrations in six coal reference materials, SRM 1632b (77.4 ng/g), SRM 1632c (94.3 ng/g), BCR 40 (433.2 ng/g), BCR 180 (125.0 ng/g), BCR 181 (135.8 ng/g), and SARM 20 (252.6 ng/g), as well as a coal fly ash, SRM 1633b (143.1 ng/g). The method is equally applicable to other types of fossil fuels including both crude and refined oils.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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-).

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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 (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 0.5-4.3 ng g(-)(1), respectively. The contribution of As in DMAs(V) ranged from 0.1 +/- 0.1 ng g(-)(1) in walnuts to 1.3 +/- 0.3 ng g(-)(1) in pine nuts. MMAs(V) was not detected in almonds, peanuts, pine nuts, sunflower seeds, or walnuts, and the highest concentration was found in pistachio nuts (0.5 +/- 0.2 ng g(-)(1)).

  12. Bioimaging of metals and biomolecules in mouse heart by laser ablation inductively coupled plasma mass spectrometry and secondary ion mass spectrometry.

    Science.gov (United States)

    Becker, J Sabine; Breuer, Uwe; Hsieh, Hui-Fang; Osterholt, Tobias; Kumtabtim, Usarat; Wu, Bei; Matusch, Andreas; Caruso, Joseph A; Qin, Zhenyu

    2010-11-15

    Bioimaging mass spectrometric techniques allow direct mapping of metal and biomolecule distributions with high spatial resolution in biological tissue. In this study laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was used for imaging of transition metals (Fe, Cu, Zn, Mn, and Ti), alkali and alkaline-earth metals (Na, K, Mg, and Ca, respectively), and selected nonmetals (such as C, P, and S) in native cryosections of mouse heart. The metal and nonmetal images clearly illustrated the shape and the anatomy of the samples. Zinc and copper were inhomogeneously distributed with average concentrations of 26 and 11 μg g(-1), respectively. Titanium and manganese were detected at concentrations reaching 1 and 2 μg g(-1), respectively. The highest regional metal concentration of 360 μg g(-1)was observed for iron in blood present in the lumen of the aorta. Secondary ion mass spectrometry (SIMS) as an elemental and biomolecular mass spectrometric technique was employed for imaging of Na, K, and selected biomolecules (e.g., phosphocholine, choline, cholesterol) in adjacent sections. Here, two different bioimaging techniques, LA-ICPMS and SIMS, were combined for the first time, yielding novel information on both elemental and biomolecular distributions.

  13. A micro-fluidic sub-microliter sample introduction system for direct analysis of Chinese rice wine by inductively coupled plasma mass spectrometry using external aqueous calibration

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Heyong [Institute of Microanalytical Systems, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (China); College of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036 (China); Liu, Jinhua [College of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036 (China); Xu, Zigang [Institute of Analytical and Applied Chemistry, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (China); Yin, Xuefeng, E-mail: yinxf@zju.edu.cn [Institute of Microanalytical Systems, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (China); College of Material Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou, 310036 (China)

    2012-07-15

    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 {mu}L), 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{sup -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{sup -1} glucose was downscaled to 0.8 {mu}L. Further reducing the sampling volume to 0.4 {mu}L, 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 {mu}L was considered to be a good compromise between sensitivity and matrix effect. The flow rate of the carrier was chosen as 20 {mu}L min{sup -1} for obtaining peaks with the highest peak height within the shortest time. Based on these observations, a microflow injection ({mu}FI) 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{sup -1} with the detection limit of 19.8 and 10.4 ng L{sup -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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Makonnen, Yoseif; Beauchemin, Diane, E-mail: diane.beauchemin@chem.queensu.ca

    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 N{sub 2} in the outer plasma gas, and 0.50% v/v H{sub 2} 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{sup +} and Ar{sub 2}{sup +} as well as oxide levels by over an order of magnitude. On the other hand, the background from NO{sup +} and ArN{sup +} 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. - Highlights: • Addition of N{sub 2} to the plasma gas and H{sub 2} as a sheath gas results in a very robust ICP. • ArO{sup +} and Ar{sub 2}{sup +} background and oxide levels are reduced by over an order of magnitude. • Multielement analysis of rock digests is possible with a simple external calibration. • No internal standardization or matrix-matching is required for accurate analysis. • Cd and Mo were accurately determined in undiluted seawater.

  16. Analytical procedure for characterization of medieval wall-paintings by X-ray fluorescence spectrometry, laser ablation inductively coupled plasma mass spectrometry and Raman spectroscopy

    Science.gov (United States)

    Syta, Olga; Rozum, Karol; Choińska, Marta; Zielińska, Dobrochna; Żukowska, Grażyna Zofia; Kijowska, Agnieszka; Wagner, Barbara

    2014-11-01

    Analytical procedure for the comprehensive chemical characterization of samples from medieval Nubian wall-paintings by means of portable X-ray fluorescence (pXRF), laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and Raman spectroscopy (RS) was proposed in this work. The procedure was used for elemental and molecular investigations of samples from archeological excavations in Nubia (modern southern Egypt and northern Sudan). Numerous remains of churches with painted decorations dated back to the 7th-14th century were excavated in the region of medieval kingdoms of Nubia but many aspects of this art and its technology are still unknown. Samples from the selected archeological sites (Faras, Old Dongola and Banganarti) were analyzed in the form of transfers (n = 26), small fragments collected during the excavations (n = 35) and cross sections (n = 15). XRF was used to collect data about elemental composition, LA-ICPMS allowed mapping of selected elements, while RS was used to get the molecular information about the samples. The preliminary results indicated the usefulness of the proposed analytical procedure for distinguishing the substances, from both the surface and sub-surface domains of the wall-paintings. The possibility to identify raw materials from the wall-paintings will be used in the further systematic, archeometric studies devoted to the detailed comparison of various historic Nubian centers.

  17. Fast sequential multi-element determination of major and minor elements in environmental samples and drinking waters by high-resolution continuum source flame atomic absorption spectrometry.

    Science.gov (United States)

    Gómez-Nieto, Beatriz; Gismera, Ma Jesús; Sevilla, Ma Teresa; Procopio, Jesús R

    2015-01-07

    The fast sequential multi-element determination of 11 elements present at different concentration levels in environmental samples and drinking waters has been investigated using high-resolution continuum source flame atomic absorption spectrometry. The main lines for Cu (324.754 nm), Zn (213.857 nm), Cd (228.802 nm), Ni (232.003 nm) and Pb (217.001 nm), main and secondary absorption lines for Mn (279.482 and 279.827 nm), Fe (248.327, 248.514 and 302.064 nm) and Ca (422.673 and 239.856 nm), secondary lines with different sensitivities for Na (589.592 and 330.237 nm) and K (769.897 and 404.414 nm) and a secondary line for Mg (202.582 nm) have been chosen to perform the analysis. A flow injection system has been used for sample introduction so sample consumption has been reduced up to less than 1 mL per element, measured in triplicate. Furthermore, the use of multiplets for Fe and the side pixel registration approach for Mg have been studied in order to reduce sensitivity and extend the linear working range. The figures of merit have been calculated and the proposed method was applied to determine these elements in a pine needles reference material (SRM 1575a), drinking and natural waters and soil extracts. Recoveries of analytes added at different concentration levels to water samples and extracts of soils were within 88-115% interval. In this way, the fast sequential multi-element determination of major and minor elements can be carried out, in triplicate, with successful results without requiring additional dilutions of samples or several different strategies for sample preparation using about 8-9 mL of sample. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Trace amounts of rare earth elements in high purity samarium oxide by sector field inductively coupled plasma mass spectrometry after separation by HPLC

    Energy Technology Data Exchange (ETDEWEB)

    Pedreira, W.R. [Instituto de Geociencias, Universidade de Brasilia (UnB), 70910-900 Brasilia, DF (Brazil) and Fundacao Jorge Duprat Figueiredo de Seguranca e Medicina do Trabalho (FUNDACENTRO), 05409-002 Sao Paulo, SP (Brazil)]. E-mail: walter.pedreira@fundacentro.gov.br; Queiroz, C.A. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), 05508-900 Sao Paulo, SP (Brazil); Abrao, A. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), 05508-900 Sao Paulo, SP (Brazil); Rocha, S.M. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), 05508-900 Sao Paulo, SP (Brazil); Vasconcellos, M.E. de [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), 05508-900 Sao Paulo, SP (Brazil); Boaventura, G.R. [Instituto de Geociencias, Universidade de Brasilia (UnB), 70910-900 Brasilia, DF (Brazil); Pimentel, M.M. [Instituto de Geociencias, Universidade de Brasilia (UnB), 70910-900 Brasilia, DF (Brazil)

    2006-07-20

    Today there is an increasing need for high purity rare earth compounds in various fields, the optical, the electronics, the ceramic, the nuclear and geochemistry. Samarium oxide has special uses in glass, phosphors, lasers and thermoelectric devices. Calcium chloride crystals treated with samarium have been employed in lasers, which produce light beams intense enough to burn metal. In general, the inductively coupled plasma mass spectrometry (ICP-MS) presents some advantages for trace element analysis, due to high sensitivity and resolution, when compared with other analytical techniques such as ICP optical emission spectrometry (ICP-OES). In this work, sector field inductively coupled plasma mass spectrometry was used. Sixteen elements (Sc, Y and 14 lanthanides) were determined selectively with the ICP-MS system using a concentration gradient method. The detection limits with the ICP-MS system were about 0.2 (La) pg mL{sup -1} to 8 (Gd) pg mL{sup -1}. The %R.S.D. of the methods varying between 0.9 and 1.5% for a set of five (n = 5) replicates was found for the IPEN's material and for the certificate reference sample. Determination of trace REEs in two high pure samarium oxides samples (IPEN and JMC) was performed. IPEN's material is highly pure (>99.99%) and was successfully analyzed without spectral interference (MO{sup +} and MOH{sup +})

  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.

    Science.gov (United States)

    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. Imaging of Selenium by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) in 2-D Electrophoresis Gels and Biological Tissues.

    Science.gov (United States)

    Cruz, Elisa Castañeda Santa; Susanne Becker, J; Sabine Becker, J; Sussulini, Alessandra

    2018-01-01

    Selenium and selenoproteins are important components of living organisms that play a role in different biological processes. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a powerful analytical technique that has been employed to obtain distribution maps of selenium in biological tissues in a direct manner, as well as in selenoproteins, previously separated by their molecular masses and isoelectric points using two-dimensional polyacrylamide gel electrophoresis (2-D PAGE). In this chapter, we present the protocols to perform LA-ICP-MS imaging experiments, allowing the distribution visualization and determination of selenium and/or selenoproteins in biological systems.

  1. Speciation of selenium in a commercial dietary supplement by liquid chromatography coupled with inductively coupled plasma-mass spectrometry (ICP-MS).

    Science.gov (United States)

    Ayouni, Linda; Barbier, Frédérique; Imbert, Jean-Louis; Lantéri, Pierre; Grenier-Loustalot, Marie-Florence

    2007-05-01

    Size exclusion and anion-exchange chromatographies coupled with inductively coupled plasma-mass spectrometry (ICP-MS) were used for the speciation of selenium (Se) in a dietary supplement. A sequential extraction method resulted in 85% recovery of Se and 78% of the Se extracted could be identified. The results obtained show that selenomethionine and its oxide are the predominant compounds, while selenite and selenomethylcysteine are present at low concentrations. Methane seleninic acid, probably arising from the oxidation of selenomethylcysteine, accounted for 22% of total Se. High-molecular-weight compounds, probably proteins, were detected in sodium dodecyl sulfate (SDS) and driselase extracts by size exclusion chromatography.

  2. A method for studies on interactions between a gold-based drug and plasma proteins based on capillary electrophoresis with inductively coupled plasma mass spectrometry detection

    DEFF Research Database (Denmark)

    Nguyen, Tam T T N; Østergaard, Jesper; Gammelgaard, Bente

    2015-01-01

    An analytical method based on capillary electrophoresis (CE) and inductively coupled plasma mass spectrometry (ICP-MS) detection was developed for studies on the interaction of gold-containing drugs and plasma proteins using auranofin as example. A detection limit of 18 ng/mL of auranofin...... was the major auranofin-interacting protein in plasma. The CE-ICP-MS method is proposed as a novel approach for kinetic studies of the interactions between gold-based drugs and plasma proteins. Graphical Abstract Development of a CE-ICP-MS based method allows for studies on interaction of the gold containing...

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

    Science.gov (United States)

    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

  4. Determination of released heavy metal elements in concrete by inductively coupled plasma mass spectrometry%混凝土中重金属元素溶出量的质谱分析

    Institute of Scientific and Technical Information of China (English)

    周学忠; 谢华林

    2012-01-01

    An inductively coupled plasma mass spectrometry (ICP-MS) with an octopole reaction/collision cell and shield torch system was employed for the simultaneous determination of released heavy metal elements in concrete. The elements Cr, Mn, Ni, Cu, Zn, As, Cd, Sn, Sb and Pb were determined by introducing the hydrogen gas or helium gas into the reaction/collision cell to eliminate the interference of multi-element molecules and ions. Ge, In and Tb were used to correct the matrix interference and drift. Under the optimal conditions, the detection limits of the 10 elements are in the range of 0. 001 ~ 0. 033 μg/L with the relative standard deviation (RSDs) 0. 85% ~2. 8% , and the recoveries of the samples were in the range of 91.1%~103.9%.%利用带八极杆碰撞/反应池和屏蔽炬技术的电感耦合等离子体质谱直接测定混凝土中Cr,Mn,Ni,Cu,Zn,As,Cd,Sn,Sb,Pb等多种重金属元素的溶出量.通过向碰撞池中引入氢气和氦气消除多元素分子离子的干扰,以50μg/L的Ge,In,Tb为内标元素校正基体干扰和漂移.10种待测元素的检出限为0.001~0.033μg/L,相对标准偏差为0.85%~2.8%,样品的加标回收率在91.1%~103.9%之间.

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

    Science.gov (United States)

    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 (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 trioleinate), of which the extrapolation allowed for the prediction of the identity [glycerol dioleinate-stearate (OOS) and glycerol oleinate-distearate (OSS)] of the nonpolar species detected by ICP MS in the oil but not detected by electrospray MS.

  6. Analytical procedure for characterization of medieval wall-paintings by X-ray fluorescence spectrometry, laser ablation inductively coupled plasma mass spectrometry and Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Syta, Olga; Rozum, Karol; Choińska, Marta [Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Zielińska, Dobrochna [Institute of Archaeology, University of Warsaw, Krakowskie Przedmieście 26/28, 00-927 Warsaw (Poland); Żukowska, Grażyna Zofia [Chemical Faculty, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw (Poland); Kijowska, Agnieszka [National Museum in Warsaw, Aleje Jerozolimskie 3, 00-495 Warsaw (Poland); Wagner, Barbara, E-mail: barbog@chem.uw.edu.pl [Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)

    2014-11-01

    Analytical procedure for the comprehensive chemical characterization of samples from medieval Nubian wall-paintings by means of portable X-ray fluorescence (pXRF), laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and Raman spectroscopy (RS) was proposed in this work. The procedure was used for elemental and molecular investigations of samples from archeological excavations in Nubia (modern southern Egypt and northern Sudan). Numerous remains of churches with painted decorations dated back to the 7th–14th century were excavated in the region of medieval kingdoms of Nubia but many aspects of this art and its technology are still unknown. Samples from the selected archeological sites (Faras, Old Dongola and Banganarti) were analyzed in the form of transfers (n = 26), small fragments collected during the excavations (n = 35) and cross sections (n = 15). XRF was used to collect data about elemental composition, LA-ICPMS allowed mapping of selected elements, while RS was used to get the molecular information about the samples. The preliminary results indicated the usefulness of the proposed analytical procedure for distinguishing the substances, from both the surface and sub-surface domains of the wall-paintings. The possibility to identify raw materials from the wall-paintings will be used in the further systematic, archeometric studies devoted to the detailed comparison of various historic Nubian centers. - Highlights: • The analytical procedure for examination of unique wall paintings was proposed. • Identification of pigments and supporting layers of wall-paintings was obtained. • Heterogeneous samples were mapped with the use of LA-ICPMS. • Anatase in the sub-surface regions of samples was detected by Raman spectroscopy.

  7. Application of femtosecond laser ablation inductively coupled plasma mass spectrometry for quantitative analysis of thin Cu(In,Ga)Se{sub 2} solar cell films

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seokhee [School of Mechatronics, Gwangju Institute of Science and Technology, 1 Oryong-dong, Buk-gu, Gwangju 500-712 (Korea, Republic of); Gonzalez, Jhanis J. [Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (United States); Applied Spectra Inc., 46665 Fremont Boulevard, Fremont, CA 94538 (United States); Yoo, Jong H. [Applied Spectra Inc., 46665 Fremont Boulevard, Fremont, CA 94538 (United States); Chirinos, Jose R. [Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (United States); Facultad de Ciencias, Universidad Central de Venezuela, Caracas 1041A (Venezuela, Bolivarian Republic of); Russo, Richard E. [Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (United States); Applied Spectra Inc., 46665 Fremont Boulevard, Fremont, CA 94538 (United States); Jeong, Sungho, E-mail: shjeong@gist.ac.kr [School of Mechatronics, Gwangju Institute of Science and Technology, 1 Oryong-dong, Buk-gu, Gwangju 500-712 (Korea, Republic of)

    2015-02-27

    This work reports that the composition of Cu(In,Ga)Se{sub 2} (CIGS) thin solar cell films can be quantitatively predicted with high accuracy and precision by femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs-LA-ICP-MS). It is demonstrated that the results are strongly influenced by sampling conditions during fs-laser beam (λ = 1030 nm, τ = 450 fs) scanning on the CIGS surface. The fs-LA-ICP-MS signals measured at optimal sampling conditions generally provide a straight line calibration with respect to the reference concentrations measured by inductively coupled plasma optical emission spectroscopy (ICP-OES). The concentration ratios predicted by fs-LA-ICP-MS showed high accuracy, to 95–97% of the values measured with ICP-OES, for Cu, In, Ga, and Se elements. - Highlights: • Laser ablation inductively coupled plasma mass spectrometry of thin film is reported. • Concentration ratio prediction with a confidence level of 95–97% is achieved. • Quantitative determination of composition is demonstrated.

  8. Multi-element analysis of water decoction of medicine food homology plants using inductively coupled plasma-tandem mass spectrometry

    Science.gov (United States)

    Fu, Liang; Shi, Shu-Yun; Chen, Xiao-Qing

    2017-07-01

    The concentration of twelve trace elements in the water decoction of medicine food homology plants (MFHP) was determined by inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). Water decoctions of MFHP were analyzed directly using the MS/MS mode after acidification by 1% (v/v) nitric acid. The polyatomic interferences were eliminated by oxygen mass shift, oxygen on-mass, and ammonia mass shift. The accuracy of the method was verified by analysis of standard reference materials. This method was utilized to investigate the water decoction composition of 16 common Chinese MFHPs. The trace elements in the water decoctions of different MFHPs presented significantly different dissolution ratios. The dissolution ratio of V was the lowest (4.21%-14.86%), whereas Zn showed the highest dissolution ratio (24.87%-86.80%). In addition, the dissolution ratio of heavy metallic elements in most MFHP was equal to or was lower than 30%. Therefore, consumption of MHFP decoction could decrease the heavy metal intake associated with MFHP use and reduce the risk of heavy metal poisoning.

  9. 2D elemental mapping of sections of human kidney stones using laser ablation inductively-coupled plasma-mass spectrometry: Possibilities and limitations

    Science.gov (United States)

    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.

  10. The use of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of toxic and essential elements in different types of food samples

    Science.gov (United States)

    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).

  11. Demonstration of femtosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements in U-10Mo nuclear fuel foils

    Energy Technology Data Exchange (ETDEWEB)

    Havrilla, George Joseph [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Gonzalez, Jhanis [Applied Spectra Inc., Fremont, CA (United States)

    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.

  12. Laser ablation-inductively coupled plasma-mass spectrometry: Examinations of the origins of polyatomic ions and advances in the sampling of particulates

    Energy Technology Data Exchange (ETDEWEB)

    Witte, Travis [Iowa State Univ., Ames, IA (United States)

    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.

  13. A novel assay method for the trace determination of Th and U in copper and lead using inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    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.

  14. Rapid Determination of Plutonium Isotopes in Environmental Samples Using Sequential Injection Extraction Chromatography and Detection by Inductively Coupled Plasma Mass Spectrometry

    DEFF Research Database (Denmark)

    Qiao, Jixin; Hou, Xiaolin; Roos, Per

    2009-01-01

    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......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....... 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 104. The duration...

  15. Survey of inorganic arsenic in marine animals and marine certified reference materials by anion exchange high-performance liquid chromatography-inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Sloth, Jens Jørgen; Larsen, Erik Huusfeldt; Julshamn, Kåre

    2005-01-01

    A method for the determination of inorganic arsenic in seafood samples using high-performance liquid chromatography-inductively coupled plasma mass spectrometry is described. The principle of the method relied on microwave-assisted alkaline dissolution of the sample, which at the same time oxidized...... arsenite [As(Ill)] to arsenate [As(V)], whereby inorganic arsenic could be determined as the single species As(V). Anion exchange chromatography using isocratic elution with aqueous ammonium carbonate as the mobile phase was used for the separation of As(V) from other coextracted organoarsenic compounds......, including arsenobetaine. The stability of organoarsenic compounds during the sample pretreatment was investigated, and no degradation/conversion to inorganic arsenic was detected. The method was employed for the determination of inorganic arsenic in a variety of seafood samples including fish, crustaceans...

  16. Determination of platinum group elements by inductively coupled plasma-mass spectrometry combined with nickel sulfide fire assay and tellurium coprecipitation

    Science.gov (United States)

    Sun, Yali; Guan, Xiyun; Du, Andao

    1998-09-01

    A method was developed for the determination of trace platinum group elements (PGEs) by nickel sulfide fire assay inductively coupled plasma-mass spectrometry (ICP-MS). With isotope dilution, the improved technique gives precise Os content data. Through the purification of the reagent nickel oxide, reagent blank was greatly reduced. Results obtained for the standard reference materials (SRM) GPt-1-GPt-7(GBW 07288-07294, China), DZ Σ-2 (GBW 07102, China) and Guilin Cu-Ni Ore are in good agreement with the recommended values for platinum group elements. The detection limits ranged from 0.01 to 0.39 ng/g. The relative standard deviations for Ru, Rh, Pd and Ir were less than 5%, for Os less than 1%, and Pt less than 8% for SRM GPt-6.

  17. Determination of picomolar levels of platinum in estuarine waters: a comparison of cathodic stripping voltammetry and isotope dilution-inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Obata, Hajime; Yoshida, Tetsuaki; Ogawa, Hiroshi

    2006-10-27

    A comparative study to determine picomolar concentrations of platinum in natural waters was performed using two different analytical techniques. Results obtained by cathodic stripping voltammetry (CSV) were compared with those obtained by isotope dilution-inductively coupled plasma mass spectrometry (ID-ICPMS) combined with anion exchange resin column extraction method. Using successive UV irradiations with low-pressure mercury (L-Hg) lamp for 4h prior to CSV analysis, the results of both methods were comparable. Without adequate photolytic decomposition, the results obtained using CSV were generally lower than those obtained using ID-ICPMS in the estuarine waters around Tokyo Bay. This difference implies the presence of organically complexed Pt species in the estuarine waters. The Pt enrichment in the middle of the Tokyo Bay estuaries probably reflects the anthropogenic release of Pt from highly populated areas in Tokyo.

  18. A rapid monitoring method for inorganic arsenic in rice flour using reversed phase-high performance liquid chromatography-inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Narukawa, Tomohiro; Chiba, Koichi; Sinaviwat, Savarin; Feldmann, Jörg

    2017-01-06

    A new rapid monitoring method by means of high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) following the heat-assisted extraction was developed for measurement of total inorganic arsenic species in rice flour. As(III) and As(V) eluted at the same retention time and completely separated from organoarsenic species by an isocratic elution program on a reversed phase column. Therefore, neither ambiguous oxidation of arsenite to arsenate nor the integration of two peaks were necessary to determine directly the target analyte inorganic arsenic. Rapid injection allowed measuring 3 replicates within 6min and this combined with a quantitative extraction of all arsenic species from rice flour by a 15min HNO3-H2O2 extraction makes this the fastest laboratory based method for inorganic arsenic in rice flour.

  19. Investigation of heavy-metal accumulation in selected plant samples using laser induced breakdown spectroscopy and laser ablation inductively coupled plasma mass spectrometry

    Science.gov (United States)

    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.

  20. Characterization of the aerosol produced by infrared femtosecond laser ablation of polyacrylamide gels for the sensitive inductively coupled plasma mass spectrometry detection of selenoproteins

    Energy Technology Data Exchange (ETDEWEB)

    Claverie, Fanny [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l' Environnement et les Materiaux, UMR 5254 CNRS- Universite de Pau et des Pays de l' Adour, Helioparc Pau-Pyrenees, 2 Avenue du President Angot, 64053 Pau Cedex 9 (France); Novalase SA, Z.I de la Briqueterie, 6 Impasse du bois de la Grange, 33610 Canejan (France); Pecheyran, Christophe [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l' Environnement et les Materiaux, UMR 5254 CNRS- Universite de Pau et des Pays de l' Adour, Helioparc Pau-Pyrenees, 2 Avenue du President Angot, 64053 Pau Cedex 9 (France)], E-mail: Christophe.pecheyran@univ-pau.fr; Mounicou, Sandra [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l' Environnement et les Materiaux, UMR 5254 CNRS- Universite de Pau et des Pays de l' Adour, Helioparc Pau-Pyrenees, 2 Avenue du President Angot, 64053 Pau Cedex 9 (France); Ballihaut, Guillaume [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l' Environnement et les Materiaux, UMR 5254 CNRS- Universite de Pau et des Pays de l' Adour, Helioparc Pau-Pyrenees, 2 Avenue du President Angot, 64053 Pau Cedex 9 (France); Laboratoire d' Ecologie Moleculaire (Microbiologie), UMR 5254 CNRS- Universite de Pau et des Pays de l' Adour, avenue de l' Universite, B.P. 1155, F-64013 Pau (France); Fernandez, Beatriz [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l' Environnement et les Materiaux, UMR 5254 CNRS- Universite de Pau et des Pays de l' Adour, Helioparc Pau-Pyrenees, 2 Avenue du President Angot, 64053 Pau Cedex 9 (France); Alexis, Joel [Laboratoire Genie de Production, Ecole Nationale d' Ingenieurs de Tarbes, 47 avenue d' Azereix BP 1629, 65016 Tarbes (France)] (and others)

    2009-07-15

    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. Pecheyran, 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 {mu}m. 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 {mu}m 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 ({delta}T{approx} 25 {+-} 5 K). This suggests that the cohesion forces between the thin particles composing these large

  1. Speciation of the bio-available iodine and bromine forms in edible seaweed by high performance liquid chromatography hyphenated with inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Romaris-Hortas, Vanessa; Bermejo-Barrera, Pilar [Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, University of Santiago de Compostela, Avenida das Ciencias, s/n. 15782 - Santiago de Compostela (Spain); Moreda-Pineiro, Jorge [Department of Analytical Chemistry, Faculty of Sciences, University of A Coruna, Campus da Zapateira, s/n. 15071, A Coruna (Spain); Moreda-Pineiro, Antonio, E-mail: antonio.moreda@usc.es [Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, University of Santiago de Compostela, Avenida das Ciencias, s/n. 15782 - Santiago de Compostela (Spain)

    2012-10-01

    Highlights: Black-Right-Pointing-Pointer Bioavailable iodine and bromine speciation in edible seaweed were developed. Black-Right-Pointing-Pointer In vitro dialyzability was used to assess the bioavailable fractions. Black-Right-Pointing-Pointer AEC hyphenated with inductively coupled plasma-mass spectrometry was used. Black-Right-Pointing-Pointer Iodide, MIT, DIT, bromide and bromate were found in dialyzates from edible seaweed. Black-Right-Pointing-Pointer Positive correlation between bioavailability and protein contents was found. - Abstract: A bioavailability study based on an in vitro dialyzability approach has been applied to assess the bio-available fractions of iodine and bromine species from edible seaweed. Iodide, iodate, 3-iodo-tyrosine (MIT), 3,5-diiodo-tyrosine (DIT), bromide and bromate were separated by anion exchange chromatography under a gradient elution mode (175 mM ammonium nitrate plus 15% (v/v) methanol, pH 3.8, as a mobile phase, and flow rates within the 0.5-1.5 mL min{sup -1} range). Inductively coupled plasma-mass spectrometry (ICP-MS) was used as a selective detector for iodine ({sup 127}I) and bromine ({sup 79}Br). Low dialyzability ratios (within the 2.0-18% range) were found for iodine species; whereas, moderate dialyzability percentages (from 9.0 to 40%) were obtained for bromine species. Iodide and bromide were the major species found in the dialyzates from seaweed, although MIT and bromate were also found in the dialyzates from most of the seaweed samples analysed. However, DIT was only found in dialyzates from Wakame, Kombu, and NIES 09 (Sargasso) certified reference material; whereas, iodate was not found in any dialyzate. Iodine dialyzability was found to be dependent on the protein content (negative correlation), and on the carbohydrate and dietary fibre levels (positive correlation). However, bromine dialyzability was only dependent on the protein amount in seaweed (negative correlation).

  2. Comparison of tunable bandpass reaction cell inductively coupled plasma mass spectrometry with conventional inductively coupled plasma mass spectrometry for the determination of heavy metals in whole blood and urine

    Science.gov (United States)

    Nixon, David E.; Neubauer, Kenneth R.; Eckdahl, Steven J.; Butz, John A.; Burritt, Mary F.

    2004-09-01

    A Dynamic Reaction Cell™ inductively coupled plasma mass spectrometer (DRC-ICP-MS) was evaluated for the determination of arsenic, lead, cadmium, mercury, and thallium in urine and whole blood. Reaction cell conditions were evaluated for suppression of ArCl + and CaCl + polyatomic interferences. The reaction gas was 5% hydrogen in argon. Lead, cadmium, mercury, and thallium were determined with the reaction cell vented. Mixture of 2.5% t-butanol, 0.5% HCl, and 2 mg Au/l plus Ga, Rh, and Bi internal standards was used to dilute whole blood and urine. Calibration was achieved using aqueous acidic standards spiked into urine matrix. Urine and whole blood addition calibration curves were nearly identical for all five elements. DRC-ICP-MS detection limits were equivalent or better than conventional ICP-MS. Within run coefficients of variation (CV's) were nearly the same for DRC-ICP-MS and conventional ICP-MS for National Institute of Standards and Technology (NIST) SRM 2670 and BioRad Lyphochek Urine Metals Control. DRC-ICP-MS within run CV's for As, Pb, Cd, and Hg were 1.9%, 4%, 1.7%, and 1.7%, respectively, for NIST 2670 and 2.9%, 1.8%, 3.4%, 1.7%, and 1.0% for BioRad urine. BioRad Lyphochek Whole Blood control concentrations and CV's were: 78 μg/l (3.8%), 284 μg/l (0.52%), and 544 μg/l (0.9%). With the exception of mercury day-to-day CV's for certified whole blood and urine controls were less than 4% on both the DRC-ICP-MS and conventional ICP-MS.

  3. Results of an interlaboratory method performance study for the size determination and quantification of silver nanoparticles in chicken meat by single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS)

    NARCIS (Netherlands)

    Weigel, Stefan; Peters, Ruud; Loeschner, Katrin; Grombe, Ringo; Linsinger, Thomas P.J.

    2017-01-01

    Single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) promises fast and selective determination of nanoparticle size and number concentrations. While several studies on practical applications have been published, data on formal, especially interlaboratory validation of sp-ICP-MS,

  4. Results of an interlaboratory method performance study for the size determination and quantification of silver nanoparticles in chicken meat by single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS)

    DEFF Research Database (Denmark)

    Weigel, Stefan; Peters, Ruud J.; Löschner, Katrin

    2017-01-01

    Single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) promises fast and selective determination of nanoparticle size and number concentrations. While several studies on practical applications have been published, data on formal, especially interlaboratory validation of sp-ICP-MS...

  5. Analysis of Isotopic Abundance of Plutonium by Multicollector-Inductively Coupled Plasma Mass Spectrometry%多接收电感耦合等离子体质谱法测量痕量钚同位素

    Institute of Scientific and Technical Information of China (English)

    张继龙; 王同兴; 李力力; 常志远; 赵永刚; 刘俊岭

    2005-01-01

    The isotopic analysis of 232Pu plutonium in 5×10-12 g/g samples using a multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) is described. IRMM-290b and uranium (UTB750) were used to correct the metrical data, and the analytical precision is about 0.5%.

  6. Determination of depleted uranium in fish: validation of a confirmatory method by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS).

    Science.gov (United States)

    D'Ilio, S; Violante, N; Senofonte, O; Petrucci, F

    2007-08-06

    Depleted uranium (DU) is a by-product of the uranium enrichment process for nuclear fuel. According to the Commission Decision 2002/657/EC, a confirmatory method for the quantification of DU in freeze-dried fish was developed by isotope ratio dynamic reaction cell inductively coupled plasma-mass spectrometry (IR-DRC-ICP-MS). A preliminary study was performed to determine the following parameters: instrumental detection limit (IDL), isotopic ratio measurement limit (IRML), percentage of DU (P(DU)) in presence of natural uranium (NU) and limit of quantification (LoQ(DU)). The analyses were carried out by means of IR-DRC-ICP-MS. Ammonia was the reaction gas used for the dynamic reaction cell. In addition, a sector field inductively coupled plasma mass spectrometer (SF-ICP-MS) was employed to calculate the within-laboratory reproducibility. For the confirmatory method the following parameters were determined: (a) trueness; (b) precision; (c) critical concentrations alpha and beta (CC(alpha), CC(beta)); (d) specificity; (e) stability. Trueness was assessed by using the recovery tests. The recovery and within-laboratory reproducibility were determined by fortifying the blank digested solution of dogfish tissue: six aliquots were fortified at 1, 1.5 and 2 times the LOQ(DU) with 25.0, 37.5 and 50.0 ng L(-1) or 4.16, 6.24, 8.32 microg kg(-1) with a recovery of -8.2, +9.5 and +9.6%, respectively and a within-laboratory reproducibility (three analytical run) of 15.5, 8.0 and 11.0%, respectively. The results for the decision limit and the detection capability were: CC(alpha) = 11.69 ng L(-1) and CC(beta) = 19.8 ng L(-1). The digested solutions resulted to be stable during testing time (60 days) and the method can be considered highly specific as well.

  7. 2D elemental mapping of sections of human kidney stones using laser ablation inductively-coupled plasma-mass spectrometry: Possibilities and limitations

    Energy Technology Data Exchange (ETDEWEB)

    Vašinová Galiová, Michaela [Department of Chemistry, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno (Czech Republic); Central European Institute of Technology (CEITEC), Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Čopjaková, Renata; Škoda, Radek [Department of Geological Sciences, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno (Czech Republic); Štěpánková, Kateřina; Vaňková, Michaela [Department of Chemistry, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno (Czech Republic); Kuta, Jan [Research Centre for Toxic Compounds in the Environment (RECETOX), Masaryk University, Kamenice 126/3, 625 00 Brno (Czech Republic); Prokeš, Lubomír [Department of Chemistry, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno (Czech Republic); Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, 611 37 Brno (Czech Republic); Kynický, Jindřich [Department of Pedology and Geology, Faculty of Forestry and Wood Technology, Mendel University in Brno, Zemědělská 3, 613 00 Brno (Czech Republic); and others

    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. - Highlights: • Elements in phosphate and oxalate urolith phases were quantified by LA-ICP-MS. • SRM NIST 1486 Bone Meal was proved suitable for quantification in uroliths. • Different ablation rates in particular phases were included at quantification. • Oxalate and apatite phases show opposite hardness order to natural minerals. • Uroliths were classified according to elemental association to phases.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ivanov, Krasimir, E-mail: kivanov1@abv.bg [Department of Chemistry, University of Agriculture, Plovdiv (Bulgaria); Zaprjanova, Penka [Tobacco and Tobacco Products Institute, Plovdiv (Bulgaria); Petkova, Milena [Department of Chemistry, University of Agriculture, Plovdiv (Bulgaria); Stefanova, Violeta; Kmetov, Veselin; Georgieva, Deyana [Department of Analytical Chemistry, Plovdiv University ' Paisii Hilendarski,' Plovdiv (Bulgaria); Angelova, Violina [Department of Chemistry, University of Agriculture, Plovdiv (Bulgaria)

    2012-05-15

    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 + HClO{sub 4} 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

  9. Evaluation of pyrolysis curves for volatile elements in aqueous standards and carbon-containing matrices in electrothermal vaporization inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Silva, A.F. [Delft University of Technology, Faculty of Applied Sciences, DelftChemTech, Julianalaan 136, 2628 BL Delft (Netherlands); Universidade Federal de Santa Catarina, Departamento de Quimica, 88040-900 Florianopolis, SC (Brazil); Welz, B. [Universidade Federal de Santa Catarina, Departamento de Quimica, 88040-900 Florianopolis, SC (Brazil); Loos-Vollebregt, M.T.C. de [Delft University of Technology, Faculty of Applied Sciences, DelftChemTech, Julianalaan 136, 2628 BL Delft (Netherlands)], E-mail: m.t.c.deloos-vollebregt@tudelft.nl

    2008-07-15

    Pyrolysis curves in electrothermal atomic absorption spectrometry (ET AAS) and electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) have been compared for As, Se and Pb in lobster hepatopancreas certified reference material using Pd/Mg as the modifier. The ET AAS pyrolysis curves confirm that the analytes are not lost from the graphite furnace up to a pyrolysis temperature of 800 deg. C. Nevertheless, a downward slope of the pyrolysis curve was observed for these elements in the biological material using ETV-ICP-MS. This could be related to a gain of sensitivity at low pyrolysis temperatures due to the matrix, which can act as carrier and/or promote changes in the plasma ionization equilibrium. Experiments with the addition of ascorbic acid to the aqueous standards confirmed that the higher intensities obtained in ETV-ICP-MS are related to the presence of organic compounds in the slurry. Pyrolysis curves for As, Se and Pb in coal and coal fly ash were also investigated using the same Pd/Mg modifier. Carbon intensities were measured in all samples using different pyrolysis temperatures. It was observed that pyrolysis curves for the three analytes in all slurry samples were similar to the corresponding graphs that show the carbon intensity for the same slurries for pyrolysis temperatures from 200 deg. C up to 1000 deg. C.

  10. Determination of As, Cd, Pb and Tl in coal by electrothermal vaporization inductively coupled plasma mass spectrometry using slurry sampling and external calibration against aqueous standards

    Energy Technology Data Exchange (ETDEWEB)

    Borges, D.L.G.; Welz, B.; Curtius, A.J. [University of Federal Santa Catarina, Florianopolis (Brazil)

    2007-06-15

    A method was developed for the determination of As, Cd, Pb and Tl by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) with slurry sample introduction using certified reference coal samples. The As-75, Cd-111, Pb-208 and Tl-205 isotopes were monitored, considering the lower probabilities of these isotopes in suffering interferences. The carrier and modifier effect of Ru added in solution was evaluated, demonstrating that sensitivity for all elements is considerably improved by the addition of 15 mg of Ru to each individual measurement. This confirms its ability to act as a physical carrier particularly for the analytes in aqueous solution. After optimization of the operational parameters, the determination of the four elements in six certified reference coal samples was carried out by external calibration against aqueous standards in 5% v= v HNO{sub 3}, resulting in good agreement between the certified or given values and the determined ones. For Tl, due to the absence of certified values, a comparison was established considering previously published data using solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry. Detection limits ({mu} g g{sup -1}) of 0.1, 0.004, 0.045 and 0.001 were achieved for As, Cd, Pb and Tl, respectively, and the precision was typically better than 10%.

  11. Metal imaging in non-denaturating 2D electrophoresis gels by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the detection of metalloproteins.

    Science.gov (United States)

    Becker, J Susanne; Lobinski, Ryszard; Becker, J Sabine

    2009-01-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was developed as a powerful analytical technique for metal imaging of 2D gels for the detection of metalloproteins in rat kidney after electrophoretic separation. Protein complexes, extracted with water, were separated in their native state in the first and second dimension by blue native gel electrophoresis (BN-PAGE). Essential and toxic metals, such as zinc, copper, iron, manganese and lead, were monitored by LA-ICP-MS after gel ablation by a focused laser beam in a way that the total surface of a selected fragment of the gel was totally ablated. The metal distribution of this part of the gel was then constructed by plotting the metal (isotope) signal intensity as a function of the x,y (isoelectric point, molecular mass) coordinates of the gel. The proteins at locations rich in metals were cut out, digested with trypsin and analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS).

  12. Application of direct solid sample analysis for the determination of chlorine in biological materials using electrothermal vaporization inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Santos de Gois, Jefferson; Pereira, Éderson R. [Departamento de Química, Universidade Federal de Santa Catarina, 88040-970 Florianópolis, SC (Brazil); Welz, Bernhard [Departamento de Química, Universidade Federal de Santa Catarina, 88040-970 Florianópolis, SC (Brazil); INCT de Energia e Ambiente do CNPq (Brazil); Borges, Daniel L.G., E-mail: daniel.borges@ufsc.br [Departamento de Química, Universidade Federal de Santa Catarina, 88040-970 Florianópolis, SC (Brazil); INCT de Energia e Ambiente do CNPq (Brazil)

    2015-03-01

    This work describes a methodology developed to carry out Cl determination in biological materials using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis. The solid samples were directly weighed into graphite ‘cups’ and inserted into the graphite furnace. The RF power and the carrier gas flow rate were optimized at 1300 W and 0.7 L min{sup −1}, respectively. Calibration could be carried out using aqueous standard solutions with pre-dried modifiers (Pd + Nd or Pd + Ca) or using solid certified reference materials with the same pre-dried modifiers or without the use of modifiers. The limit of quantification was determined as 5 μg g{sup −1} under optimized conditions and the Cl concentration was determined in five certified reference materials with certified concentrations for Cl, in addition to three certified reference materials, for which certified values for Cl were unavailable; in the latter case, the results were compared with those obtained using high-resolution continuum source molecular absorption spectrometry. Good agreement at a 95% statistical confidence level was achieved between determined and certified or reference values. - Highlights: • Direct determination of chlorine in solid biological materials is described for the first time using ICP-MS. • Calibration against aqueous standards is feasible. • The method is accurate and sensitive, regardless of the composition of the solid sample.

  13. Method Development for Rapid Analysis of Natural Radioactive Nuclides Using Sector Field Inductively Coupled Plasma Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lim, J.M.; Ji, Y.Y.; Lee, H.; Park, J.H.; Jang, M.; Chung, K.H.; Kang, M.J.; Choi, G.S. [Korea Atomic Energy Research Institute (Korea, Republic of)

    2014-07-01

    As an attempt to reduce the social costs and apprehension arising from radioactivity in the environment, an accurate and rapid assessment of radioactivity is highly desirable. Naturally occurring radioactive materials (NORM) are widely spread throughout the environment. The concern with radioactivity from these materials has therefore been growing for the last decade. In particular, radiation exposure in the industry when handling raw materials (e.g., coal mining and combustion, oil and gas production, metal mining and smelting, mineral sands (REE, Ti, Zr), fertilizer (phosphate), and building materials) has been brought to the public's attention. To decide the proper handling options, a rapid and accurate analytical method that can be used to evaluate the radioactivity of radionuclides (e.g., {sup 238}U, {sup 235}U, {sup 232}Th, {sup 226}Ra, and {sup 40}K) should be developed and validated. Direct measuring methods such as alpha spectrometry, a liquid scintillation counter (LSC), and mass-spectrometry are usually used for the measurement of radioactivity in NORM samples, and they encounter the most significant difficulties during pretreatment (e.g., purification, speciation, and dilution/enrichment). Since the pretreatment process consequently plays an important role in the measurement uncertainty, method development and validation should be performed. Furthermore, a-spectrometry has a major disadvantage of a long counting time, while it has a prominent measurement capability at a very low activity level of {sup 238}U, {sup 235}U, {sup 232}Th, and {sup 226}Ra. Contrary to the α-spectrometry method, a measurement technique using ICP-MS allow radioactivity in many samples to be measured in a short time period with a high degree of accuracy and precision. In this study, a method was developed for a rapid analysis of natural radioactive nuclides using ICP-MS. A sample digestion process was established using LiBO{sub 2} fusion and Fe co-precipitation. A magnetic

  14. Imaging of metals, metalloids, and non-metals by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in biological tissues.

    Science.gov (United States)

    Becker, J Sabine; Becker, J Susanne

    2010-01-01

    The determination of the localization and distribution of essential and beneficial metals (e.g., Cu, Fe, Zn, Mn, Co, Ti, Al, Ca, K, Na, Cr and others), toxic metals (like Cd, Pb, Hg, U), metalloids (e.g., As, Se, Sb), and non-metals (such as C, S, P, Cl, I) in biological tissues is a challenging task for life science studies. Over the past few years, the development and application of mass spectrometric imaging (MSI) techniques for elements has been rapidly growing in the life sciences in order to investigate the uptake and the transport of both essential and toxic metals in plant and animal sections. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a very sensitive and efficient trace, surface, and isotopic analytical technique for biological samples. LA-ICP-MS is increasingly utilized as an elemental mass spectrometric technique using double-focusing sector field (LA-ICP-SFMS) or quadrupole mass spectrometers (LA-ICP-QMS) to produce images of detailed regionally specific element distributions in thin biological tissue sections. Nowadays, MSI studies focus on brain research for studying neurodegenerative diseases such as Alzheimer's or Parkinson's, stroke, or tumor growth, or for the imaging of cancer biomarkers in tissue sections.The combination of the mass spectrometry imaging of metals by LA-ICP-MS with proteomics using biomolecular mass spectrometry (such as MALDI-MS or ESI-MS) to identify metal-containing proteins has become an important strategy in the life sciences. Besides the quantitative imaging of metals, non-metals and metalloids in biological tissues, LA-ICP-MS has been utilized for imaging metal-containing proteins in a 2D gel after electrophoretic separation of proteins. Recent progress in applying LA-ICP-MS in life science studies will be reviewed including the imaging of thin slices of biological tissue and applications in proteome analysis in combination with MALDI/ESI-MS to analyze metal-containing proteins.

  15. Novel applications of high performance ion chromatography-inductively coupled plasma mass spectrometry (HPIC-ICP-MS)

    CERN Document Server

    Hann, S

    2001-01-01

    This work demonstrates the development of highly sensitive and selective analytical methods, which make use of the hyphenation of high performance ion chromatography (HPIC) to inductively coupled plasma sector field mass spectrometry (ICP-SFMS). On-line coupling a chromatographic separation method with an elemental detection method provides two advantages: (1) the components of a possibly interfering matrix can be separated allowing accurate and precise ultra trace analysis of the element of interest and (2) elemental species of an element can be separated and quantified. In this work, matrix separation methods for interference free determination of 232Th, 234U, 235U and 238U in geological matrices were developed and employed. Furthermore HPIC-ICP-SFMS was applied for ultra trace analysis of Pd in environmental and geological matrices. The usefulness of HPIC-ICP-SFMS for speciation studies was demonstrated by investigating the interaction of an anti-cancer drug (cisplatin) with guanosine monophosphates.

  16. Analysis of radium-226 in high salinity wastewater from unconventional gas extraction by inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    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.

  17. Flow-injection technique for determination of uranium and thorium isotopes in urine by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    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.

  18. Determination of methylmercury in the tuna tissue by High performance liquid chromatography with Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    LV Lei; Jiang Zhi-gang; Li Qun; Zhang Shuai

    2009-01-01

    This study mainly applied one kind oftechnologies to determine the methylmercury in the tuna tissue with high performance liquid chromagraphy-inductively coupled plasma nlass spectrometry.We choosed the optmaum conditiom including that the mobile phase Was water with 5% methanol,2-mercaptoethanol,0.06mol/Lammomum acetate and pH6.8.The sample amount was 1OOuL and the flow rate was 0.4mL/min.The optimum checking conditions is that RF power was 1500W,integral time was 0.3s sampling depth Was 8.0mm,velocity of carrier gas Was 0.75L/min and velocity of auxiliary gas Was 0.40L/min.In this con~tiom.the calibration CUrVe was linear when the concentra tions od methylmercury was in the range of 0-4ug/mL(r=0.9996),the detection limit can achieve 9ng/L,RSD is 8.2%,and the addition recovery is 75%-97%.The results show this method is simple,rapid and sensitive and can be used for the daily analysis of tuna samples.

  19. Method for the quantification of vanadyl porphyrins in fractions of crude oils by High Performance Liquid Chromatography-Flow Injection-Inductively Coupled Plasma Mass Spectrometry

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2011-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-01-15

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

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

    Science.gov (United States)

    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.

  3. Simultaneous determination of arsenic and mercury species in rice by ion-pairing reversed phase chromatography with inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    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.

  4. Element bioimaging of liver needle biopsy specimens from patients with Wilson's disease by laser ablation-inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    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.

  5. Rapid determination of plutonium isotopes in environmental samples using sequential injection extraction chromatography and detection by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    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 determination of Pu isotopes in environmental risk assessment and emergency preparedness scenarios.

  6. 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.

    Science.gov (United States)

    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.

  7. Inductively coupled plasma mass spectrometry in comparison with neutron activation and ion chromatography with UV/VIS detection for the determination of lanthanides in plant materials.

    Science.gov (United States)

    Bulska, Ewa; Danko, Bożena; Dybczyński, Rajmund S; Krata, Agnieszka; Kulisa, Krzysztof; Samczyński, Zbigniew; Wojciechowski, Marcin

    2012-08-15

    Analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for determination of lanthanides in plant materials was investigated and compared with neutron activation analysis (NAA) as well as ion chromatography (IC) with UV-VIS detection. Two sample preparation protocols were tested: (i) microwave assisted digestion by concentrated nitric acid; (ii) microwave digestion involving silica and fluoride removal, followed by the selective and quantitative lanthanides group separation from the plant matrix. Several Certified Reference Materials (CRM) of plant origin were used for the evaluation of the accuracy of the applied analytical procedures. The consistency of results, obtained by various methods, enabled to establish the tentative recommended values (TRV) for several missing elements in one of CRMs. The ICP-MS, due to its very high sensitivity, has the potential to contribute to this aim. The discrepancy of the results obtained by various methods was discussed in a view of possible matrix effects related to the composition of investigated materials. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Determination of sulfur and selected trace elements in metallothionein-like proteins using capillary electrophoresis hyphenated to inductively coupled plasma mass spectrometry with an octopole reaction cell

    Energy Technology Data Exchange (ETDEWEB)

    Proefrock, Daniel; Leonhard, Peter; Prange, Andreas [GKSS Research Centre Geesthacht, Institute for Coastal Research, Max Planck Strasse, 21502, Geesthacht (Germany)

    2003-09-01

    The determination of sulfur in biologically relevant samples such as metalloproteins is described. The analytical methodology used is based on robust on-line coupling between capillary electrophoresis (CE) and octopole reaction cell inductively-coupled plasma mass spectrometry (ORC-ICP-MS). Polyatomic ions that form in the plasma and interfere with the determination of S at mass 32 are minimised by addition of xenon to the collision cell. The method has been applied to the separation and simultaneous element-specific detection of sulfur, cadmium, copper, and zinc in commercially available metallothionein preparations (MT) and metallothionein-like proteins (MLP) extracted from liver samples of bream (Abramis brama L.) caught in the river Elbe, Germany. Instrumental detection limits have been calculated according to the German standard procedure DIN 32645 for the determination of sulfur and some simultaneously measured trace elements in aqueous solution. For sulfur detection limits down to 1.3 {mu}g L{sup -1} ({sup 34}S) and 3.2 {mu}g L{sup -1} ({sup 32}S) were derived. For the other trace elements determined simultaneously detection limits ranging from 300 ng L{sup -1} ({sup 58}Ni) to 500 ng L{sup -1} ({sup 66}Zn, {sup 55}Mn) were achieved. For quantification of sulfur and cadmium in a commercially available MT preparation under hyphenated conditions the use of external calibration is suggested. Finally, the need for proper sample-preparation technique will be discussed. (orig.)

  9. Evaluation of microwave and ultrasound extraction procedures for arsenic speciation in bivalve mollusks by liquid chromatography–inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Clarissa M.M.; Nunes, Matheus A.G. [Departamento de Química, Universidade Federal de Santa Maria, Santa Maria, RS (Brazil); Barbosa, Isa S.; Santos, Gabriel L. [Instituto de Química, Universidade Federal da Bahia, Salvador, BA (Brazil); Peso-Aguiar, Marlene C. [Instituto de Biologia, Universidade Federal da Bahia, Salvador, BA (Brazil); Korn, Maria G.A. [Instituto de Química, Universidade Federal da Bahia, Salvador, BA (Brazil); Flores, Erico M.M. [Departamento de Química, Universidade Federal de Santa Maria, Santa Maria, RS (Brazil); Dressler, Valderi L., E-mail: vdressler@gmail.com [Departamento de Química, Universidade Federal de Santa Maria, Santa Maria, RS (Brazil)

    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{sup −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. - Highlights: • Method development for As speciation analysis by LC–ICP-MS • Evaluation of microwave and ultrasonic radiation for sample preparation • Investigation on As species content in mollusks.

  10. Direct trace-elemental analysis of urine samples by laser ablation-inductively coupled plasma mass spectrometry after sample deposition on clinical filter papers.

    Science.gov (United States)

    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.

  11. [Analysis of X-Ray Fluorescence Spectroscopy and Plasma Mass Spectrometry of Pangxidong Composite Granitoid Pluton and Its Implications for Magmatic Differentiation].

    Science.gov (United States)

    Zeng, Chang-yu; Ding, Ru-xin; Li, Hong-zhong; Zhou, Yong-zhang; Niu, Jia; Zhang, Jie-tang

    2015-11-01

    Pangxidong composite granitoid pluton located in the southwestern margin of Yunkai massif. The metamorphic grade of this pluton increases from outside to inside, that is, banded-augen granitic gneisses, gneissoid granites and granites distribute in order from edge to core. X-Ray Fluorescence Spectroscopy and Plasma Mass Spectrometry are conducted to study the geochemical characteristics of the three types of rocks. The result shows that all the three types of rocks are peraluminous rocks and their contents of main elements and rare earth elements change gradually. From granitic gneisses to granites, the contents of Al₂O₃, CaO, MgO, TiO₂, total rare earth elements and light rare earth elements increase, but the contents of SiO₂ and heavy rare earth elements decrease. It is suggested that the phylogenetic relationship exists between granitic gneisses, gneissoid granites and granites during the multi-stage tectonic evolution process. Furthermore, the remelting of metamorphosed supracrustal rocks in Yunkai massif is probably an important cause of granitoid rocks forming. The evolutionary mechanism is probably that SiO₂ and heavy rare earth elements were melt out from the protolith and gradually enriched upward, but Al₂O₃, CaO, MgO, TiO₂ and light rare earth elements enriched downward.

  12. Development of an ion chromatography-inductively coupled plasma-mass spectrometry method to determine inorganic arsenic in liver from chickens treated with roxarsone.

    Science.gov (United States)

    Conklin, Sean D; Shockey, Nohora; Kubachka, Kevin; Howard, Karyn D; Carson, Mary C

    2012-09-19

    Roxarsone, (4-hydroxy-3-nitrophenyl)arsonic acid, is an arsenic-containing compound that has been approved as a feed additive for poultry and swine since the 1940s; however, little information is available regarding residual arsenic species present in edible tissues. We developed a novel method for the extraction and quantification of arsenic species in chicken liver. A strongly basic solution solubilized the liver, and ultrafiltration removed macromolecules and particulate material. Ion chromatography separated the species [arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, (4-hydroxy-3-aminophenyl)arsonic acid, (4-hydroxy-3-acetaminophenyl)arsonic acid, and roxarsone] in the extracts, which were then detected by inductively coupled plasma-mass spectrometry. The extraction oxidized most arsenite to arsenate. For fortification concentrations at 2 μg kg(-1) and above, recoveries ranged from 70 to 120%, with relative standard deviations from 7 to 34%. We detected roxarsone, its 3-amino and 3-acetamido metabolites, inorganic arsenic, and additional unknown arsenic species in livers from roxarsone-treated chickens. Both the originating laboratory and a second laboratory validated the method.

  13. Simultaneous analysis 26 mineral element contents from highly consumed cultured chicken overexposed to arsenic trioxide by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    He, Ying; Sun, Bonan; Li, Siwen; Sun, Xiao; Guo, Ying; Zhao, Hongjing; Wang, Yu; Jiang, Guangshun; Xing, Mingwei

    2016-11-01

    This study assessed the impacts of dietary arsenic trioxide (As2O3) on 26 mineral element contents in the liver and kidney of chicken. A total of 100 male Hy-line cocks were randomly divided into 2 groups (50 chickens in each group), including an arsenic-treated group (basic diet supplemented with As2O3 at 30 mg/kg) and a control group (basal diet). The feeding experiment lasted for 90 days and the experimental animals were given free access to feed and water. We determined 26 mineral elements in the liver and kidney by inductively coupled plasma mass spectrometry (ICP-MS). The results showed that nine element levels (Al, Mn, Co, Cu, Zn, Se, Cd, Ba, and Pb) were significantly decreased (P chickens exposed to As2O3 compared to the control chickens where three element levels (Ni, As, and Hg) increased significantly (P chickens exposed to As2O3 compared to the control chickens where four element levels (Mo, As, Cd, and Hg) increased significantly (P chicken, and the effects vary from organ to organ. The aim of this study is to provide references for further study of heavy metal poisoning by detecting the contents of minerals induced by arsenic in chicken.

  14. Determination of vanadium species in sediment, mussel and fish muscle tissue samples by liquid chromatography-inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Colina, Marinela [Universidad del Zulia, Facultad de Ciencias, Departamento de Quimica, Laboratorio de Quimica Ambiental, Maracaibo 4011, Zulia (Venezuela)]. E-mail: M.Colina@shu.ac.uk; Gardiner, P.H.E. [Sheffield Hallam University, Howard Street, Sheffield S1 1WB, Sheffield (United Kingdom); Rivas, Zulay [Instituto para la Conservacion del Lago de Maracaibo (ICLAM), Maracaibo, Plaza de las Banderas (Venezuela); Troncone, Federico [Instituto para la Conservacion del Lago de Maracaibo (ICLAM), Maracaibo, Plaza de las Banderas (Venezuela)

    2005-05-04

    Vanadium is introduced into the environment during the extraction of petrochemical products and in the production of steels and insecticides. In this study, a liquid chromatographic method for the separation of V(IV) and V(V) as ethylenediaminetetra acetic acid (EDTA) complexes was developed using reversed-phase ion-pair liquid chromatography with inductively coupled plasma-mass spectrometry detection. A C-8 reversed-phase column, 15 cm long, was used to separate the species. A solution containing ammonium acetate 0.06 M, tetrabutylammonium hydroxide 10 mM, ammonium di-phosphate 10 mM and EDTA 2.5 mM at pH 6 was used as the mobile phase in order to avoid the use of organic solvents that reduce the sensitivity of the determination. To prevent changes in distribution of the vanadium species, samples should be prepared freshly. The method developed was applied to the study the vanadium speciation in sediment, mussel and fish muscle samples collected from Lake Maracaibo, Venezuela. The concentration ranges of V(IV) and V(V) in sediment samples were 0.7-61 and 1.4-2.3 {mu}g g{sup -1}, respectively. The method is simple and has adequate sensitivity for these practical applications.

  15. Comparison of sample digestion techniques for the determination of trace and residual catalyst metal content in single-wall carbon nanotubes by inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Grinberg, Patricia, E-mail: patricia.grinberg@nrc.ca [Measurement Science and Standards, National Research Council Canada, Ottawa (Canada); Sturgeon, Ralph E. [Measurement Science and Standards, National Research Council Canada, Ottawa (Canada); Diehl, Liange de O.; Bizzi, Cezar A. [Measurement Science and Standards, National Research Council Canada, Ottawa (Canada); Chemistry Department, Universidade Federal de Santa Maria, Santa Maria (Brazil); Flores, Erico M.M. [Chemistry Department, Universidade Federal de Santa Maria, Santa Maria (Brazil)

    2015-03-01

    A single-wall carbon nanotube material produced by laser ablation of renewable biochar in the presence of Ni and Co catalyst was characterized for residual catalyst (Co and Ni) as well as trace metal impurity content (Fe, Mo, Cr, Pb and Hg) by isotope dilution ICP-MS following sample digestion. Several matrix destruction procedures were evaluated, including a multi-step microwave-assisted acid digestion, dry ashing at 450 °C and microwave-induced combustion with oxygen. Results were benchmarked against those derived from neutron activation analysis and also supported by solid sampling continuum source GF-AAS for several of the elements. Although laborious to execute, the multi-step microwave-assisted acid digestion proved to be most reliable for recovery of the majority of the analytes, although content of Cr remained biased low for each approach, likely due to its presence as refractory carbide. - Highlights: • Determination of trace and residual catalyst metal content in Single-Wall Carbon Nanotubes by Inductively Coupled Plasma Mass Spectrometry. • Comparative study of digestion methodology combined with high precision isotope dilution ICP-MS for quantitation of elements of toxicologic relevance. • Results were benchmarked against those derived from neutron activation analysis and also supported by solid sampling continuum source GF-AAS for several of the elements.

  16. Determination of Cu, Mn, Ni and Sn in gasoline by electrothermal vaporization inductively coupled plasma mass spectrometry, and emulsion sample introduction

    Science.gov (United States)

    Saint'Pierre, Tatiana D.; Dias, Lúcia Felicidade; Pozebon, Dirce; Aucélio, Ricardo Q.; Curtius, Adilson J.; Welz, Bernhard

    2002-12-01

    Trace metals in fuels, except in the case of additives, are usually undesirable and normally they occur in very low concentrations in gasoline, requiring sensitive techniques for their determination. Coupling of electrothermal vaporization with inductively coupled plasma mass spectrometry minimizes the problems related to the introduction of organic solvents into the plasma. Furthermore, sample preparation as oil-in-water emulsions reduces problems related to gasoline analysis. In this work, a method for determination of Cu, Mn, Ni and Sn in gasoline is proposed. Samples were prepared by forming a 10-fold diluted emulsion with a surfactant (Triton X-100), after treatment with concentrated HNO 3. The sample emulsion was pre-concentrated in the graphite tube by repeated pipetting and drying. External calibration was used with aqueous standards in a purified gasoline emulsion. Six samples from different gas stations were analyzed, and the analyte concentrations were found to be in the μg l -1 range or below. The limits of detection were 0.22, 0.02, 0.38 and 0.03 μg l -1 for Cu, Mn, Ni and Sn, respectively. The accuracy of the method was estimated using a recovery test.

  17. Determination of major, minor and trace elements in rock samples by laser ablation inductively coupled plasma mass spectrometry: Progress in the utilization of borate glasses as targets

    Science.gov (United States)

    Leite, Tácito Dantas F.; Escalfoni, Rainério, Jr.; da Fonseca, Teresa Cristina O.; Miekeley, Norbert

    2011-05-01

    The present work is a continuation of a research study performed at our laboratory aiming at the multielement analysis of rock samples (basalts and shale) by inductively coupled plasma mass spectrometry in combination with laser ablation using borate glasses as analytical targets. Argon, nitrogen-argon mixtures and helium were evaluated as cell gases, the latter confirming its better performance. Different operational parameters of the laser, such as gas flow, energy, focus, scanning speed and sampling frequency were optimized. External calibration was made with standards prepared by fusion of geological reference materials (basalts 688 and BCR-2, obsidian SRM 278, and shale SGR-1) of different mass fractions in the meta-tetra borate matrix. Coefficients of determination ( R2) were > 0.99 for 30 elements from o total of 40 determined. Method validation was then performed using additional certified reference materials (BHVO-2, BIR-1, SCo-1) produced as borate targets in a similar way. Accuracies were better than 10% for most of the elements studied and analytical precisions, calculated from the residual standard deviations of calibration curves were, typically, between 6% and 10%. Additionally, the semiquantitative TotalQuant® technique was applied, which gave, within the expected uncertainty for this calibration technique, concordant results when compared to the quantitative external calibration procedure. Both methods were then used for the analysis of marine shale samples, which are of great geological interest in petroleum prospecting.

  18. Thallium Analysis in Environmental Samples by Inductively Coupled Plasma Mass Spectrometry; Analisis de Talio en Muestras Ambientales por Espectrometria de Masas con Fuente de Plasma de Acoplamiento Inductivo

    Energy Technology Data Exchange (ETDEWEB)

    Higueras, I.; Fernandez, M.; Conde, E.; Gajate, A.

    2008-08-06

    Due to its high toxicity, thallium has been considered by the US Environmental Protection Agency as one of the priority pollutants to be controlled. While being a highly toxic element, thallium has been studied to a much lesser degree than other toxic elements, mainly because thallium is often undetected by classical analytical methods. Thallium is a rare and dispersed element that occurs mainly in sulfur-containing ores. Thus, it is a potential pollutant to surrounding environment, if Tl-rich mineral and/or their industrial wastes are not properly disposed. In this work an Inductively Coupled Plasma Mass Spectrometry analytical procedure has been developed in order to determine thallium in environmental solid samples and its application to the study of this element as a potential pollutant associated with natural and anthropogenic activities. The analytical procedure has been validated by the use of appropriate reference materials, and through the isotope dilution technique as a primary method of measurement. Finally, the developed procedure has been applied to several samples from a mining area, as one of the scenarios where thallium it is likely to occur. (Author) 87 refs.

  19. Simultaneous determination of bromine and chlorine in coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis.

    Science.gov (United States)

    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.

  20. Determination of minor and trace elements in aromatic spices by micro-wave assisted digestion and inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    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.

  1. Characterization of gold nanoparticle uptake by tomato plants using enzymatic extraction followed by single-particle inductively coupled plasma-mass spectrometry analysis.

    Science.gov (United States)

    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.

  2. Laser-induced breakdown spectroscopy and inductively coupled plasma-mass spectrometry for determination of Cr in soils from Brits District, South Africa

    Directory of Open Access Journals (Sweden)

    A. A. Ambushe

    2015-10-01

    Full Text Available Laser-induced breakdown spectroscopy (LIBS is an emerging analytical technique, which can be used to perform elemental analysis of any material, irrespective of its physical state. In this study, the LIBS technique has been applied for quantification of total Cr in soil samples collected from polluted areas of Brits, North West Province, South Africa. A Q-switched neodymium-yttrium aluminium garnet (Nd-YAG laser (10 Hz, λ = 1064 nm was employed for generation of a laser-induced plasma on the surface of the soil sample. The atomic emission lines were recorded using an Andor Shamrock SR-303i spectrometer, fitted with an intensified charge-coupled device (ICCD camera. Detailed investigation of experimental parameters such as gate delay time, gate width and laser pulse energy was conducted. Soil samples were dried, finely ground, sieved and thereafter pelletized before LIBS analysis. Calibration curve for the quantification of Cr was constructed using certified reference materials of soils and sediments. The concentrations of Cr in soil samples varied from 111 to 3180 mg/kg. In order to test the validity of the LIBS results, inductively coupled plasma-mass spectrometry (ICP-MS was also employed for determination of Cr. The results obtained using LIBS were found to be in good agreement with those of ICP-MS.DOI: http://dx.doi.org/10.4314/bcse.v29i3.3

  3. Solid sampling electrothermal vaporization inductively coupled plasma mass spectrometry for the direct determination of Hg in different materials using isotope dilution with a gaseous phase for calibration

    Science.gov (United States)

    Resano, M.; Gelaude, I.; Dams, R.; Vanhaecke, F.

    2005-03-01

    This paper evaluates the potential of electrothermal vaporization-inductively coupled plasma mass spectrometry (ETV-ICPMS) for the direct determination of Hg in solid samples, using a 200Hg-enriched gaseous phase for calibration based on isotope dilution. Three different samples were studied, BCR CRM 320 River sediment, IAEA-086 Hair and a real (wet) freshwater fish sample (M1). The samples selected show important differences in their matrix composition, and especially the fish sample constitutes a challenge as a result of its high water content (≈80%). The main conclusion of the work is that the calibration approach investigated succesfully corrects for all the matrix effects (suppression) observed during Hg vaporization, allowing accurate values to be obtained in all cases. Moreover, practically the same operating conditions could be used for all sample types. The method finally proposed presents interesting features for the direct determination of this challenging element in solid samples, such as: a low sample consumption (a few milligrams), a high sample throughput (10 min/sample), a low limit of detection (6 ng g -1) and a reduced risk of analyte losses or contamination. Precision values depend on the homogeneity of the sample studied, and are typically in the vicinity of 10% RSD, except for the more inhomogenous river sediment (18% RSD).

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

    Science.gov (United States)

    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 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.

  5. Chemical speciation studies on DU contaminated soils using flow field flow fractionation linked to inductively coupled plasma mass spectrometry (FlFFF-ICP-MS).

    Science.gov (United States)

    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. This journal is © The Royal Society of Chemistry 2012

  6. Elemental Quantitative Distribution and Statistical Analysis on Cross Section of Stainless Steel Sheet by Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    Qian-hua LUO; Hai-zhou WANG

    2015-01-01

    An innovative application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) technique in illustrating elemental distributions on stainless steel sheets was presented. The technique proved to be a systematic and accurate ap-proach in producing visual images or maps of elemental distributions at cross-sectional surface of a stainless steel sheet. Two stain-less steel sheets served as research objects: 3 mm×1 300 mm hot-rolled stainless steel plate and 1 mm×1 260 mm cold-rolled plate. The cross-sectional surfaces of the two samples at 1/4 position along the width direction were scanned (raster area-44 mm2 and 11 mm2) with a focused laser beam (wavelength 213 nm, diameter of laser crater 100 μm, and laser power 1.6 mJ) in a laser abla-tion chamber. The laser ablation system was coupled to a quadrupole ICP-MS, which made the detection of ion intensities of27Al+, 44Ca+,47Ti+,55Mn+ and56Fe+ within an area of interest possible. One-dimensional (1D) content line distribution maps and two-dimensional (2D) contour maps for speciifc positions or areas were plotted to indicate the element distribution of a target area with high accuracy. Statistic method was used to analyze the acquired data by calculating median contents, maximum segregation, sta-tistic segregation and content-frequency distribution.

  7. A comparison of the use of refractive index (RI) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for the provenance establishment of glass bottles.

    Science.gov (United States)

    May, Christopher D; Watling, R John

    2009-01-01

    The use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been compared with the traditional method of refractive index (RI) measurement for the establishment of the provenance of glass bottles. Using the RI method alone, it is not possible to discriminate between certain glass bottles produced up to 18 days apart from a single manufacturing plant. Furthermore, variations in RI within a single bottle can be large enough to invalidate co-provenance establishment using this technique alone. Determination of the trace elemental composition of bottles collected over a 1-month period confirmed that minimal variation of trace metal distribution occurred within individual bottles made during this period. Therefore, the trace element composition of any fragment of glass from a broken bottle may be considered representative of the elemental composition of the entire bottle. In addition, statistical comparison of the distribution of approximately 38 of the 56 analytes that were determined established that it was possible to discriminate between two glass bottles manufactured in the same plant two hours apart. Using this methodology it has been possible to develop an analytical protocol to significantly improve the accurate comparison and provenance establishment of forensic glass evidence.

  8. Method validation for determination of metals in Vitis labrusca L. grapevine leaf extracts by inductively coupled plasma mass spectrometry (ICP-MS

    Directory of Open Access Journals (Sweden)

    LIANE V.V. BOKOWSKI

    Full Text Available ABSTRACT Vitis labrusca L. is the main species used for wine and juice production in Brazil. The grapevine leaves can be used both as functional foods and as cheapest sources for the extraction of phenolic compounds. Besides the antioxidant activity, grapevine leaves exhibited significant anti-inflammatory activity. Therefore, the aim of this study was to develop and validate an analytical methodology to determine the metals selenium (96Se, chromium (53Cr, nickel (62Ni, cadmium (111Cd and lead (206Pb in 30 samples of grapevine leaf extracts (Vitis labrusca, Bordo cultivar using inductively coupled plasma mass spectrometry (ICP-MS. To obtain the grapevine leaf extracts the samples were milled, weighed and digested in microwave oven with nitric acid. The method showed linearity, precision, accuracy and limits of quantification and detection acceptable for INMETRO protocol validation of analytical methods. Therefore, the method using ICP-MS was developed and validated to determine metals concentrations in grapevine leaves of Vitis labrusca L. and the proposed method could be applied in routine analytical laboratory.

  9. Comparative Study of Metal Quantification in Neurological Tissue Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Imaging and X-ray Fluorescence Microscopy.

    Science.gov (United States)

    Davies, Katherine M; Hare, Dominic J; Bohic, Sylvain; James, Simon A; Billings, Jessica L; Finkelstein, David I; Doble, Philip A; Double, Kay L

    2015-07-07

    Redox-active metals in the brain mediate numerous biochemical processes and are also implicated in a number of neurodegenerative diseases. A number of different approaches are available for quantitatively measuring the spatial distribution of biometals at an image resolution approaching the subcellular level. Measured biometal levels obtained using laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS; spatial resolution 15 μm × 15 μm) were within the range of those obtained using X-ray fluorescence microscopy (XFM; spatial resolution 2 μm × 7 μm) and regional changes in metal concentration across discrete brain regions were replicated to the same degree. Both techniques are well suited to profiling changes in regional biometal distribution between healthy and diseased brain tissues, but absolute quantitation of metal levels varied significantly between methods, depending on the metal of interest. Where all possible variables affect metal levels, independent of a treatment/phenotype are controlled, either method is suitable for examining differences between experimental groups, though, as with any method for imaging post mortem brain tissue, care should be taken when interpreting the total metal levels with regard to physiological concentrations.

  10. Determination of major, minor and trace elements in rock samples by laser ablation inductively coupled plasma mass spectrometry: Progress in the utilization of borate glasses as targets

    Energy Technology Data Exchange (ETDEWEB)

    Leite, Tacito Dantas F. [Departmento de Quimica da Pontificia Universidade Catolica do Rio de Janeiro, Rua Marques de Sao Vicente 225, 22451-900 Rio de Janeiro (Brazil); Universidade Estadual de Goias (UEG) (Brazil); Instituto Federal de Educacao, Ciencia e Tecnologia de Brasilia (IFB) (Brazil); Escalfoni, Rainerio [Departmento de Quimica da Pontificia Universidade Catolica do Rio de Janeiro, Rua Marques de Sao Vicente 225, 22451-900 Rio de Janeiro (Brazil); Centro de Pesquisas Leopoldo A. Miguez de Mello da Petrobras (CENPES) (Brazil); Fonseca, Teresa Cristina O. da [Centro de Pesquisas Leopoldo A. Miguez de Mello da Petrobras (CENPES) (Brazil); Miekeley, Norbert, E-mail: miekeley@puc-rio.br [Departmento de Quimica da Pontificia Universidade Catolica do Rio de Janeiro, Rua Marques de Sao Vicente 225, 22451-900 Rio de Janeiro (Brazil)

    2011-05-15

    The present work is a continuation of a research study performed at our laboratory aiming at the multielement analysis of rock samples (basalts and shale) by inductively coupled plasma mass spectrometry in combination with laser ablation using borate glasses as analytical targets. Argon, nitrogen-argon mixtures and helium were evaluated as cell gases, the latter confirming its better performance. Different operational parameters of the laser, such as gas flow, energy, focus, scanning speed and sampling frequency were optimized. External calibration was made with standards prepared by fusion of geological reference materials (basalts 688 and BCR-2, obsidian SRM 278, and shale SGR-1) of different mass fractions in the meta-tetra borate matrix. Coefficients of determination (R{sup 2}) were > 0.99 for 30 elements from o total of 40 determined. Method validation was then performed using additional certified reference materials (BHVO-2, BIR-1, SCo-1) produced as borate targets in a similar way. Accuracies were better than 10% for most of the elements studied and analytical precisions, calculated from the residual standard deviations of calibration curves were, typically, between 6% and 10%. Additionally, the semiquantitative TotalQuant (registered) technique was applied, which gave, within the expected uncertainty for this calibration technique, concordant results when compared to the quantitative external calibration procedure. Both methods were then used for the analysis of marine shale samples, which are of great geological interest in petroleum prospecting.

  11. Validation of the determination of the B isotopic composition in Roman glasses with laser ablation multi-collector inductively coupled plasma-mass spectrometry

    Science.gov (United States)

    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.

  12. Determination of mercury compounds in fish by microwave-assisted extraction and liquid chromatography-vapor generation-inductively coupled plasma mass spectrometry

    Science.gov (United States)

    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).

  13. 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.

    Science.gov (United States)

    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‰.

  14. Evaluation of the Forensic Utility of Scanning Electron Microscopy-Energy Dispersive Spectroscopy and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry for Printing Ink Examinations.

    Science.gov (United States)

    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.

  15. Standard test method for analysis of urine for uranium-235 and uranium-238 isotopes by inductively coupled plasma-mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2010-01-01

    1.1 This test method covers the determination of the concentration of uranium-235 and uranium-238 in urine using Inductively Coupled Plasma-Mass Spectrometry. This test method can be used to support uranium facility bioassay programs. 1.2 This method detection limits for 235U and 238U are 6 ng/L. To meet the requirements of ANSI N13.30, the minimum detectable activity (MDA) of each radionuclide measured must be at least 0.1 pCi/L (0.0037 Bq/L). The MDA translates to 47 ng/L for 235U and 300 ng/L for 238U. Uranium– 234 cannot be determined at the MDA with this test method because of its low mass concentration level equivalent to 0.1 pCi/L. 1.3 The digestion and anion separation of urine may not be necessary when uranium concentrations of more than 100 ng/L are present. 1.4 Units—The values stated in picoCurie per liter units are to be regarded as standard. The values given in parentheses are mathematical conversions to SI units that are provided for information only and are not considered standard. 1....

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

    Science.gov (United States)

    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. © The Author(s) 2016.

  17. Metallomics for drug development: serum protein binding and analysis of an anticancer tris(8-quinolinolato)gallium(III) drug using inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    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%.

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

    Directory of Open Access Journals (Sweden)

    Allan Philippe

    Full Text Available 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.

  19. A high-throughput solid-phase extraction microchip combined with inductively coupled plasma-mass spectrometry for rapid determination of trace heavy metals in natural water.

    Science.gov (United States)

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Arsenic speciation in rice by capillary electrophoresis/inductively coupled plasma mass spectrometry: enzyme-assisted water-phase microwave digestion.

    Science.gov (United States)

    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.

  1. Microwave dissolution of plant tissue and the subsequent determination of trace lanthanide and actinide elements by inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. 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

    Science.gov (United States)

    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.

  3. Fast preconcentration of trace rare earth elements from environmental samples by di(2-ethylhexyl)phosphoric acid grafted magnetic nanoparticles followed by inductively coupled plasma mass spectrometry detection

    Science.gov (United States)

    Yan, Ping; He, Man; Chen, Beibei; Hu, Bin

    2017-10-01

    In this work, di(2-ethylhexyl)phosphoric acid (P204) grafted magnetic nanoparticles were synthesized by fabricating P204 onto Fe3O4@TiO2 nanoparticles based on Lewis acid-base interaction between Ti and phosphate group under weakly acidic condition. The prepared Fe3O4@TiO2@P204 nanoparticles exhibited excellent selectivity for rare earth elements, and good anti-interference ability. Based on it, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for fast preconcentration and determination of trace rare earth elements in environmental samples. Under the optimal conditions, the detection limits of rare earth elements were in the range of 0.01 (Tm)-0.12 (Nd) ng L- 1 with an enrichment factor of 100-fold, and the relative standard deviations ranged from 4.9 (Pr) to 10.7% (Er). The proposed method was successfully applied to the determination of rare earth elements in environmental samples, including river water, lake water, seawater and sediment.

  4. Precise determination of rare earth elements, thorium and uranium in chondritic meteorites by inductively coupled plasma mass spectrometry. A comparative study with radiochemical neutron activation analysis

    Energy Technology Data Exchange (ETDEWEB)

    Shinotsuka, Kazunori; Ebihara, Mitsuru [Department of Chemistry, Faculty of Science, Tokyo Metropolitan University, Tokyo (Japan)

    1997-02-20

    An inductively coupled plasma mass spectrometry (ICP-MS) procedure for determining trace amounts of rare earth elements (REEs), Th and U in chondritic meteorites (chondrites) is presented. As chondrites have low contents of these elements (10{sup -2} to 10{sup -4}xcrustal rock averages), the procedure was designed to be performed in as small a scale as possible in order to reduce the procedural blank. Serious matrix effects (ion suppression) may be caused by high Fe contents (20-35 wt.), which could be eliminated by applying appropriate internal standards (Rh for Y, In and Tl for lanthanides, and Bi for Th and U) and dilution factors (10{sup 4} for Y and 10{sup 3} for the rest of elements). Radiochemical neutron activation analysis (RNAA) was also applied for determining 10 REEs (La, Ce, Nd, Sm, Eu, Gd, Tb, Tm, Yb and Lu) in chondrites. It is found that both ICP-MS and RNAA have comparable detection limits for REEs. ICP-MS, however, has the great advantage that all REEs (including Y), Th and U can be determined with similar precision. Three Antarctic chondrites for which some anomalous REE abundances had been reported by RNAA, were also analyzed by ICP-MS but no anomalies were found, which implies the limitation of RNAA data in discussing the REE abundances in detail.

  5. Arsenic Species in Edible Seaweeds Using In Vitro Biomimetic Digestion Determined by High-Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Yan-Fang Zhao

    2014-01-01

    Full Text Available 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.

  6. Determination of trace elements in medicinal activated charcoal using slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry with low vaporization temperature.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Boulyga, Sergei F; Heumann, Klaus G

    2006-01-01

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

  8. Determination of uranium isotopic composition and 236U content of soil samples and hot particles using inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Boulyga, S F; Becker, J S

    2001-07-01

    As a result of the accident at the Chernobyl nuclear power plant (NPP) the environment was contaminated with spent nuclear fuel. The 236U isotope was used in this study to monitor the spent uranium from nuclear fallout in soil samples collected in the vicinity of the Chernobyl NPP. Nuclear track radiography was applied for the identification and extraction of hot radioactive particles from soil samples. A rapid and sensitive analytical procedure was developed for uranium isotopic ratio measurement in environmental samples based on double-focusing inductively coupled plasma mass spectrometry (DF-ICP-MS) with a MicroMist nebulizer and a direct injection high-efficiency nebulizer (DIHEN). The performance of the DF-ICP-MS with a quartz DIHEN and plasma shielded torch was studied. Overall detection efficiencies of 4 x 10(-4) and 10(-3) counts per atom were achieved for 238U in DF-ICP-QMS with the MicroMist nebulizer and DIHEN, respectively. The rate of formation of uranium hydride ions UH+/U+ was 1.2 x 10(-4) and 1.4 x 10(-4), respectively. The precision of short-term measurements of uranium isotopic ratios (n = 5) in 1 microg L(-1) NBS U-020 standard solution was 0.11% (238U/235U) and 1.4% (236U/238U) using a MicroMist nebulizer and 0.25% (235U/238U) and 1.9% (236U/P38U) using a DIHEN. The isotopic composition of all investigated Chernobyl soil samples differed from those of natural uranium; i.e. in these samples the 236U/238U ratio ranged from 10(-5) to 10(-3). Results obtained with ICP-MS, alpha- and gamma-spectrometry showed differences in the migration properties of spent uranium, plutonium, and americium. The isotopic ratio of uranium was also measured in hot particles extracted from soil samples.

  9. Metallurgical and chemical characterization of copper alloy reference materials within laser ablation inductively coupled plasma mass spectrometry: Method development for minimally-invasive analysis of ancient bronze objects

    Energy Technology Data Exchange (ETDEWEB)

    Walaszek, Damian, E-mail: damian.walaszek@empa.ch [Laboratory for Analytical Chemistry, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf (Switzerland); University of Warsaw, Faculty of Chemistry, Pasteura 1, 02-093 Warsaw (Poland); Senn, Marianne [Laboratory for Analytical Chemistry, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf (Switzerland); Faller, Markus [Laboratory for Jointing Technology and Corrosion, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf (Switzerland); Philippe, Laetitia [Laboratory for Mechanics of Materials and Nanostructures, Swiss Federal Laboratories for Materials Science and Technology, Feuerwerkstrasse 39, CH-3602 Thun (Switzerland); Wagner, Barbara; Bulska, Ewa [University of Warsaw, Faculty of Chemistry, Pasteura 1, 02-093 Warsaw (Poland); Ulrich, Andrea [Laboratory for Analytical Chemistry, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf (Switzerland)

    2013-01-01

    The chemical composition of ancient metal objects provides important information for manufacturing studies and authenticity verification of ancient copper or bronze artifacts. Non- or minimal-destructive analytical methods are preferred to mitigate visible damage. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) enables the determination of major elements as well as impurities down to lower ppm-levels, however, accuracy and precision of analysis strongly depend on the homogeneity of reference materials used for calibration. Moreover, appropriate analytical procedures are required e.g. in terms of ablation strategies (scan mode, spot size, etc.). This study reviews available copper alloy (certified) reference materials — (C)RMs from different sources and contributes new metallurgical data on homogeneity and spatial elemental distribution. Investigations of the standards were performed by optical and scanning electron microscopy with X-ray spectrometry (SEM-EDX) for the following copper alloy and bronze (certified) reference materials: NIST 454, BAM 374, BAM 211, BAM 227, BAM 374, BAM 378, BAS 50.01-2, BAS 50.03-4, and BAS 50.04-4. Additionally, the influence of inhomogeneities on different ablation and calibration strategies is evaluated to define an optimum analytical strategy in terms of line scan versus single spot ablation, variation of spot size, selection of the most appropriate RMs or minimum number of calibration reference materials. - Highlights: ► New metallographic data for copper alloy reference materials are provided. ► Influence of RMs homogeneity on quality of LA-ICPMS analysis was evaluated. ► Ablation and calibration strategies were critically discussed. ► An LA-ICPMS method is proposed for analyzing most typical ancient copper alloys.

  10. 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.

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    García-Poyo, M. Carmen; Grindlay, Guillermo; Gras, Luis [Department of Analytical Chemistry, Nutrition and Food Sciences, University of Alicante, P.O. Box 99, 03080 – Alicante (Spain); Loos-Vollebregt, Margaretha T.C. de, E-mail: margaretha.deloos@ugent.be [Delft University of Technology, Faculty of Applied Sciences, Analytical Biotechnology, Julianalaan 67, 2628 BC Delft (Netherlands); Ghent University, Department of Analytical Chemistry, Krijgslaan 281 - S12, 9000 Ghent (Belgium); Mora, Juan, E-mail: juan.mora@ua.es [Department of Analytical Chemistry, Nutrition and Food Sciences, University of Alicante, P.O. Box 99, 03080 – Alicante (Spain)

    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{sup −1}) have been compared with the corresponding signals for a 1% w w{sup −1−} nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for {sup 128}Te{sup +}, {sup 78}Se{sup +} and {sup 75}As{sup +} were significantly higher when using sulfuric acid matrices (up to 2.2-fold for {sup 128}Te{sup +} and {sup 78}Se{sup +} and 1.8-fold for {sup 75}As{sup +} in the presence of 5 w w{sup -1} sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for {sup 31}P{sup +} is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for {sup 128}Te{sup +}, {sup 78}Se{sup +}, {sup 75}As{sup +} and {sup 31}P{sup +} are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S{sup +} 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

  12. Results of an interlaboratory method performance study for the size determination and quantification of silver nanoparticles in chicken meat by single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS)

    OpenAIRE

    Weigel, Stefan; Peters, Ruud; Loeschner, Katrin; Grombe, Ringo; Linsinger, Thomas P.J.

    2017-01-01

    Single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) promises fast and selective determination of nanoparticle size and number concentrations. While several studies on practical applications have been published, data on formal, especially interlaboratory validation of sp-ICP-MS, is sparse. An international interlaboratory study was organized to determine repeatability and reproducibility of the determination of the median particle size and particle number concentration of ...

  13. Method validation for high resolution sector field inductively coupled plasma mass spectrometry determination of the emerging contaminants in the open ocean: Rare earth elements as a case study

    Science.gov (United States)

    Wysocka, Irena; Vassileva, Emilia

    2017-02-01

    Analytical procedure for the determination of fourteen rare earth elements (REEs) in the seawater samples has been developed and validated. The elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) at ultra-trace level were measured by high resolution sector field inductively coupled plasma mass spectrometry (HR ICP-SFMS) after off-line analytes pre-concentration and matrix separation. The sample pre-treatment was carried out by commercially available automated system seaFAST-pico™, which is a low-pressure ion chromatography technique, based on solid phase extraction principles. Efficient elimination of seawater matrix and up to 50-fold pre-concentration of REEs enabled their accurate and precise quantification at ng L- 1 level. A validation approach in line with the requirements of ISO/IEC 17025 standard and Eurachem guidelines were followed. With this in mind, selectivity, working range, linearity, recovery (from 92% to 102%), repeatability (1%-4%), intermediate precision (2%-6%), limits of detection (0.001-0.08 ng L- 1) were systematically assessed. The total uncertainty associated to each result was estimated and the main sources of uncertainty sorted out. All major contributions to the combined uncertainty of the obtained results were identified and propagated together, following the ISO/GUM guidelines. The relative expanded uncertainty was estimated at range from 10.4% to 11.6% (k = 2). Demonstration of traceability of measurement results was also presented. Due to the low limits of detection, this method enables the determination of ultra-low levels of REEs in the open seawater as well as small variations in their concentrations. The potential of the proposed analytical procedure, based on combination of seaFAST-pico™ for sample preparation and HR ICP-SFMS, was demonstrated by direct analysis of seawater form different regions of the world.

  14. Cerium oxide-deposited mesoporous silica nanoparticles for the determination of carcinoembryonic antigen in serum using inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Choi, H.W. [Department of Chemistry, NSBI, Dankook University, 126 Jukjeon-dong, Suji-gu, Yongin-si, Gyeonggi-do 448-701 (Korea, Republic of); Lee, K.H.; Hur, N.H. [Department of Chemistry, Sogang University, Shinsu-dong, Mapo-gu, Seoul (Korea, Republic of); Lim, H.B., E-mail: plasma@dankook.ac.kr [Department of Chemistry, NSBI, Dankook University, 126 Jukjeon-dong, Suji-gu, Yongin-si, Gyeonggi-do 448-701 (Korea, Republic of)

    2014-10-17

    Highlights: • Sandwich-type immunoassay using ICP-MS and nanoparticles to determine biomarkers. • CeO{sub 2}-deposited mesoporous silica nanoparticles were synthesized as a probe. • Ratiometric measurement significantly improved the calibration linearity. • Excellent detection limit was achieved by signal amplification. - Abstract: CeO{sub 2}-deposited mesoporous silica nanoparticles were synthesized as a probe to determine carcinoembryonic antigen (CEA) in serum by inductively coupled plasma-mass spectrometry (ICP-MS). The prepared mesoporous nanoparticles were modified and tagged to the target for sandwich-type immunoassay. Fe{sub 3}O{sub 4} magnetic nanoparticles (MNPs) were also synthesized and immobilized with antibody to extract the target biomarker. The calibration curve of the synthesized CeO{sub 2}-deposited silica nanoparticles, which was plotted by the signal ratio of {sup 140}Ce/{sup 57}Fe measured by ICP-MS vs. the concentration of CEA, showed excellent linearity and sensitivity owing to the signal amplification and low spectral interference. Under optimal conditions, the sandwich-type analytical method was applied to determine CEA in serum spiked in the range of 0.001–5 ng mL{sup −1} and showed a limit of detection of 0.36 ng mL{sup −1}. Since the deposited CeO{sub 2} in the mesoporous silica layer can be substituted by other metal compounds, various kinds of metal-deposited nanoparticles can be prepared as probe materials for multiplex detection in bioanalysis.

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

    Science.gov (United States)

    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.

  16. Modern sampling and analytical methods for the determination of trace elements in marine particulate material using magnetic sector inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Bowie, Andrew R; Townsend, Ashley T; Lannuzel, Delphine; Remenyi, Tomas A; van der Merwe, Pier

    2010-08-31

    Trace elements often limit phytoplankton growth in the ocean, and the quantification of particulate forms is essential to fully understand their biogeochemical cycling. There is presently a lack of reliable measurements on the trace elemental content of marine particles, in part due to the inadequacies of the sampling and analytical methods employed. Here we report on the development of a series of state-of-the-art trace metal clean methods to collect and process oceanic particulate material in open-ocean and sea ice environments, including sampling, size-fractionated filtration, particle digestions and analysis by magnetic sector inductively coupled plasma-mass spectrometry (ICP-MS). Particular attention was paid to the analysis of certified reference materials (CRMs) and field blanks, which are typically the limiting factor for the accurate analysis of low concentrations of trace metals in marine particulate samples. Theoretical detection limits (3 s of the blank) were low for all 17 elements considered, and varied according to filter material and porosity (sub-microg L(-1) for polycarbonate filters and 1-2 microg L(-1) for quartz and polyester filters). Analytical accuracy was verified using fresh water CRMs, with excellent recoveries noted (93-103%). Digestion efficiencies for various acid combinations were assessed using sediment and plankton CRMs. Using nitric acid only, good recoveries (79-90%) were achieved for Mo, Cd, Ba, Pb, Mn, Fe, Co, Ni, Cu, Zn and Ga. The addition of HF was necessary for the quantitative recovery of the more refractory trace elements such as U, Al, V and Cr. Bioactive elements such as P can also be analysed and used as a biomass normaliser. Our developed sampling and analytical methods proved reliable when applied during two major field programs in both the open Southern Ocean and Antarctic sea ice environments during the International Polar Year in 2007. Trace elemental data are presented for particulate samples collected in both

  17. Ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry for the determination of Cr, Fe, Cu, Zn and Se in cereals

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Shih-Yi [Department of Chemistry, National Sun Yat-sen University, Kaohsiung 80424, Taiwan (China); Jiang, Shiuh-Jen, E-mail: sjjiang@faculty.nsysu.edu.tw [Department of Chemistry, National Sun Yat-sen University, Kaohsiung 80424, Taiwan (China); Department of Medical Laboratory Science and Biotechnology, Kaohsiung Medical University, Kaohsiung 80708, Taiwan (China); Sahayam, A.C. [National Centre for Compositional Characterisation of Materials (CCCM), Hyderabad (India)

    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{sup −1} methane (CH{sub 4}) 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{sup −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{sup −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. - Highlights: • Determination of Cr, Fe, Cu, Zn and Se in cereal samples • Ultrasonic slurry sampling in combination with DRC-ICP-MS • Better sensitivity with thioacetamide modifier in ETV • Decreased sample preparation time with solid sampling • Validation with NIST SRM 1568a Rice Flour and NIST SRM 1567a Wheat Flour.

  18. 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

    Science.gov (United States)

    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.

  19. Application of the Zr/Hf ratio in the determination of hafnium in geochemical samples by high-resolution inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Liu, Ya Xuan; Li, Qing Xia; Ma, Na; Sun, Xiao Ling; Bai, Jin Feng; Zhang, Qin

    2014-12-02

    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.

  20. 87Sr/86Sr isotope ratio measurements by laser ablation multicollector inductively coupled plasma mass spectrometry: Reconsidering matrix interferences in bioapatites and biogenic carbonates

    Science.gov (United States)

    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.

  1. Pharmacokinetics and tissue distribution of novel platinum containing anticancer agent BP‐C1 studied in rabbits using sector field inductively coupled plasma mass spectrometry

    Science.gov (United States)

    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

  2. Exploiting dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) for sequential determination of trace elements in blood using a dilute-and-shoot procedure.

    Science.gov (United States)

    Batista, Bruno Lemos; Rodrigues, Jairo Lisboa; Nunes, Juliana Andrade; Souza, Vanessa Cristina de Oliveira; Barbosa, Fernando

    2009-04-20

    Inductively coupled plasma mass spectrometry with quadrupole (q-ICP-MS) and dynamic reaction cell (DRC-ICP-MS) were evaluated for sequential determination of As, Cd, Co, Cr, Cu, Mn, Pb, Se, Tl, V and Zn in blood. The method requires as little as 100 microL of blood. Prior to analysis, samples (100 microL) were diluted 1:50 in a solution containing 0.01% (v/v) Triton X-100 and 0.5% (v/v) nitric acid. The use of the DRC was only mandatory for Cr, Cu, V and Zn. For the other elements the equipment may be operated in a standard mode (q-ICP-MS). Ammonia was used as reaction gas. Selection of best flow rate of ammonium gas and optimization of the quadrupole dynamic band-pass tuning parameter (RPq) were carried out, using a ovine base blood for Cr and V and a synthetic matrix solution (SMS) for Zn and Cu diluted 1:50 and spiked to contain 1 microg L(-1) of each element. Method detection limits (3 s) for (75)As, (114)Cd, (59)Co, (51)Cr, (63)Cu (55)Mn, (208)Pb, (82)Se, (205)Tl, (51)V, and (64)Zn were 14.0, 3.0, 11.0, 7.0, 280, 9.0, 3.0, 264, 0.7, 6.0 and 800 ng L(-1), respectively. Method validation was accomplished by the analysis of blood Reference Materials produced by the L'Institut National de Santé Publique du Quebec (Canada).

  3. Determination of (236)U in environmental samples by single extraction chromatography coupled to triple-quadrupole inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Yang, Guosheng; Tazoe, Hirofumi; Yamada, Masatoshi

    2016-11-09

    In order to measure trace (236)U and (236)U/(238)U in environmental samples with a high matrix effect, a novel and simple method was developed that makes the digestion and purification procedures compatible with advanced triple-quadrupole inductively coupled plasma-mass spectrometry. A total dissolution of sample with HF + HNO3 + HClO4 was followed by chromatographic separation with a single resin column containing normal type DGA resin (N,N,N',N'-tetra-n-octyldiglycolamide) as the extractant system. The analytical accuracy and precision of (236)U/(238)U ratios, measured as (236)U(16)O(+)/(238)U(16)O(+), were examined by using the reference materials IAEA-135, IAEA-385, IAEA-447, and JSAC 0471. The low method detection limit (3.50 × 10(-6) Bq kg(-1)) makes it possible to perform routine monitoring of environmental (236)U due to global fallout combined with the Fukushima Daiichi Nuclear Power Plant accident fallout (>10(-5) Bq kg(-1)). Finally, the developed method was successfully applied to measure (236)U/(238)U ratios and (236)U activities in soil samples contaminated by the accident. The low (236)U/(238)U atom ratios ((1.50-13.5) × 10(-8)) and (236)U activities ((2.25-14.1) × 10(-2) mBq kg(-1)) indicate (236)U contamination was mainly derived from global fallout in the examined samples.

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

    Science.gov (United States)

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

    2017-03-01

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

  5. Slurry sampling flow injection chemical vapor generation inductively coupled plasma mass spectrometry for the determination of trace Ge, As, Cd, Sb, Hg and Bi in cosmetic lotions

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wei-Ni [Department of Chemistry, National Sun Yat-sen University, Kaohsiung 80424, Taiwan (China); Jiang, Shiuh-Jen, E-mail: sjjiang@faculty.nsysu.edu.tw [Department of Chemistry, National Sun Yat-sen University, Kaohsiung 80424, Taiwan (China); Department of Medical Laboratory Science and Biotechnology, Kaohsiung Medical University, Kaohsiung 80708, Taiwan (China); Chen, Yen-Ling [Department of Fragrance and Cosmetic Science, Kaohsiung Medical University, Kaohsiung 80708, Taiwan (China); Sahayam, A.C. [National Centre for Compositional Characterisation of Materials (CCCM), Hyderabad (India)

    2015-02-20

    Highlights: • Determination of Ge, As, Cd, Sb, Hg and Bi in cosmetic lotions in a single run. • Accurate analysis using isotope dilution and standard addition methods. • Vapor generation ICP-MS yielded superior detection limits compared to ETV-ICP-MS. • No sample dissolution increased sample through put. • Analysis of GBW09305 Cosmetic (Cream) reference material for accuracy. - Abstract: A slurry sampling inductively coupled plasma mass spectrometry (ICP-MS) method has been developed for the determination of Ge, As, Cd, Sb, Hg and Bi in cosmetic lotions using flow injection (FI) vapor generation (VG) as the sample introduction system. A slurry containing 2% m/v lotion, 2% m/v thiourea, 0.05% m/v L-cysteine, 0.5 μg mL{sup −1} Co(II), 0.1% m/v Triton X-100 and 1.2% v/v HCl was injected into a VG-ICP-MS system for the determination of Ge, As, Cd, Sb, Hg and Bi without dissolution and mineralization. Because the sensitivities of the analytes in the slurry and that of aqueous solution were quite different, an isotope dilution method and a standard addition method were used for the determination. This method has been validated by the determination of Ge, As, Cd, Sb, Hg and Bi in GBW09305 Cosmetic (Cream) reference material. The method was also applied for the determination of Ge, As, Cd, Sb, Hg and Bi in three cosmetic lotion samples obtained locally. The analysis results of the reference material agreed with the certified value and/or ETV-ICP-MS results. The detection limit estimated from the standard addition curve was 0.025, 0.1, 0.2, 0.1, 0.15, and 0.03 ng g{sup −1} for Ge, As, Cd, Sb, Hg and Bi, respectively, in original cosmetic lotion sample.

  6. Solvent bar microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry for the speciation of inorganic arsenic in water samples

    Energy Technology Data Exchange (ETDEWEB)

    Pu Xuli; Chen Beibei [Department of Chemistry, Wuhan University, Wuhan 430072 (China); Hu Bin [Department of Chemistry, Wuhan University, Wuhan 430072 (China)], E-mail: binhu@whu.edu.cn

    2009-07-15

    A new method of solvent bar microextraction (SBME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the speciation of As(III) and As(V) in water samples was developed. The method is based on the chelation of As(III) and ammonium pyrrolidine dithiocarbamate (APDC) under the selected conditions, and the As(III)-PDC complex could be extracted into the organic phase, while As(V) remained in aqueous solution. The post-extraction organic phase was directly injected into ETV-ICP-MS for determination of As(III) with the use of iridium as permanent chemical modifier. As(V) was reduced to As(III) by L-cysteine and was then subjected to SBME prior to total As determination. The assay of As(V) was based on subtracting As(III) from total As. The factors affecting on the SBME, such as organic solvent, sample pH, chelating reagent concentration, stirring rate and extraction time, and chemical modification of iridium in ETV-ICP-MS have been studied. Under the optimized conditions, the enrichment factor of 220-fold could be achieved in 15 min extraction, the limit of detection (LOD) for As(III) was 0.32 pg mL{sup - 1}, and the relative standard deviation (RSD) was 8.8% (0.1 ng mL{sup - 1}, n = 9). Compared with hollow fiber liquid phase microextraction (HF-LPME), SBME has a higher enrichment factor and faster extraction kinetics. In order to validate the accuracy of the method, a Certified Reference Material of GSBZ50004-88 (No. 200420) water sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also applied to the speciation of inorganic As in environmental waters with satisfactory results.

  7. Qualitative and quantitative spectro-chemical analysis of dates using UV-pulsed laser induced breakdown spectroscopy and inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    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. Copyright © 2016 Elsevier B

  8. Polymer monolithic capillary microextraction on-line coupled with inductively coupled plasma-mass spectrometry for the determination of trace Au and Pd in biological samples

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaolan; He, Man; Chen, Beibei; Hu, Bin, E-mail: binhu@whu.edu.cn

    2014-11-01

    A novel method based on on-line polymer monolithic capillary microextraction (CME)-inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace Au and Pd in biological samples. For this purpose, poly(glycidyl methacrylate-ethylene dimethacrylate) monolith was prepared and functionalized with mercapto groups. The prepared monolith exhibited good selectivity to Au and Pd, and good resistance to strong acid with a long life span. Factors affecting the extraction efficiency of CME, such as sample acidity, sample flow rate, eluent conditions and coexisting ion interference were investigated in detail. Under the optimal conditions, the limits of detection (LODs, 3σ) were 5.9 ng L{sup −1} for Au and 8.3 ng L{sup −1} for Pd, and the relative standard deviations (RSDs, c = 50 ng L{sup −1}, n = 7) were 6.5% for Au and 1.1% for Pd, respectively. The developed method was successfully applied to the determination of Au and Pd in human urine and serum samples with the recovery in the range of 84–118% for spiked samples. The developed on-line polymer monolithic CME-ICP-MS method has the advantages of rapidity, simplicity, low sample/reagent consumption, high sensitivity and is suitable for the determination of trace Au and Pd in biological samples with limited amount available and complex matrix. - Highlights: • An on-line CME-ICP-MS method was developed for Au and Pd analysis in human fluids. • Poly(GMA-EDMA-SH) monolith exhibited good selectivity for Au/Pd and acid-resistance. • The method is rapid, simple, and sensitive with low sample/reagents consumption.

  9. Elevated metallothionein-bound cadmium concentrations in urine from bladder carcinoma patients, investigated by size exclusion chromatography-inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Wolf, Christian [Department of Molecular Trace Element Research in the Life Sciences, Helmholtz Centre Berlin for Materials and Energy, Glienicker Str. 100, 14109 Berlin (Germany)], E-mail: wolf@helmholtz-berlin.de; Strenziok, Romy [Department of Urology, Charite University Medicine Berlin, Campus Benjamin Franklin, Hindenburgdamm 30, 12203 Berlin (Germany); Kyriakopoulos, Antonios [Department of Molecular Trace Element Research in the Life Sciences, Helmholtz Centre Berlin for Materials and Energy, Glienicker Str. 100, 14109 Berlin (Germany)

    2009-01-12

    Cadmium is discussed as being involved in the development of transitional cell carcinoma (TCC) of the bladder and can be observed in urine of these patients. Investigations of urinary samples from bladder cancer patients and normal controls were carried out with special emphasis on metallothionein (MT)-bound cadmium. Compounds that are constituents of urine were separated in urine samples by means of size exclusion chromatography and cadmium was monitored continuously with a hyphenated inductively coupled plasma mass spectrometry (ICP-MS) system. MT-bound cadmium was quantified by peak area integration, taking into account the intensity of the rhodium signal which was added continuously before ICP-MS detection. The obtained results show that urinary cadmium is predominantly bound to the observed MT-fraction. The median of the MT-bound cadmium concentration in the control group was found to be 0.8 {mu}g L{sup -1} whereas the cancer group has a median of 1.8 {mu}g L{sup -1}. The variance of the data in the cancer group is much higher than in the controls. However, the urinary MT-bound cadmium is significantly elevated in the cancer group; odds-ratio test: 7.11 (95% C.I.: 1.89-26.80), taking into account the total protein content. Due to the fact that only one main cadmium-containing fraction was observed, there is no necessity to separate the MT-fraction before cadmium determination in urine samples in future studies.

  10. Quantitative Metabolite Profiling of an Amino Group Containing Pharmaceutical in Human Plasma via Precolumn Derivatization and High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry.

    Science.gov (United States)

    Li, Sanwang; Klencsár, Balázs; Balcaen, Lieve; Cuyckens, Filip; Lynen, Frederic; Vanhaecke, Frank

    2017-02-07

    Quantitative determination of the candidate drug molecule and its metabolites in biofluids and tissues is an inevitable step in the development of new pharmaceuticals. Because of the time-consuming and expensive nature of the current standard technique for quantitative metabolite profiling, i.e., radiolabeling followed by high-performance liquid chromatography (HPLC) with radiodetection, the development of alternative methodologies is of great interest. In this work, a simple, fast, sensitive, and accurate method for the quantitative metabolite profiling of an amino group containing drug (levothyroxine) and its metabolites in human plasma, based on precolumn derivatization followed by HPLC-inductively coupled plasma mass spectrometry (ICPMS), was developed and validated. To introduce a suitable "heteroelement" (defined here as an element that is detectable with ICPMS), an inexpensive and commercially available reagent, tetrabromophthalic anhydride (TBPA) was used for the derivatization of free NH2-groups. The presence of a known number of I atoms in both the drug molecule and its metabolites enabled a cross-validation of the newly developed derivatization procedure and quantification based on monitoring of the introduced Br. The formation of the derivatives was quantitative, providing a 4:1 stoichiometric Br/NH2 ratio. The derivatives were separated via reversed-phase HPLC with gradient elution. Bromine was determined via ICPMS at a mass-to-charge ratio of 79 using H2 as a reaction gas to ensure interference-free detection, and iodine was determined at a mass-to-charge ratio of 127 for cross-validation purposes. The method developed shows a fit-for-purpose accuracy (recovery between 85% and 115%) and precision (repeatability <15% RSD). The limit of quantification (LoQ) for Br was approximately 100 μg/L.

  11. The in vivo biodistribution and fate of CdSe quantum dots in the murine model: a laser ablation inductively coupled plasma mass spectrometry study.

    Science.gov (United States)

    Wang, TsingHai; Hsieh, HuiAn; Hsieh, YiKong; Chiang, ChiShiun; Sun, YuhChang; Wang, ChuFang

    2012-12-01

    Understanding the cytotoxicity of quantum dots strongly relies upon the development of new analytical techniques to gather information about various aspects of the system. In this study, we demonstrate the in vivo biodistribution and fate of CdSe quantum dots in the murine model by means of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). By comparing the hot zones of each element acquired from LA-ICP-MS with those in fluorescence images, together with hematoxylin and eosin-stained images, we are able to perceive the fate and in vivo interactions between quantum dots and rat tissues. One hour after intravenous injection, we found that all of the quantum dots had been concentrated inside the spleen, liver and kidneys, while no quantum dots were found in other tissues (i.e., muscle, brain, lung, etc.). In the spleen, cadmium-114 signals always appeared in conjunction with iron signals, indicating that the quantum dots had been filtered from main vessels and then accumulated inside splenic red pulp. In the liver, the overlapped hot zones of quantum dots and those of phosphorus, copper, and zinc showed that these quantum dots have been retained inside hepatic cells. Importantly, it was noted that in the kidneys, quantum dots went into the cortical areas of adrenal glands. At the same time, hot zones of copper appeared in proximal tubules of the cortex. This could be a sign that the uptake of quantum dots initiates certain immune responses. Interestingly, the intensity of the selenium signals was not proportional to that of cadmium in all tissues. This could be the result of the decomposition of the quantum dots or matrix interference. In conclusion, the advantage in spatial resolution of LA-ICP-MS is one of the most powerful tools to probe the fate, interactions and biodistribution of quantum dots in vivo.

  12. Removal of high-salinity matrices through polymer-complexation-ultrafiltration for the detection of trace levels of REEs using inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Duan, Hualing; Lin, Jijun; Gong, Zhenbin; Huang, Jiahua; Yang, Shifeng

    2015-10-01

    The polymer-complexation-ultrafiltration (PCUF) technique was applied to separate trace levels of rare earth elements (REEs), including scandium, yttrium and the lanthanides, from high-salinity matrices prior to their determination by inductively coupled plasma mass spectrometry (ICP-MS). The REEs were converted into REE-polymer complexes using the water-soluble polymer polyacrylic acid (PAA) at a specified pH, retained on the ultrafiltration membrane of centrifugal filter units, and finally eluted using diluted nitric acid to achieve separation from matrices with relatively high levels of various inorganic ions, such as sodium, potassium, calcium, magnesium, and chlorine ions. Numerous factors affecting the PCUF efficiency were optimized. The optimal conditions included the addition of 30 mg L(-1) of PAA, a pH of 7.5, a reaction time of 40 min at room temperature, and 5.0 mL of 3% nitric acid (v/v) eluent. Under these conditions, the analytes were quantitatively separated and recovered, with a resulting relative standard deviation (RSD) of less than 4.0% (0.05 µg L(-1), n=5) and standard addition recoveries between 89.2% (La) and 95.8% (Sm) for matrices of various salinities. The blank samples for the method ranged from 0.0003 µg L(-1) (Dy) to 0.0031 µg L(-1) (Sc), and the limits of quantification (LOQs, 10σ) were between 0.0006 µg L(-1) (Dy) and 0.0026 µg L(-1) (Sc). Furthermore, the salinity of the sample exhibited no effect on the REE-polymer complex formation process. Finally, the method was successfully applied for the determination of trace levels of dissolved Sc, Y, and lanthanides in coastal and estuarine seawater samples.

  13. Evaluation of gel electrophoresis techniques and laser ablation-inductively coupled plasma-mass spectrometry for screening analysis of Zn and Cu-binding proteins in plankton.

    Science.gov (United States)

    Jiménez, Maria S; Rodriguez, L; Bertolin, Juan R; Gomez, Maria T; Castillo, Juan R

    2013-01-01

    The determination of metal-binding proteins in plankton is important because of their involvement in photosynthesis, which is fundamental to the biogeochemical cycle of the oceans and other ecosystems. We have elaborated a new strategy for screening of Cu and Zn-containing proteins in plankton on the basis of separation of proteins by use of Blue-Native PAGE (BN-PAGE), which entails use of a non-denaturing Tris-tricine system and detection of metals in the proteins by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). For comparison, denaturing PAGE based on Tris-glycine and Tris-tricine systems and Anodic-Native PAGE have also been investigated. A large number of protein bands with MW between 20 and 75 kDa were obtained by use of Tris-glycine PAGE but detection of metals by LA-ICP-MS was unsuccessful because of loss of metals from the proteins during the separation process. Different protein extraction, purification, and preconcentration methods were evaluated, focussing on both issues-achieving the best extraction and characterization of the proteins while maintaining the integrity of metal-protein binding in the plankton sample. Use of 25 mmol L(-1) Tris-HCl and a protease inhibitor as extraction buffer with subsequent ultrafiltration and acetone precipitation was the most efficient means of sample preparation. Two Cu and Zn proteins were detected, a protein band corresponding to a MW of 60 kDa and another poorly resolved band with a MW between 15 and 35 kDa.

  14. Analysis of polyacrylamide gels for trace metals using diffusive gradients in thin films and laser ablation inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Warnken, Kent W; Zhang, Hao; Davison, William

    2004-10-15

    A simple method for the analysis of polyacrylamide diffusive gradients in thin film (DGT) gels by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), employing a novel use of (115)In internal standardization, has been developed. This method allows the determination of Co, Ni, Cu, Zn, Cd, and Pb concentrations (at the DGT filter face) or fluxes in sediments at a spatial resolution of 100 microm. Single-layered gels, using an optimized laser defocus of 4000 microm at 400 mJ power, showed high precision (generally approximately 10%) and a linear response during solution deployment. Of the elements Sc, In, Ba, La, Ce, and Tb, Ba most closely tracked variations in laser energy and showed the highest analytical precision but could not be used as an internal standard due to its elevated presence in natural sediments. Therefore, internal standardization, necessary to normalize data collected on different days, was carried out using (115)In contained within a second layer of backing gel and dried along with the analyte layer as a dual-gel disk. This multilayered gel standard required a laser defocus setting of 1000 microm and a laser power of approximately 800 mJ. Analytical precision for a 64-spot ablation grid at 100-microm spacing was approximately 10%. Verification of this method was carried out on DGT sediment probes deployed in Priest Pot (English Lake District). Results obtained by conventional slicing techniques and aqueous elution agreed with laser ablation results when the different sampling areas were considered. The elution results varied by a factor of laser ablation technique showed a variability of approximately 4, indicating localized elevated concentrations of Co. This higher resolution LA-ICPMS method could ultimately lead to an improved understanding of the geochemical processes responsible for metal uptake and release in sediments.

  15. Comparison of 265 nm Femtosecond and 213 nm Nanosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry for Pb Isotope Ratio Measurements.

    Science.gov (United States)

    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.

  16. Novel bioimaging techniques of metals by laser ablation inductively coupled plasma mass spectrometry for diagnosis of fibrotic and cirrhotic liver disorders.

    Directory of Open Access Journals (Sweden)

    Pornwilard M-M

    Full Text Available BACKGROUND AND AIMS: Hereditary disorders associated with metal overload or unwanted toxic accumulation of heavy metals can lead to morbidity and mortality. Patients with hereditary hemochromatosis or Wilson disease for example may develop severe hepatic pathology including fibrosis, cirrhosis or hepatocellular carcinoma. While relevant disease genes are identified and genetic testing is applicable, liver biopsy in combination with metal detecting techniques such as energy-dispersive X-ray spectroscopy (EDX is still applied for accurate diagnosis of metals. Vice versa, several metals are needed in trace amounts for carrying out vital functions and their deficiency due to rapid growth, pregnancy, excessive blood loss, and insufficient nutritional or digestive uptake results in organic and systemic shortcomings. Established in situ techniques, such as EDX-ray spectroscopy, are not sensitive enough to analyze trace metal distribution and the quantification of metal images is difficult. METHODS: In this study, we developed a quantitative biometal imaging technique of human liver tissue by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS in order to compare the distribution of selected metals in cryo-sections of healthy and fibrotic/cirrhotic livers. RESULTS: Most of the metals are homogeneous distributed within the normal tissue, while they are redirected within fibrotic livers resulting in significant metal deposits. Moreover, total iron and copper concentrations in diseased liver were found about 3-5 times higher than in normal liver samples. CONCLUSIONS: Biometal imaging via LA-ICP-MS is a sensitive innovative diagnostic tool that will impact clinical practice in identification and evaluation of hepatic metal disorders and to detect subtle metal variations during ongoing hepatic fibrogenesis.

  17. Detection of metals in proteins by means of polyacrylamide gel electrophoresis and laser ablation-inductively coupled plasma-mass spectrometry: application to selenium.

    Science.gov (United States)

    Chéry, Cyrille C; Günther, Detlef; Cornelis, Rita; Vanhaecke, Frank; Moens, Luc

    2003-10-01

    The capabilities of laser ablation-inductively coupled plasma-mass spectrometry for the detection of trace elements in a gel after gel electrophoresis were systematically studied. Figures of merit, such as limit of detection, linearity, and repeatability, were evaluated for various elements (Li, V, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Pd, Ag, Cd, Pt, Tl, Pb). Two ablation strategies were followed: single hole drilling, relevant for ablation of spots after two-dimensional (2-D) separations, and ablation with translation, i.e., on a line, relevant for one-dimensional (1-D) separations. This technique was applied to the detection of selenoproteins in red blood cells extracts after a 1-D separation (sodium dodecyl sulfate-polyacrylamide gel electrophoresis) and the detection of selenium-containing proteins in yeast after 2-D electrophoresis (2-DE). The detection procedure was further improved by using the dynamic reaction cell technology, which allowed the removal of the Ar_2(+) interference and hence the use of the most abundant Se isotope, (80)Se. Reaction gases were compared (methane, carbon monoxide, ammonia, oxygen and the combination of argon (collision gas) and hydrogen (reaction gas)). In each instance, the reaction cell parameters were optimized in order to obtain the lowest detection limit for Se (as (80)Se(+), (82)Se(+) or (77)Se(+); and as (80)Se(16)O(+), (82)Se(16)O(+) or (77)Se(16)O(+) with O(2) as the reaction gas). Carbon monoxide was found to offer the best performance. The detection limit with the use of DRC and He as transport gas was 0.07 microg Se g(-1) gel with single hole drilling and 0.15 microg Se g(-1) gel for ablation with translation.

  18. Imaging of metals in biological tissue by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS): state of the art and future developments.

    Science.gov (United States)

    Sabine Becker, J

    2013-02-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is well established as a sensitive trace and ultratrace analytical technique with multielement capability for bioimaging of metals and studying metallomics in biological and medical tissue. Metals and metalloproteins play a key role in the metabolism and formation of metal-containing deposits in the brain but also in the liver. In various diseases, analysis of metals and metalloproteins is essential for understanding the underlying cellular processes. LA-ICP-MS imaging (LA-ICP-MSI) combined with other complementary imaging techniques is a sophisticated tool for investigating the regional and cellular distribution of metals and related metal-containing biomolecules. On the basis of successful routine techniques for the elemental bioimaging of cryosections by LA-ICP-MSI with a spatial resolution between 200 and ~10 µm, the further development used online laser microdissection ICP-MSI to study the metal distribution in small biological sample sections (at the cellular level from 10 µm to the submicrometer range). The use of mass spectrometric imaging of metals and also nonmetals is demonstrated on a series of biological specimens. This article discusses the state of the art of bioimaging of metals in thin biological tissue sections by LA-ICP-MSI with spatial resolution at the micrometer scale, future developments and prospects for quantitative imaging techniques of metals in the nanometer range. In addition, combining quantitative elemental imaging by LA/laser microdissection-ICP-MSI with biomolecular imaging by matrix-assisted laser desorption/ionization-MSI will be challenging for future life science research.

  19. Validation of the determination of the B isotopic composition in Roman glasses with laser ablation multi-collector inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Devulder, Veerle [Department of Analytical Chemistry, Ghent University, Krijgslaan 281-S12, 9000 Ghent (Belgium); Department of Earth and Environmental Sciences, Katholieke Universiteit Leuven, Celestijnenlaan 200 E-box 2408, 3001 Leuven (Belgium); Gerdes, Axel [Institute of Geoscience, Goethe Universität, Altenhoeferallee 1, 60438 Frankfurt am Main (Germany); Vanhaecke, Frank, E-mail: Frank.Vanhaecke@UGent.be [Department of Analytical Chemistry, Ghent University, Krijgslaan 281-S12, 9000 Ghent (Belgium); Degryse, Patrick [Department of Earth and Environmental Sciences, Katholieke Universiteit Leuven, Celestijnenlaan 200 E-box 2408, 3001 Leuven (Belgium)

    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 δ{sup 11}B 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. - Highlights: • First use of LA-MC-ICP-MS for B isotopic analysis of ancient glass • Careful validation of LA-MC-ICP-MS approach • Similar precision & accuracy via solution MC-ICP-MS after isolation of B • Enhancement of sample throughput & reduction of sample consumption • Improved conditions for archeometric research on (pre-)Roman glass.

  20. 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

    Energy Technology Data Exchange (ETDEWEB)

    Takano, Shotaro, E-mail: shotaro@inter3.kuicr.kyoto-u.ac.jp [Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan); Tanimizu, Masaharu [Kochi Institute for Core Sample Research, Japan Agency for Marine-Earth Science and Technology, 200 Monobe Otsu, Nankoku 783-8502 (Japan); Hirata, Takafumi [Laboratory for Planetary Sciences, Division of Earth and Planetary Sciences, Kyoto University, Kitashirakawa Oiwake-cho, Kyoto 606-8502 (Japan); Sohrin, Yoshiki [Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan)

    2013-06-19

    Graphical abstract: -- Highlights: •A simple analytical method for determining the Cu isotopic composition in seawater using an ethylenediaminetriacetic acid chelating resin was developed. •The accuracy was evaluated via addition of NIST SRM976 or {sup 65}Cu-enriched standard to seawater. •δ{sup 65}Cu of seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples from the northwestern Pacific Ocean were firstly determined. -- Abstract: 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 2 L 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{sup 65}Cu was 0.40–0.68‰.

  1. Multielement trace determinations in A1 2O 3 ceramic powders by inductively coupled plasma mass spectrometry with special reference to on-line trace preconcentration

    Science.gov (United States)

    Pollmann, D.; Leis, F.; Tölg, G.; Tschöpel, P.; Broekaert, J. A. C.

    1994-12-01

    The use of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of trace elements in Al 2O 3 powders is reported. Special interest is given to a preconcentration of the trace elements by on-line coupling of chromatography to ICP-MS. This is based on the complexation of Co, Cu, Cr, Fe, Ga, Mn, Ni, V and Zn with hexamethylene-dithiocarbamate (HMDC), their preconcentration on a C18 RP column by reversed phase liquid chromatography and their elution with CH 3OH-H 2O mixtures. A direct coupling of the HPLC system to the ICP-MS has been realized by high pressure pneumatic nebulization using desolvation. With the Chromatographie method developed, removal of the AI by at least 99% was achieved. For the trace elements V, Fe, Ni, Co, Cu and Ga, high and reproducible recoveries (ranging from 96-99%) were reached. The method developed has been shown to considerably enhance the power of detection as compared with direct procedures, namely down to 0.02-0.16 ( μg/g for V and Fe, respectively. The possibilities of the method are shown by the determinations of V, Mn, Fe, Ni, Co, Cu, Zn and Ga at the μg/g level in A1 2O 3 powders. The accuracy of the method at the 0.06 to 9.0 μg/g level for Co and Fe, respectively, is demonstrated by a comparison with results of independent methods from the literature.

  2. Gold nanoparticles as intermediate ligands for polymer monolithic capillary microextraction of trace rare earth elements followed by inductively coupled plasma mass spectrometry detection

    Science.gov (United States)

    Cai, Yabing; Chen, Beibei; He, Man; Liu, Xiaolan; Bin, Hu

    2017-01-01

    In this work, a novel method of Au nanoparticles (NPs) modified polymer monolithic capillary microextraction (CME) on-line coupling with inductively coupled plasma-mass spectrometry (ICP-MS) was developed for the determination of trace rare earth elements (REEs) in environmental and biological samples. The poly(glycidyl methacrylate-ethylene dimethacrylate) monolithic capillary was prepared, functionalized with thiol ligands for the attaching of Au NPs, and then modified with mercaptosuccinic acid to provide massive carboxyl groups which have high affinity to REEs. With the modification of Au NPs, the adsorption capacity of the monolith towards target REEs has been improved by 3 to 6.5 times. Under the optimized conditions, the limits of detection of the developed method for REEs were in the range of 0.16 (Tb)-0.85 (Gd) ng L- 1. The enrichment factor was 25-fold with the sample throughput of 10 h- 1. And the relative standard deviations were between 2.7 (Lu) and 9.8% (Dy) (c = 10 ng L- 1, n = 9). The accuracy of the method was validated by the analysis of a standard stock solution of GSB04-1789-2004 and a Certified Reference Material of GBW07301a stream sediment. The proposed method was applied for the analysis of trace REEs in seawater samples as well as human whole blood with good recoveries. The prepared monolith is featured with strong anti-interference ability, superior adsorption capacity as well as long lifespan, and the developed monolithic CME-ICP-MS is sensitive, simple and rapid for the analysis of trace/ultra-trace REEs in environmental and biological samples with complex matrix.

  3. Determinations of rare earth element abundance and U-Pb age of zircons using multispot laser ablation-inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    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

  4. Combining single-particle inductively coupled plasma mass spectrometry and X-ray absorption spectroscopy to evaluate the release of colloidal arsenic from environmental samples.

    Science.gov (United States)

    Gomez-Gonzalez, Miguel Angel; Bolea, Eduardo; O'Day, Peggy A; Garcia-Guinea, Javier; Garrido, Fernando; Laborda, Francisco

    2016-07-01

    Detection and sizing of natural colloids involved in the release and transport of toxic metals and metalloids is essential to understand and model their environmental effects. Single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS) was applied for the detection of arsenic-bearing particles released from mine wastes. Arsenic-bearing particles were detected in leachates from mine wastes, with a mass-per-particle detection limit of 0.64 ng of arsenic. Conversion of the mass-per-particle information provided by SP-ICP-MS into size information requires knowledge of the nature of the particles; therefore, synchrotron-based X-ray absorption spectroscopy (XAS) was used to identify scorodite (FeAsO4·2H2O) as the main species in the colloidal particles isolated by ultrafiltration. The size of the scorodite particles detected in the leachates was below 300-350 nm, in good agreement with the values obtained by TEM. The size of the particles detected by SP-ICP-MS was determined as the average edge of scorodite crystals, which show a rhombic dipyramidal form, achieving a size detection limit of 117 nm. The combined use of SP-ICP-MS and XAS allowed detection, identification, and size determination of scorodite particles released from mine wastes, suggesting their potential to transport arsenic. Graphical abstract Analytical approach for the detection and size characterization of As-bearing particles by SP-ICP-MS and XAS in environmental samples.

  5. Determination of Metal Levels in Shamma (Smokeless Tobacco) with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) in Najran, Saudi Arabia

    Science.gov (United States)

    Brima, Eid Ibrahim

    2016-10-01

    Objective: The use of Shamma (smokeless tobacco) by certain groups is giving rise to health problems, including cancer, in parts of Saudi Arabia. Our objective was to determine metals levels in Shamma using inductively coupled plasma mass spectrometry (ICP-MS). Methods: Thirty-three samples of Shamma (smokeless tobacco) were collected, comprising four types: brown Shamma (n = 14.0), red Shamma (n = 9.0), white Shamma (n = 4.0), and yellow Shamma (n = 6.0). All samples were collected randomly from Shamma users in the city of Najran. Levels of 11 elements (Al, As, Cd, Co, Cr, Cu, Li, Mn, Ni, Pb, and Zn) were determined by ICP-MS. Results: A mixed standard (20 ppb) of all elements was used for quality control, and average recoveries ranged from 74.7% to 112.2%. The highest average concentrations were found in the following order: Al (598.8–812.2 μg/g), Mn (51.0–80.6 μg/g), and Ni (23.2–53.3 μg/g) in all four Shamma types. The lowest concentrations were for As (0.7–1.0 μg/g) and Cd (0.0–0.06 μg/g). Conclusions: The colour of each Shamma type reflects additives mixed into the tobacco. Cr and Cu were showed significant differences (P < 0.05) among Shamma types. Moreover, Pb levels are higher in red and yellow Shamma, which could be due to use (PbCrO4) as yellow colouring agent and lead tetroxide, Pb3O4 as a red colouring agent. The findings from this study can be used to raise public awareness about the safety and health effects of Shamma, which is clearly a source of oral exposure to metals. Creative Commons Attribution License

  6. Urinary iodine: comparison of a simple method for its determination in microplates with measurement by inductively-coupled plasma mass spectrometry

    Science.gov (United States)

    Haap, Michael; Roth, Heinz Jürgen; Huber, Thomas; Dittmann, Helmut; Wahl, Richard

    2017-01-01

    The aim of our study was to develop and validate an inexpensive, rapid, easy to use quantitative method to determine urinary iodine without major procurement costs for equipment. The rationale behind introducing this method is the increasing demand for urinary iodine assessments. Our study included 103 patients (76 female, 27 male), age (arithmetic mean) 52 ± 17.3 years. Urinary iodine was determined in microplates by a modification of the Sandell-Kolthoff reaction. The results were compared with inductively-coupled plasma mass spectrometry (ICP-MS) for iodine, considered as reference method. Geometric mean of urinary iodine determined by the Sandell-Kolthoff reaction method was 62.69 μg/l (95% confidence interval 53.16–73.92) whereas by the ICP-MS method it was 65.53 μg/l (95% confidence interval 54.77–78.41). Passing-Bablok regression equations for both methods gave y = 3.374 + 0.873x (y: Sandell-Kolthoff method, x: ICP-MS). Spearman´s correlation coefficient was 0.981, indicating a very high degree of agreement between the two methods. Bland-Altman plots showed no significant systematic difference between the two methods. The modified Sandell-Kolthoff method using microtiter plate technique presented here is a simple, inexpensive semi-automated method to determine urinary iodine with very little toxic waste. Comparison with the ICP-MS-technique yielded a good agreement between the two methods. PMID:28045077

  7. Comparative Investigation between In Situ Laser Ablation Versus Bulk Sample (Solution Mode) Inductively Coupled Plasma Mass Spectrometry (ICP-MS) Analysis of Trinitite Post-Detonation Materials.

    Science.gov (United States)

    Dustin, Megan K; Koeman, Elizabeth C; Simonetti, Antonio; Torrano, Zachary; Burns, Peter C

    2016-09-01

    In the event of the interception of illicit nuclear materials or detonation of a nuclear device, timely and accurate deciphering of the chemical and isotopic composition of pertinent samples is pivotal in enhancing both nuclear security and source attribution. This study reports the results from a first time (to our knowledge), detailed comparative investigation conducted of Trinitite post-detonation materials using both solution mode (SM) and laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS) techniques. Trace element abundances determined for bulk Trinitite samples subsequent to digestion and preparation for SM-ICP-MS analysis compare favorably to calculated median concentrations based on LA-ICP-MS analyses for the identical samples. The trace element concentrations obtained by individual LA-ICP-MS analyses indicate a large scatter compared to the corresponding bulk sample SM-ICP-MS results for the same sample; this feature can be attributed to the incorporation into the blast melt of specific, precursor accessory minerals (minerals in small quantities, such as carbonates, sulfates, chlorites, clay, and mafic minerals) present at ground zero. The favorable comparison reported here validates and confirms the use of the LA-ICP-MS technique in obtaining accurate forensic information at high spatial resolution in nuclear materials for source attribution purposes. This investigation also reports device-like (240)Pu/(239)Pu ratios (∼0.022) for Pu-rich regions of the blast melt that are also characterized by higher Ca and U contents, which is consistent with results from previous studies. © The Author(s) 2016.

  8. A dipole-assisted solid-phase extraction microchip combined with inductively coupled plasma-mass spectrometry for online determination of trace heavy metals in natural water.

    Science.gov (United States)

    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.

  9. 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.

    Science.gov (United States)

    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).

  10. Quantitative characterization of gold nanoparticles by field-flow fractionation coupled online with light scattering detection and inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Schmidt, Bjørn; Loeschner, Katrin; Hadrup, Niels; Mortensen, Alicja; Sloth, Jens J; Koch, Christian Bender; Larsen, Erik H

    2011-04-01

    An analytical platform coupling asymmetric flow field-flow fractionation (AF(4)) with multiangle light scattering (MALS), dynamic light scattering (DLS), and inductively coupled plasma mass spectrometry (ICPMS) was established and used for separation and quantitative determination of size and mass concentration of nanoparticles (NPs) in aqueous suspension. Mixtures of three polystyrene (PS) NPs between 20 and 100 nm in diameter and mixtures of three gold (Au) NPs between 10 and 60 nm in diameter were separated by AF(4). The geometric diameters of the separated PS NPs and the hydrodynamic diameters of the Au and PS NPs were determined online by MALS and DLS, respectively. The three separated Au NPs were quantified by ICPMS and recovered at 50-95% of the injected masses, which ranged between approximately 8-80 ng of each nanoparticle size. Au NPs adhering to the membrane in the separation channel was found to be a major cause for incomplete recoveries. The lower limit of detection (LOD) ranged between 0.02 ng Au and 0.4 ng Au, with increasing LOD by increasing nanoparticle diameter. The analytical platform was applied to characterization of Au NPs in livers of rats, which were dosed with 10 nm, 60 nm, or a mixture of 10 and 60 nm nanoparticles by intravenous injection. The homogenized livers were solubilized in tetramethylammonium hydroxide (TMAH), and the recovery of Au NPs from the livers amounted to 86-123% of their total Au content. In spite of successful stabilization with bovine serum albumin even in alkaline medium, separation of the Au NPs by AF(4) was not possible due to association with undissolved remains of the alkali-treated liver tissues as demonstrated by electron microscopy images.

  11. Speciation analysis of arsenic in prenatal and children's dietary supplements using microwave-enhanced extraction and ion chromatography-inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xing; Chen, Beibei; He, Man; Zhang, Yiwen; Xiao, Guangyang; Hu, Bin, E-mail: binhu@whu.edu.cn

    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{sup −1} and 0.054 μg L{sup −1} with the relative standard deviations (RSDs, n = 7, c = 5 μg L{sup −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{sup −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. - Highlights: • 4-Mercaptophenylboronic acid functionalized magnetic beads were prepared and characterized. • ICP-MS based magnetic immunoassay approach was developed for quantification of glycoproteins. • AFP and CEA were quantified simultaneously with Au and Ag NPs as element tags. • The developed method exhibited good selectivity and sensitivity for target glycoproteins.

  13. Determination of rare earth elements in seawater by inductively coupled plasma mass spectrometry with off-line column preconcentration using 2,6-diacetylpyridine functionalized Amberlite XAD-4.

    Science.gov (United States)

    Karadaş, Cennet; Kara, Derya; Fisher, Andrew

    2011-03-18

    An off-line column preconcentration technique using a micro-column of 2,6 diacetylpyridine functionalized Amberlite XAD-4 with inductively coupled plasma mass spectrometry (ICP-MS) as a means of detection has been developed. The aim of the method was to determine rare earth elements (REEs) (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) in seawater. Sample solutions (2-10 mL) were passed through the column which was then washed with ultra-pure water to remove residual matrix. The adsorbed cations on the resin were eluted by using 2 mL of 0.1 mol L(-1) HNO(3) containing 10 ng mL(-1) indium as an internal standard. The eluent was analyzed for the metal concentrations using ICP-MS. Sample pH as well as the sample and eluent flow rates were optimized. The sorption capacity of resin was determined by the batch process, by equilibrating 0.05 g of the resin with solutions of 50 mL of 25 mg L(-1) of individual metal ions for 4h at pH 6.0 at 26°C. The sorption capacities for the resin were found to range between 47.3 μmol g(-1) (for Lu) and 136.7 μmol g(-1) (for Gd). Limits of detection (3σ), without any preconcentration, ranged from 2 ng L(-1) to 10.3 ng L(-1) (for Tm and Lu respectively). The proposed method was applied to the determination of REEs in seawater and tap water samples.

  14. Multielemental fractionation in pine nuts (Pinus pinea) from different geographic origins by size-exclusion chromatography with UV and inductively coupled plasma mass spectrometry detection.

    Science.gov (United States)

    Gómez-Ariza, J L; Arias-Borrego, A; García-Barrera, T

    2006-07-21

    Pine nuts (Pinus pinea) from different geographical origin in Spain and Portugal have been investigated concerning total element content and metal-biomolecules size distribution patterns Mn, Zn, Ni and Cu. All the studied metals were at the highest concentration in pine nuts from Faro and at the lowest from Cataluña. The most abundant element in samples was Mn at concentrations in the range of 26 microg g(-1) (Cataluña) to 559 microg g(-1) (Faro). Zn was also present at high concentration in samples, from 25 microg g(-1) (Cataluña) to 113 microg g(-1) (Faro). To a deeper insight to obtain classification rules for samples, pine nuts were analyzed by size-exclusion chromatography (SEC) with UV detection and inductively coupled plasma mass spectrometry (ICP-MS). Two columns were used covering the molecular weigh range from pine nuts from Huelva. This column allows good discrimination in the range of 2126-1352 Da in which a lot of peaks can be used to differentiate samples. The UV profiles obtained with the high molecular weight (HMW) column allows a poorer differentiation of samples, but pine nuts from Huelva, Castilla and Madrid are clearly distinguished to the others. In relation to fractionation patterns of metals, Mn allows a good discrimination between samples (LMW column), Cu was the only one associated to fractions at MW > 70 kDa in sample from Cádiz, and profiles of Ni and Zn are clearly different in terms of abundance of peaks. All these chromatographic profiles for elements give valuable information about the geographical origin of the studied samples and the differences found are discussed in this work.

  15. Using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to characterize copper, zinc and mercury along grizzly bear hair providing estimate of diet.

    Science.gov (United States)

    Noël, Marie; Christensen, Jennie R; Spence, Jody; Robbins, Charles T

    2015-10-01

    We enhanced an existing technique, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to function as a non-lethal tool in the temporal characterization of trace element exposure in wild mammals. Mercury (Hg), copper (Cu), cadmium (Cd), lead (Pb), iron (Fe) and zinc (Zn) were analyzed along the hair of captive and wild grizzly bears (Ursus arctos horribilis). Laser parameters were optimized (consecutive 2000 μm line scans along the middle line of the hair at a speed of 50 μm/s; spot size=30 μm) for consistent ablation of the hair. A pressed pellet of reference material DOLT-2 and sulfur were used as external and internal standards, respectively. Our newly adapted method passed the quality control tests with strong correlations between trace element concentrations obtained using LA-ICP-MS and those obtained with regular solution-ICP-MS (r(2)=0.92, 0.98, 0.63, 0.57, 0.99 and 0.90 for Hg, Fe, Cu, Zn, Cd and Pb, respectively). Cross-correlation analyses revealed good reproducibility between trace element patterns obtained from hair collected from the same bear. One exception was Cd for which external contamination was observed resulting in poor reproducibility. In order to validate the method, we used LA-ICP-MS on the hair of five captive grizzly bears fed known and varying amounts of cutthroat trout over a period of 33 days. Trace element patterns along the hair revealed strong Hg, Cu and Zn signals coinciding with fish consumption. Accordingly, significant correlations between Hg, Cu, and Zn in the hair and Hg, Cu, and Zn intake were evident and we were able to develop accumulation models for each of these elements. While the use of LA-ICP-MS for the monitoring of trace elements in wildlife is in its infancy, this study highlights the robustness and applicability of this newly adapted method.

  16. Measurement of the isotopic composition of uranium micrometer-size particles by femtosecond laser ablation-inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Hubert, Amélie, E-mail: amelie.hubert@cea.fr [CEA, DAM, DIF, F-91297 Arpajon (France); Claverie, Fanny [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, UMR 5254, Hélioparc Pau-Pyrénées, 2 Avenue du Président Angot, 64053 Pau (France); Novalase SA, ZI de la Briqueterie, 6 Impasse du Bois de la Grange, 33610 Canejan (France); Pécheyran, Christophe [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement, UMR 5254, Hélioparc Pau-Pyrénées, 2 Avenue du Président Angot, 64053 Pau (France); Pointurier, Fabien [CEA, DAM, DIF, F-91297 Arpajon (France)

    2014-03-01

    In this paper, we will describe and indicate the performance of a new method based on the use of femtosecond laser ablation (fs-LA) coupled to a quadrupole-based inductively coupled plasma mass spectrometer (ICP-QMS) for analyzing the isotopic composition of micrometer-size uranium particles. The fs-LA device was equipped with a high frequency source (till 10 kHz). We applied this method to 1–2 μm diameter-uranium particles of known isotopic composition and we compared this technique with the two techniques currently used for uranium particle analysis: Secondary Ionization Mass Spectrometry (SIMS) and Fission Track Thermal Ionization Mass Spectrometry (FT-TIMS). By optimizing the experimental conditions, we achieved typical accuracy and reproducibility below 4% on {sup 235}U/{sup 238}U for short transient signals of only 15 s related to 10 to 200 pg of uranium. The detection limit (at the 3 sigma level) was ∼ 350 ag for the {sup 235}U isotope, meaning that {sup 235}U/{sup 238}U isotope ratios in natural uranium particles of ∼ 220 nm diameter can be measured. We also showed that the local contamination resulting from the side deposition of ablation debris at ∼ 100 μm from the ablation crater represented only a small percentage of the initial uranium signal of the ablated particle. Despite the use of single collector ICP-MS, we were able to demonstrate that fs-LA-ICP-MS is a promising alternative technique for determining uranium isotopic composition in particle analysis. - Highlights: • An infrared femtosecond laser ablation device coupled to an ICP-MS is used. • The isotopic composition of micrometer-size U particles is measured. • Results are in good agreement with the ones obtained by other relevant techniques. • Detection limit is 350 attograms for the {sup 235}U isotope • {sup 235}U/{sup 238}U ratios can be measured in 220 nm diameter natural uranium particles.

  17. Determination of uranium isotopic composition and {sup 236}U content of soil samples and hot particles using inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, S.F. [Radiation Physics and Chemistry Problems Inst., Minsk (Belarus); Becker, J.S. [Central Department for Analytical Chemistry, Research Centre Juelich (Germany)

    2001-07-01

    As a result of the accident at the Chernobyl nuclear power plant (NPP) the environment was contaminated with spent nuclear fuel. The {sup 236}U isotope was used in this study to monitor the spent uranium from nuclear fallout in soil samples collected in the vicinity of the Chernobyl NPP. Nuclear track radiography was applied for the identification and extraction of hot radioactive particles from soil samples. A rapid and sensitive analytical procedure was developed for uranium isotopic ratio measurement in environmental samples based on double-focusing inductively coupled plasma mass spectrometry (DF-ICP-MS) with a MicroMist nebulizer and a direct injection high-efficiency nebulizer (DIHEN). The performance of the DF-ICP-MS with a quartz DIHEN and plasma shielded torch was studied. Overall detection efficiencies of 4 x 10{sup -4} and 10{sup -3} counts per atom were achieved for {sup 238}U in DF-ICP-QMS with the MicroMist nebulizer and DIHEN, respectively. The rate of formation of uranium hydride ions UH{sup +}/U{sup +} was 1.2 x 10{sup -4} and 1.4 x 10{sup -4}, respectively. The precision of short-term measurements of uranium isotopic ratios (n = 5) in 1 {mu}g L{sup -1} NBS U-020 standard solution was 0.11% ({sup 238}U/{sup 235}U) and 1.4% ({sup 236}U/{sup 238}U) using a MicroMist nebulizer and 0.25% ({sup 235}U/{sup 238}U) and 1.9% ({sup 236}U/{sup 238}U) using a DIHEN. The isotopic composition of all investigated Chernobyl soil samples differed from those of natural uranium; i.e. in these samples the {sup 236}U/{sup 238}U ratio ranged from 10{sup -5} to 10{sup -3}. Results obtained with ICP-MS, {alpha}- and {gamma}-spectrometry showed differences in the migration properties of spent uranium, plutonium, and americium. The isotopic ratio of uranium was also measured in hot particles extracted from soil samples. (orig.)

  18. Analysis of metal-binding proteins separated by non-denaturating gel electrophoresis using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    Science.gov (United States)

    Becker, J Susanne; Mounicou, Sandra; Zoriy, Miroslav V; Becker, J Sabine; Lobinski, Ryszard

    2008-09-15

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have become established as very efficient and sensitive biopolymer and elemental mass spectrometric techniques for studying metal-binding proteins (metalloproteins) in life sciences. Protein complexes present in rat tissues (liver and kidney) were separated in their native state in the first dimension by blue native gel electrophoresis (BN-PAGE). Essential and toxic metals, such as zinc, copper, iron, nickel, chromium, cadmium and lead, were detected by scanning the gel bands using quadrupole LA-ICP-MS with and without collision cell as a microanalytical technique. Several proteins were identified by using MALDI-TOF-MS together with a database search. For example, on one protein band cut from the BN-PAGE gel and digested with the enzyme trypsin, two different proteins - protein FAM44B and cathepsin B precursor - were identified. By combining biomolecular and elemental mass spectrometry, it was possible to characterize and identify selected metal-binding rat liver and kidney tissue proteins.

  19. Stability Performance of Inductively Coupled Plasma Mass Spectrometry-Phenotyped Kernel Minerals Concentration and Grain Yield in Maize in Different Agro-Climatic Zones.

    Science.gov (United States)

    Mallikarjuna, Mallana Gowdra; Thirunavukkarasu, Nepolean; Hossain, Firoz; Bhat, Jayant S; Jha, Shailendra K; Rathore, Abhishek; Agrawal, Pawan Kumar; Pattanayak, Arunava; Reddy, Sokka S; Gularia, Satish Kumar; Singh, Anju Mahendru; Manjaiah, Kanchikeri Math; Gupta, Hari Shanker

    2015-01-01

    Deficiency of iron and zinc causes micronutrient malnutrition or hidden hunger, which severely affects ~25% of global population. Genetic biofortification of maize has emerged as cost effective and sustainable approach in addressing malnourishment of iron and zinc deficiency. Therefore, understanding the genetic variation and stability of kernel micronutrients and grain yield of the maize inbreds is a prerequisite in breeding micronutrient-rich high yielding hybrids to alleviate micronutrient malnutrition. We report here, the genetic variability and stability of the kernel micronutrients concentration and grain yield in a set of 50 maize inbred panel selected from the national and the international centres that were raised at six different maize growing regions of India. Phenotyping of kernels using inductively coupled plasma mass spectrometry (ICP-MS) revealed considerable variability for kernel minerals concentration (iron: 18.88 to 47.65 mg kg(-1); zinc: 5.41 to 30.85 mg kg(-1); manganese: 3.30 to 17.73 mg kg(-1); copper: 0.53 to 5.48 mg kg(-1)) and grain yield (826.6 to 5413 kg ha(-1)). Significant positive correlation was observed between kernel iron and zinc within (r = 0.37 to r = 0.52, p kernel minerals concentration and grain yield. Most of the variation was contributed by genotype main effect for kernel iron (39.6%), manganese (41.34%) and copper (41.12%), and environment main effects for both kernel zinc (40.5%) and grain yield (37.0%). Genotype main effect plus genotype-by-environment interaction (GGE) biplot identified several mega environments for kernel minerals and grain yield. Comparison of stability parameters revealed AMMI stability value (ASV) as the better representative of the AMMI stability parameters. Dynamic stability parameter GGE distance (GGED) showed strong and positive correlation with both mean kernel concentrations and grain yield. Inbreds (CM-501, SKV-775, HUZM-185) identified from the present investigation will be useful in

  20. Analytical evaluation of nebulizers for the introduction of acetic acid extracts aiming at the determination of trace elements by inductively coupled plasma mass spectrometry

    Science.gov (United States)

    de Gois, Jefferson S.; Maranhão, Tatiane de A.; Oliveira, Fernando J. S.; Frescura, Vera L. A.; Curtius, Adilson J.; Borges, Daniel L. G.

    2012-11-01

    Most of the official procedures aiming at classification of solid waste toxicity take into account metal solubility and bioavailability by means of extraction experiments using acetic acid solutions. Hence, the aim of this work was to investigate and optimize conditions to suppress the effect of acetic acid on the determination of trace elements using inductively coupled plasma mass spectrometry. The performance of four nebulizers (cross-flow (CFN), ultrasonic (USN), Meinhard (MN) and MicroMist (MMN)) were compared as to their efficiency in minimizing spectral and non-spectral effects on the determination of Ag, As, Ba, Cd, Cr, Hg, Pb and Se, with the ultimate goal to analyze acetic acid extracts obtained from solid waste residues. Operating conditions (desolvation temperatures for USN, RF power and nebulizer gas flow rates) were optimized individually for each nebulizer and for all analytes maintained in 0.14 mol L- 1 HNO3 solutions and in solutions prepared with acetic acid and acetic acid + NaOH, adjusted to pH 2.88 and 4.93, respectively. Pronounced non-spectral interferences for 75As and 82Se were observed in the presence of acetic acid for CF and MN, although to a less extent also for MMN and USN. Signal increase for blank solutions measured at m/z 208 (208Pb) for CFN and MN, 107 (107Ag) for USN and MN coupled to a cyclonic chamber and, m/z 82 (82Se) for USN was observed, indicating an increased risk of spectral interference upon an increase in the concentration of acetic acid. Signal increase at specific m/z ratios, however, was not significant when the MMN was used, with the exception of m/z 52 (52Cr) in acetic acid solutions, arising from the formation of 40Ar12C+. This same effect was noticed for all nebulizers, although at noticeably different intensities. A signal stability study was performed, demonstrating that variations in the analytical signal were within a 20% range for all analytes, with the exception of Hg, after continuous aspiration for 70 min

  1. Determination of As, Cd, Pb, and Hg in urine using inductively coupled plasma mass spectrometry with the direct injection high efficiency nebulizer

    Science.gov (United States)

    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

  2. Using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to characterize copper, zinc and mercury along grizzly bear hair providing estimate of diet

    Energy Technology Data Exchange (ETDEWEB)

    Noël, Marie, E-mail: marie.noel@stantec.com [Stantec Consulting Ltd. 2042 Mills Road, Unit 11, Sidney BC V8L 4X2 (Canada); Christensen, Jennie R., E-mail: jennie.christensen@stantec.com [Stantec Consulting Ltd. 2042 Mills Road, Unit 11, Sidney BC V8L 4X2 (Canada); Spence, Jody, E-mail: jodys@uvic.ca [School of Earth and Ocean Sciences, Bob Wright Centre A405, University of Victoria, PO BOX 3065 STN CSC, Victoria, BC V8W 3V6 (Canada); Robbins, Charles T., E-mail: ctrobbins@wsu.edu [School of the Environment and School of Biological Sciences, Washington State University, Pullman, WA 99164-4236 (United States)

    2015-10-01

    We enhanced an existing technique, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to function as a non-lethal tool in the temporal characterization of trace element exposure in wild mammals. Mercury (Hg), copper (Cu), cadmium (Cd), lead (Pb), iron (Fe) and zinc (Zn) were analyzed along the hair of captive and wild grizzly bears (Ursus arctos horribilis). Laser parameters were optimized (consecutive 2000 μm line scans along the middle line of the hair at a speed of 50 μm/s; spot size = 30 μm) for consistent ablation of the hair. A pressed pellet of reference material DOLT-2 and sulfur were used as external and internal standards, respectively. Our newly adapted method passed the quality control tests with strong correlations between trace element concentrations obtained using LA-ICP-MS and those obtained with regular solution-ICP-MS (r{sup 2} = 0.92, 0.98, 0.63, 0.57, 0.99 and 0.90 for Hg, Fe, Cu, Zn, Cd and Pb, respectively). Cross-correlation analyses revealed good reproducibility between trace element patterns obtained from hair collected from the same bear. One exception was Cd for which external contamination was observed resulting in poor reproducibility. In order to validate the method, we used LA-ICP-MS on the hair of five captive grizzly bears fed known and varying amounts of cutthroat trout over a period of 33 days. Trace element patterns along the hair revealed strong Hg, Cu and Zn signals coinciding with fish consumption. Accordingly, significant correlations between Hg, Cu, and Zn in the hair and Hg, Cu, and Zn intake were evident and we were able to develop accumulation models for each of these elements. While the use of LA-ICP-MS for the monitoring of trace elements in wildlife is in its infancy, this study highlights the robustness and applicability of this newly adapted method. - Highlights: • LA-ICP-MS provides temporal trace metal exposure information for wild grizzly bears. • Cu and Zn temporal exposures provide

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

    Energy Technology Data Exchange (ETDEWEB)

    Chainet, Fabien, E-mail: fabien.chainet@ifpen.fr [IFP Energies nouvelles, Rond-point de l' échangeur de Solaize, BP 3, 69360 Solaize (France); Lienemann, Charles-Philippe; Ponthus, Jeremie [IFP Energies nouvelles, Rond-point de l' échangeur de Solaize, BP 3, 69360 Solaize (France); Pécheyran, Christophe; Castro, Joaudimir; Tessier, Emmanuel; Donard, Olivier François Xavier [LCABIE-IPREM, UMR 5254, CNRS-UPPA, Helioparc, 2 av. Pr. Angot, 64053 Pau (France)

    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 ({sup 14}N{sup 14}N{sup +} and {sup 12}C{sup 16}O{sup +}) initially present on {sup 28}Si. 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 (D{sub 3}–D{sub 16}) 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

  4. Automated preconcentration of Fe, Zn, Cu, Ni, Cd, Pb, Co, and Mn in seawater with analysis using high-resolution sector field inductively-coupled plasma mass spectrometry.

    Science.gov (United States)

    Rapp, Insa; Schlosser, Christian; Rusiecka, Dagmara; Gledhill, Martha; Achterberg, Eric P

    2017-07-11

    A rapid, automated, high-throughput analytical method capable of simultaneous analysis of multiple elements at trace and ultratrace levels is required to investigate the biogeochemical cycle of trace metals in the ocean. Here we present an analytical approach which uses a commercially available automated preconcentration device (SeaFAST) with accurate volume loading and in-line pH buffering of the sample prior to loading onto a chelating resin (WAKO) and subsequent simultaneous analysis of iron (Fe), zinc (Zn), copper (Cu), nickel (Ni), cadmium (Cd), lead (Pb), cobalt (Co) and manganese (Mn) by high-resolution inductively-coupled plasma mass spectrometry (HR-ICP-MS). Quantification of sample concentration was undertaken using isotope dilution for Fe, Zn, Cu, Ni, Cd and Pb, and standard addition for Co and Mn. The chelating resin is shown to have a high affinity for all analyzed elements, with recoveries between 83 and 100% for all elements, except Mn (60%) and Ni (48%), and showed higher recoveries for Ni, Cd, Pb, Co and Mn in direct comparison to an alternative resin (NOBIAS Chelate-PA1). The reduced recoveries for Ni and Mn using the WAKO resin did not affect the quantification accuracy. A relatively constant retention efficiency on the resin over a broad pH range (pH 5-8) was observed for the trace metals, except for Mn. Mn quantification using standard addition required accurate sample pH adjustment with optimal recoveries at pH 7.5 ± 0.3. UV digestion was necessary to increase recovery of Co and Cu in seawater by 15.6% and 11.4%, respectively, and achieved full break-down of spiked Co-containing vitamin B12 complexes. Low blank levels and detection limits could be achieved (e.g., 0.029 nmol L(-1) for Fe and 0.028 nmol L(-1) for Zn) with the use of high purity reagents. Precision and accuracy were assessed using SAFe S, D1, and D2 reference seawaters, and results were in good agreement with available consensus values. The presented method is ideal for

  5. 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

    Energy Technology Data Exchange (ETDEWEB)

    Praphairaksit, Narong [Iowa State Univ., Ames, IA (United States)

    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 ~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 ~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 of signal for even the most

  6. Quantitative analysis of major and trace elements in NH4HF2-modified silicate rock powders by laser ablation - inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Zhang, Wen; Hu, Zhaochu; Liu, Yongsheng; Yang, Wenwu; Chen, Haihong; Hu, Shenghong; Xiao, Hongyan

    2017-08-29

    In this paper, we described a NH4HF2 digestion method as sample preparation for the rapid determination of major and trace elements in silicate rocks using laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). Sample powders digested by NH4HF2 at 230 °C for 3 h form ultrafine powders with a typical grain size d80 rocks have a consistent grain morphology and size, allowing us to produce pressed powder pellets that have excellent cohesion and homogeneity suitable for laser ablation micro-analysis without the addition of binder. The influences of the digestion parameters were investigated and optimized, including the evaporation stage of removing residual NH4HF2, sample homogenization, selection of the digestion vessel and calibration strategy of quantitative analysis. The optimized NH4HF2 digestion method was applied to dissolve six silicate rock reference materials (BCR-2, BHVO-2, AGV-2, RGM-2, GSP-2, GSR-1) covering a wide range of rock types. Ten major elements and thirty-five trace elements were simultaneously analyzed by LA-ICP-MS. The analytical results of the six reference materials generally agreed with the recommended values, with discrepancies of less than 10% for most elements. The analytical precision is within 5% for most major elements and within 10% for most trace elements. Compared with previous methods of LA-ICP-MS bulk analysis, our method enables the complete dissolution of refractory minerals, such as zircon, in intermediate-acidic intrusive rocks and limits contamination as well as the loss of volatile elements. Moreover, there are many advantages for the new technique, including reducing matrix effects between reference materials and samples, spiking the internal standard simply and feasibly and sample batch processing. The applicability filed of the new technique in this study was focused on the whole-rock analysis of igneous rock samples, which are from basic rocks to acid rocks (45% rock analysis. Copyright © 2017

  7. Online analysis of europium and gadolinium species complexed or uncomplexed with humic acid by capillary electrophoresis-inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Kautenburger, Ralf; Nowotka, Karsten; Beck, Horst Philipp

    2006-03-01

    Detailed information on the geochemical behavior of radioactive and toxic metal ions under environmental conditions (in geological matrices and aquifer systems) is needed in order to assess the long-term safety of waste repositories. This includes knowledge of the mechanisms of relevant geochemical reactions, as well as associated thermodynamic and kinetic data. Several previous studies have shown that humic acid can play an important role in the immobilization or mobilization of metal ions due to complexation and colloid formation. In our project we investigate the complexation behavior of (purified Aldrich) humic acid and its influence on the migration of the lanthanides europium and gadolinium (homologs of the actinides americium and curium) in the ternary system consisting of these heavy metals, humic acid and kaolinite (KGa-1b) under almost natural conditions. Capillary electrophoresis (CE, Beckman Coulter P/ACE MDQ), with its excellent separation performance, was hyphenated with a homemade interface to inductively coupled plasma mass spectrometry (ICP-MS, VG Elemental PlasmaQuad 3) giving a system that is highly sensitive to the rare-earth element species of europium and gadolinium with humic acid. The humic acid used was also halogenated with iodine, which acted as an ICP-MS marker. To couple CE to ICP-MS, a fused silica CE capillary was flexibly fitted into a MicroMist 50 mul nebulizer with a Cinnabar cyclonic spray chamber in the external homemade interface. The chamber was chilled to a temperature of 4 degrees C to optimize the sensitivity. 200 ppb of cesium were added to the CE separation buffer so that the capillary flow could be observed. A make-up fluid including 4 ppb Ho as an internal standard was combined with the flow from the capillary within the interface in order to get a fluid throughput high enough to maintain continuous nebulization. Very low detection limits were achieved: 125 ppt for 153Eu and 250 ppt for 158Gd. Using this optimized CE

  8. Determination of Cd, Hg, Pb and Tl in coal and coal fly ash slurries using electrothermal vaporization inductively coupled plasma mass spectrometry and isotopic dilution

    Energy Technology Data Exchange (ETDEWEB)

    Maia, S.M.; Pozebon, D.; Curtius, A.J. [Univ. Federal de Santa Catarina, Florianopolis, SC (Brazil)

    2003-07-01

    A method has been investigated for the determination of Cd, Hg, Pb and Tl in coal and in coal fly ash, using slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry and isotope dilution. The slurry, 25 mg ml{sup -1}, was prepared by mixing the powdered sample (less than or equal to 36 - 45 mm) with acid solutions (nitric acid for coal and nitric and hydrofluoric acids for coal fly ash) and submitting the mixture to an ultrasonic agitation, letting it stand afterwards in a water bath at 60{sup o}C for 2 h. An ultrasonic probe was used to homogenize the slurry in the autosampler cup just before its introduction into the graphite tube. The best conditions were determined regarding analyte sensitivity, furnace temperature program, amount of modifier, acid concentration, gas flow rate and particle size. For Hg, the pyrolysis stage was omitted and a low vaporization temperature was used (450 - 1000{sup o}C); the residual matrix was eliminated in the first step of the following cycle. The modifiers used were: Pd for Cd and Tl; Au, Ir or Pd for Hg; Ir or Pd for Pb. The accuracy of the method was checked by analyzing six certified coal reference materials (SARM 20, SARM 19, BCR No. 40, BCR No. 180, BCR No. 181 and NIST 1630a) and one certified coal fly ash (NIST 1633b). With one exception (Hg in BCR No. 180), the found concentrations were typically within 95% confidence interval of the certified values, or close enough to the recommended values, as long as the samples were ground to a small enough particle size. The limits of detection were typically around 0.08 {mu}g g{sup -1}, 0.03 {mu}g g{sup -1}, 1 {mu}g g{sup -1} and 0.02 {mu}g g{sup -1} for Cd, Hg, Pb and Tl, respectively. The precision was also adequate with relative standard deviations of usually < 5%.

  9. Imaging of nutrient elements in the leaves of Elsholtzia splendens by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    Science.gov (United States)

    Wu, Bei; Zoriy, Miroslav; Chen, Yingxu; Becker, J Sabine

    2009-04-15

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of nutrient elements (such as K, Mg, Mn, Cu, P, S and B) in the leaves of Elsholtzia splendens. The plant leaves were scanned directly with a focused Nd:YAG laser in the laser ablation chamber. The ablated material was transported with argon as carrier gas to a quadrupole-based ICP-MS (ICP-QMS), and the ion intensities of (39)K(+), (24)Mg(+), (55)Mn(+), (63)Cu(+), (31)P(+), (34)S(+) and (11)B(+) were measured by ICP-QMS to study the distribution of the elements of interest. The imaging technique using LA-ICP-MS on plant leaves does not require any sample preparation. Carbon ((13)C(+)) was used as an internal standard element to compensate for the difference in the amount of material ablated. Additional experiments were performed in order to study the influence of the water content of the analyzed leaves on the intensity signal of the analyte. For quantification purposes, standard reference material (NIST SRM 1515 Apple Leaves) was selected and doped with standard solutions of the analytes within the concentration range of 0.1-2000 mg L(-1). The synthetic laboratory standards together with the samples were measured by LA-ICP-MS. The shape and structure of the leaves was clearly given by LA-ICP-MS imaging of all the elements measured. The elemental distribution varied according to the element, but with a high content in the veins for all the elements investigated. Specifically, Cu was located uniformly in the mesophyll with a slightly higher concentration in the main vein. High ion intensity was measured for S with a high amount of this element in the veins similar to the images of the metals, whereas most of the B was detected at the tip of the leaf. With synthetic laboratory standard calibration, the concentrations of elements in the leaves measured by LA-ICP-MS were between 20 microg g(-1) for Cu and 14,000 microg g(-1) for K.

  10. [Characterization of matrix effects in microanalysis of sulfide minerals by laser ablation-inductively coupled plasma-mass spectrometry based on an element pair method].

    Science.gov (United States)

    Yuan, Ji-hai; Zhan, Xiu-chun; Hu, Ming-yue; Zhao, Ling-hao; Sun, Dong-yang

    2015-02-01

    Matrix effect between reference materials and samples is one of the major factors affecting the accuracy of analytical results by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). However, there is no method or calculation formula to quantify matrix effect between standards and samples up to date. In this paper, the linear correlation coefficient r of the Ii/I(is-Ci)/Cis graphs of element pairs were used to characterize the matrix effect, which took the ratios of concentrations (ci/ c(is)) and intensities (Ii/Iis) of the analytical element and internal standard element as x-axis and gamma-axis, respectively. Matrix effects of 6 element pairs in 13 glass reference materials, 2 sulfide reference materials and 2 sulfide minerals using Fe as internal standard was studied, with the linear correlation coefficient r of Fe-Cu, Fe-Zn element pairs both less than 0. 999 and trace Fe--Mn, Fe--Co, Fe--Ga, Fe--Pb element pairs all better than 0.999. Matrix effects of 3 major element pairs in 2 sulfide ref- erence materials and 6 sulfide minerals using S as internal standard was also studied, with the linear correlation coefficient r of S--Fe, S--Cu, S--Zn all less than 0.999. The great majority of relative errors of EMPA analytical results for major elements in sulfide minerals were greater than 10%, whether analyzed using Fe as internal standard with glass reference materials as external standard, or S as internal standard with sulfide reference materials MASS-1, IMER-1 as external standard, respectively. But the most analytical results for trace elements calibrated by glass reference materials using Fe as internal standard were well agreed with sulfide standard MASS-1, with the relative errors less than 15%. The results showed that matrix effects existed in glass reference materials, sulfide reference materials and sulfide minerals, and it also proved a certain rationality and practicability for quantification of matrix effect using the linear

  11. Biomonitoring of essential and toxic metals in single hair using on-line solution-based calibration in laser ablation inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Dressler, Valderi L; Pozebon, Dirce; Mesko, Marcia Foster; Matusch, Andreas; Kumtabtim, Usarat; Wu, B; Sabine Becker, J

    2010-10-15

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a powerful and sensitive surface analytical technique for the determination of concentration and distribution of trace metals within biological systems at micrometer spatial resolution. LA-ICP-MS allows easy quantification procedures if suitable standard references materials (SRM) are available. In this work a new SRM-free approach of solution-based calibration method in LA-ICP-MS for element quantification in hair is described. A dual argon flow of the carrier gas and nebulizer gas is used. A dry aerosol produced by laser ablation (LA) of biological sample and a desolvated aerosol generated by pneumatic nebulization (PN) of standard solutions are carried by two different flows of argon as carrier or nebulizer gas, respectively and introduced separately in the injector tube of a special ICP torch, through two separated apertures. Both argon flows are mixed directly in the ICP torch. External calibration via defined standard solutions before analysis of single hair was employed as calibration strategy. A correction factor, calculated using hair with known analyte concentration (measured by ICP-MS), is applied to correct the different elemental sensitivities of ICP-MS and LA-ICP-MS. Calibration curves are obtained by plotting the ratio of analyte ion M(+)/(34)S(+) ion intensities measured using LA-ICP-MS in dependence of analyte concentration in calibration solutions. Matrix-matched on-line calibration in LA-ICP-MS is carried out by ablating of human hair strands (mounted on a sticky tape in the LA chamber) using a focused laser beam in parallel with conventional nebulization of calibration solutions. Calibrations curves of Li, Na, Mg, Al, K, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Mo, Ag, Cd, I, Hg, Pb, Tl, Bi and U are presented. The linear correlation coefficients (R) of calibration curves for analytes were typically between 0.97 and 0.999. The limits of detection (LODs) of

  12. 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

    Energy Technology Data Exchange (ETDEWEB)

    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

  13. Asymmetrical flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry for sizing SeNPs for packaging applications

    Science.gov (United States)

    Palomo-Siguero, María; Vera, Paula; Echegoyen, Yolanda; Nerin, Cristina; Cámara, Carmen; Madrid, Yolanda

    2017-06-01

    This paper describes the application of Asymmetrical Flow Field-Flow Fractionation (AF4) coupled to diode array detector (DAD) and inductively coupled plasma mass spectrometry (AF4-UV-ICP-MS) to characterize selenium nanoparticles (SeNPs) in an aqueous acrylic adhesive to be used in a multilayer food packaging material. SeNPs were synthesized using a solution-phase approach based on the reduction of selenite with ascorbic acid in presence of different stabilizers compatible with food industry such as polysaccharides (chitosan (poly(D-glucosamine) and hydroxyethylcellulose (HEC)) and non-ionic surfactants (Triton X-100 (t-octylphenoxypolyethoxyethanol), 2,4,7,9-tetramethyl 5decyne-4,7-diol ethoxylate, and isotridecanol ethoxylate). Several parameters such as pH, ascorbic acid and stabilizers concentration, and compatibility of the stabilizer with the adhesive were evaluated. SeNPs suspensions with spherical morphology were obtained except when isotridecanol ethoxylate was employed which provides SeNPs with a nanorod morphology. AF4-DAD-ICP-MS was further applied for sizing the different SeNPs preparations. DAD was used as detector for selecting the best AF4 separation conditions before coupling to ICP-MS to ensure unequivocal identification of NPs. AF4 calibration with polystyrene latex (PSL) beads of known sizes allowed size determination of the different SeNPs. The following estimated hydrodynamic sizes (expressed as the mean ± standard deviation, n = 6 replicates) were found: chitosan-SeNPs- (26 ± 3 nm), TritonX100-SeNPs (22 ± 10 nm) HEC- SeNPs (91 ± 8 nm) and 2,4,7,9-tetramethyl 5decyne-4,7-diol ethoxylate- SeNPs (59 ± 4 nm). The proposed methodology was successfully applied to the characterization in terms of size of aqueous acrylic adhesives containing SeNPs Results from AF4-ICP-MS and TEM shown that only those SeNPs obtained with non-ionic surfactants and HEC were compatible with the adhesive. The results reported here evidence the usefulness of AF4-ICP

  14. Comparison of extraction procedures for the determination of arsenic and other elements in lobster tissue by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Brisbin, Judith A; Caruso, Joseph A

    2002-07-01

    A variety of extraction procedures were evaluated for the extraction of arsenic and other analytes from lobster tissue samples using inductively coupled plasma mass spectrometry (ICP-MS) detection. Soxhlet, room temperature mixing, sonication, microwave assisted, supercritical carbon dioxide and subcritical water extractions were evaluated for a variety of solvent systems and optimum conditions determined using a partially defatted Lobster Hepatopancreas marine certified reference material, TORT-2 (National Research Council of Canada). The solubility trends and solvents into which the analytes extracted gave an indication as to the polar/non-polar nature of the compounds present. Analytes that prefer water are probably more polar or inorganic, while those preferring methanol solutions are less polar or organic in nature. Arsenic, cadmium, cobalt, molybdenum and selenium were probably all present in TORT-2 in both polar inorganic and non-polar organic forms. While TORT-2 may have contained similar amounts of selenium in both forms, the results suggested that more of the arsenic was present as less polar or more organic compounds, and cobalt existed mainly as more polar or inorganic species. Most of the extraction techniques suggested that, although there may be some less polar organic forms present, more of the cadmium was probably present as polar inorganic compounds. Additionally, most techniques indicated that molybdenum was possibly all less polar or more organic in nature. In general, microwave assisted extraction (MAE) yielded comparable or improved recoveries for all of the analytes monitored and usually required less solvent. Additionally, MAE proved to be the mildest, fastest, least complicated and most reproducible extraction technique evaluated. MAE at 75 degrees C for 2 min exposure time yielded quantitative recovery of arsenic from TORT-2. These conditions were evaluated for lobster tissue samples purchased from a local restaurant. Separate evaluation

  15. Stability Performance of Inductively Coupled Plasma Mass Spectrometry-Phenotyped Kernel Minerals Concentration and Grain Yield in Maize in Different Agro-Climatic Zones.

    Directory of Open Access Journals (Sweden)

    Mallana Gowdra Mallikarjuna

    Full Text Available Deficiency of iron and zinc causes micronutrient malnutrition or hidden hunger, which severely affects ~25% of global population. Genetic biofortification of maize has emerged as cost effective and sustainable approach in addressing malnourishment of iron and zinc deficiency. Therefore, understanding the genetic variation and stability of kernel micronutrients and grain yield of the maize inbreds is a prerequisite in breeding micronutrient-rich high yielding hybrids to alleviate micronutrient malnutrition. We report here, the genetic variability and stability of the kernel micronutrients concentration and grain yield in a set of 50 maize inbred panel selected from the national and the international centres that were raised at six different maize growing regions of India. Phenotyping of kernels using inductively coupled plasma mass spectrometry (ICP-MS revealed considerable variability for kernel minerals concentration (iron: 18.88 to 47.65 mg kg(-1; zinc: 5.41 to 30.85 mg kg(-1; manganese: 3.30 to 17.73 mg kg(-1; copper: 0.53 to 5.48 mg kg(-1 and grain yield (826.6 to 5413 kg ha(-1. Significant positive correlation was observed between kernel iron and zinc within (r = 0.37 to r = 0.52, p < 0.05 and across locations (r = 0.44, p < 0.01. Variance components of the additive main effects and multiplicative interactions (AMMI model showed significant genotype and genotype × environment interaction for kernel minerals concentration and grain yield. Most of the variation was contributed by genotype main effect for kernel iron (39.6%, manganese (41.34% and copper (41.12%, and environment main effects for both kernel zinc (40.5% and grain yield (37.0%. Genotype main effect plus genotype-by-environment interaction (GGE biplot identified several mega environments for kernel minerals and grain yield. Comparison of stability parameters revealed AMMI stability value (ASV as the better representative of the AMMI stability parameters. Dynamic stability

  16. Spectrometer system using a modular echelle spectrograph and a laser-driven continuum source for simultaneous multi-element determination by graphite furnace absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Geisler, Sebastian; Okruss, Michael; Becker-Ross, Helmut; Huang, Mao Dong, E-mail: huang@isas.de; Esser, Norbert; Florek, Stefan

    2015-05-01

    A multi-element absorption spectrometer system has been developed based on a laser-driven xenon continuum source and a modular simultaneous echelle spectrograph (MOSES), which is characterized by a minimized number of optical components resulting in high optical throughput, high transmittance and high image quality. The main feature of the new optical design is the multifunction usage of a Littrow prism, which is attached on a rotation stage. It operates as an order-sorter for the echelle grating in a double-pass mode, as a fine positioning device moving the echelle spectrum on the detector, and as a forwarder to address different optical components, e.g., echelle gratings, in the setup. Using different prisms, which are mounted back to back on the rotation stage, a multitude of different spectroscopic modes like broad-range panorama observations, specific UV–VIS and NIR studies or high resolution zoom investigations of variable spectral channels can be realized. In the UV panorama mode applied in this work, MOSES has simultaneously detectable wavelength coverage from 193 nm to 390 nm with a spectral resolution λ/Δλ of 55,000 (3-pixel criterion). In the zoom mode the latter can be further increased by a factor of about two for a selectable section of the full wavelength range. The applicability and the analytical performance of the system were tested by simultaneous element determination in a graphite furnace, using eight different elements. Compared to an instrument operating in the optimized single line mode, the achieved analytical sensitivity using the panorama mode was typically a factor of two lower. Using the zoom mode for selected elements, comparable sensitivities were obtained. The results confirm the influence of the different spectral resolutions. - Highlights: • Echelle spectrometer with a full frame CCD array detector • High and variable spectral resolution from λ/Δλ of 55,000 to 95,000 • Laser-driven continuum light source

  17. Multi-Element Composition of Honey as a Suitable Tool for Its Authenticity Analysis

    Directory of Open Access Journals (Sweden)

    Oroian Mircea

    2015-06-01

    Full Text Available The aim of this study was to evaluate the composition of 36 honey samples of 4 different botanical origins (acacia, sun flower, tilia and honeydew from the North East region of Romania. An inductively coupled plasma-mass spectrometry (ICP-MS method was used to determine 27 elements in honey (Ag, Al, As, Ba, Be, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ga, K, Li, Mg, Mn, Na, Ni, Pb, Rb, Se, Sr, Tl, U, V and Zn. We would like to achieve the following goal: to demonstrate that the qualitative and quantitative multi-element composition determination of honey can be used as a suitable tool to classify honey according to its botanical origin. The principal component analysis allowed the reduction of the 27 variables to 2 principal components which explained 74% of the total variance. The dominant elements which were strongly associated with the principal component were K, Mg and Ca. Discriminant models obtained for each kind of botanical honey confirmed that the differentiation of honeys according to their botanical origin was mainly based on multi-element composition. A correct classification of all samples was achieved with the exception of 11.1% of honeydew honeys.

  18. Assessment of the Halogen Content of Brazilian Inhalable Particulate Matter (PM10) Using High Resolution Molecular Absorption Spectrometry and Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry, with Direct Solid Sample Analysis.

    Science.gov (United States)

    de Gois, Jefferson S; Almeida, Tarcisio S; Alves, Jeferson C; Araujo, Rennan G O; Borges, Daniel L G

    2016-03-15

    Halogens in the atmosphere play an important role in climate change and also represent a potential health hazard. However, quantification of halogens is not a trivial task, and methods that require minimum sample preparation are interesting alternatives. Hence, the aim of this work was to evaluate the feasibility of direct solid sample analysis using high-resolution continuum source molecular absorption spectrometry (HR-CS MAS) for F determination and electrothermal vaporization-inductively coupled plasma mass spectrometry (ETV-ICP-MS) for simultaneous Cl, Br, and I determination in airborne inhalable particulate matter (PM10) collected in the metropolitan area of Aracaju, Sergipe, Brazil. Analysis using HR-CS MAS was accomplished by monitoring the CaF molecule, which was generated at high temperatures in the graphite furnace after the addition of Ca. Analysis using ETV-ICP-MS was carried out using Ca as chemical modifier/aerosol carrier in order to avoid losses of Cl, Br, and I during the pyrolysis step, with concomitant use of Pd as a permanent modifier. The direct analysis approach resulted in LODs that were proven adequate for halogen determination in PM10, using either standard addition calibration or calibration against a certified reference material. The method allowed the quantification of the halogens in 14 PM10 samples collected in a northeastern coastal city in Brazil. The results demonstrated variations of halogen content according to meteorological conditions, particularly related to rainfall, humidity, and sunlight irradiation.

  19. A comparison of laser ablation-inductively coupled plasma-mass spectrometry and high-resolution continuum source graphite furnace molecular absorption spectrometry for the direct determination of bromine in polymers

    Science.gov (United States)

    de Gois, Jefferson S.; Van Malderen, Stijn J. M.; Cadorim, Heloisa R.; Welz, Bernhard; Vanhaecke, Frank

    2017-06-01

    This work describes the development and comparison of two methods for the direct determination of Br in polymer samples via solid sampling, one using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and the other using high-resolution continuum source graphite furnace molecular absorption spectrometry with direct solid sample analysis (HR-CS SS-GF MAS). The methods were optimized and their accuracy was evaluated by comparing the results obtained for 6 polymeric certified reference materials (CRMs) with the corresponding certified values. For Br determination with LA-ICP-MS, the 79Br+ signal could be monitored interference-free. For Br determination via HR-CS SS-GF MAS, the CaBr molecule was monitored at 625.315 nm with integration of the central pixel ± 1. Bromine quantification by LA-ICP-MS was performed via external calibration against a single CRM while using the 12C+ signal as an internal standard. With HR-CS SS-GF MAS, Br quantification could be accomplished using external calibration against aqueous standard solutions. Except for one LA-ICP-MS result, the concentrations obtained with both techniques were in agreement with the certified values within the experimental uncertainty as evidenced using a t-test (95% confidence level). The limit of quantification was determined to be 100 μg g- 1 Br for LA-ICP-MS and 10 μg g- 1 Br for HR-CS SS-GF MAS.

  20. A novel methodology for rapid digestion of rare earth element ores and determination by microwave plasma-atomic emission spectrometry and dynamic reaction cell-inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Helmeczi, Erick; Wang, Yong; Brindle, Ian D

    2016-11-01

    Short-wavelength infrared radiation has been successfully applied to accelerate the acid digestion of refractory rare-earth ore samples. Determinations were achieved with microwave plasma-atomic emission spectrometry (MP-AES) and dynamic reaction cell - inductively coupled plasma-mass spectrometry (DRC-ICP-MS). The digestion method developed was able to tackle high iron-oxide and silicate matrices using only phosphoric acid in a time frame of only 8min, and did not require perchloric or hydrofluoric acid. Additionally, excellent recoveries and reproducibilities of the rare earth elements, as well as uranium and thorium, were achieved. Digestions of the certified reference materials OREAS-465 and REE-1, with radically different mineralogies, delivered results that mirror those obtained by fusion processes. For the rare-earth CRM OKA-2, whose REE data are provisional, experimental data for the rare-earth elements were generally higher than the provisional values, often exceeding z-values of +2. Determined values for Th and U in this reference material, for which certified values are available, were in excellent agreement. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. 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.

    Science.gov (United States)

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

    2014-01-02

    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. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. 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.

    Science.gov (United States)

    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 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.

  3. Bead Injection Extraction Chromatography using High-capacity Lab-on-Valve as a Front End to Inductively Coupled Plasma Mass Spectrometry for Rapid Urine Radiobioassay

    DEFF Research Database (Denmark)

    Qiao, Jixin; Hou, Xiaolin; Roos, Per

    2013-01-01

    A novel bead injection (BI) extraction chromatographic microflow system exploiting high-capacity lab-on-valve (LOV) platform coupled with inductively coupled plasma mass spectrometric detection is developed for rapid and automated determination of plutonium in human urine. A microconduit (1 mL) i...

  4. Influence of one- and two-dimensional gel electrophoresis procedure on metal-protein bindings examined by electrospray ionization mass spectrometry, inductively coupled plasma mass spectrometry, and ultrafiltration.

    Science.gov (United States)

    Schmidt, Anne-Christine; Störr, Bianca; Kummer, Nicolai-Alexeji

    2011-08-15

    Three independent methods, (i) electrospray ionization mass spectrometry (ESI-MS), (ii) carrying out the complete protein preparation procedure required for protein gel electrophoresis (GE) including extraction, precipitation, washing, and desalting with subsequent microwave digestion of the produced protein fractions for metal content quantification, and (iii) ultrafiltration for separating protein-bound and unbound metal fractions, were employed to elucidate the influences of protein sample preparation and GE running conditions on metal-protein bindings. A treatment of the protein solution with acetone instead of trichloroacetic acid or ammonium sulfate for precipitate formation led to a strongly enhanced metal binding capacity. The desalting step of the resolubilized protein sample caused a metal loss between 10 and 35%. The omission of some extraction buffer additives led to a diminished metal binding capacity of protein fractions obtained from the sample preparation procedure for GE, whereas a tenside addition to the protein solution inhibited metal-protein bindings. The binding stoichiometry of Cu and Zn-protein complexes determined by ESI-MS was influenced by the type of the metal salt which was applied to the protein solution. A higher pH value of the sample solution promoted the metal ion complexation by the proteins. Ultrafiltration experiments revealed a higher Cu- and Zn-binding capacity of the model protein lysozyme in both resolubilization buffers for 1D- and 2D-GE compared to the protein extraction buffer. Strongly diminished metal binding capacities of lysozyme were recorded in the running buffer of 1D-GE and in the gel staining solutions.

  5. Measurements of {beta} or {alpha} emitter long lived radionuclides using inductively coupled plasma mass spectrometry; Dosage a tres bas niveau de radionucleides a longue periode emetteurs {beta} ou {alpha} par spectrometrie de masse a couplage plasma inductif

    Energy Technology Data Exchange (ETDEWEB)

    Provitina, O.

    1993-10-18

    The measurement of long-lived radionuclides is highly important for characterizing nuclear wastes for their later storage. The main techniques are {alpha} spectrometry, {beta} counting and {gamma} spectrometry. The large period of these isotopes leads to low specific activity needing time consuming measurements. Moreover, the radiometric techniques are often limited by problems of interferences involving several steps of pretreatments. Among these steps, the specific extraction with crown ethers is highly selective for the separation of {sup 99}Tc, {sup 129}I and {sup 135}Cs. The radiometric techniques are here replaced by inductively coupled plasma mass spectroscopy (ICP-MS) the advantages of which are: few interferences, sensitivity which does not depend on the radiologic period as compared to radiochemistry. ICP-MS can then measure {sup 237}Np in enriched uranium matrix and reduce by a factor of 4 the sample pretreatment and the duration of the analysis usually performed by {alpha} spectrometry. Another technique, electrothermal vaporization (ETV), is consequently used. Crown ether extraction-ETV-ICP-MS is employed for measuring the long lived radionuclides {sup 99}Tc and {sup 129}I. The conditions of the extraction and the parameters of the ETV and the ICP-MS are studied and optimized. The methods optimized (extraction, electrothermal vaporization) are validated in the case of {sup 99}Tc, in real samples. The spike method is required to quantify technetium, the quantification with calibration leading to bad results. The results obtained are in good agreement with the expected values. Extraction of technetium on anionic resin and its measurement by the spike method with pneumatic nebulization-ICP-MS is also performed on other samples. Measured values are also in agreement with expected values, but the method of extraction is more time consuming (half a day) than the extraction with crown ether (one hour). (author). 54 figs., 38 tabs.

  6. 多接收电感耦合等离子体质谱法测定Nd同位素标准物质%Nd Isotopic Measurements of Reference Materials Using Multicollector-Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    唐索寒; 何学贤; 王进辉; 朱祥坤

    2005-01-01

    The precision and accuracy of Nd isotope analysis using multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) is verified through repeated measurements of standard reference materials of JMC Nd2O3 and GBW04419. A mixed solution of Nd separated from hundreds of geological samples is measured for 143Nd/144Nd ratio, which produces excellent long-term repeatability. This solution, named as CAGS-Nd-1, can be used as an in-house reference material for monitoring instrument stability during Nd isotope measurements.

  7. 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

    Energy Technology Data Exchange (ETDEWEB)

    Novak, Petra [Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000, Ljubljana (Slovenia); Jožef Stefan International Postgraduate School, Jamova 39, 1000, Ljubljana (Slovenia); Zuliani, Tea [Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000, Ljubljana (Slovenia); Milačič, Radmila [Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000, Ljubljana (Slovenia); Jožef Stefan International Postgraduate School, Jamova 39, 1000, Ljubljana (Slovenia); Ščančar, Janez, E-mail: janez.scancar@ijs.si [Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, 1000, Ljubljana (Slovenia); Jožef Stefan International Postgraduate School, Jamova 39, 1000, Ljubljana (Slovenia)

    2016-04-07

    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{sup −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{sup −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

  8. Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lazarov, Marina, E-mail: m.lazarov@mineralogie.uni-hannover.de; 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 δ{sup 65}Cu 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 ({sup 32}S{sup 33}S){sup +} and ({sup 32}S-{sup 16}O{sup 17}O){sup +} do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn–H or doubly-charged Sn{sup 2+} 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 δ{sup 65}Cu 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/cm{sup 2} 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/cm{sup 2} which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible

  9. Fractionation of phosphorus and trace elements species in soybean flour and common white bean seeds by size exclusion chromatography-inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Koplík, Richard; Pavelková, Hana; Cincibuchová, Jana; Mestek, Oto; Kvasnicka, Frantisek; Suchánek, Miloslav

    2002-04-25

    Soluble species of phosphorus, sulfur, selenium and eight metals (Mn, Fe, Co, Ni, Cu, Zn, Mo and Cd) in soybean flour and common white bean seeds were investigated by size exclusion chromatography (SEC) and inductively coupled plasma mass spectrometry (ICP-MS). Samples were extracted by 0.02 mol l(-1) Tris-HCI buffer solution (pH 7.5). Fractionation of sample extracts by preparative scale SEC was accomplished using a Fractogel EMD BioSEC column (600 x 16 mm) and 0.02 mol l(-1) Tris-HCl buffer solution (pH 7.5) as mobile phase (flow rate: 2 ml min(-1)). A 2-ml sample was injected. Contents of elements in chromatographic fractions were determined by AAS, ICP-AES and ICP-MS. The elution profiles of P, Fe, Co, Ni, Cu, Zn and Mo in both samples were similar. Main species of Co, Ni, Cu, Zn and Mo were found in the low molecular weight region (2-5 kDa), whereas Fe is predominantly bound to high molecular weight compounds (180 kDa). The dominant phosphorus fraction was detected in the medium molecular weight region (10-30 kDa) and the other fraction in the low molecular weight region. Isotachophoretic analysis of chromatographic fractions revealed that the main phosphorus compound in the medium molecular weight region is phytic acid. SEC on Superdex 75 and Superdex Peptide columns (300 x 10 mm) was performed in on-line hyphenation with ICP-MS. The same mobile phase was used with a flow rate of 0.5 ml min(-1); volume of injected sample was 200 microl. Element specific chromatograms were obtained by continuous nebulization of effluent into ICP-mass spectrometer measuring intensities of 47(PO)+ and 48(SO)+ oxide ions and 55Mn, 57Fe, 59Co, 62Ni, 65Cu, 66Zn, 82Se, 95Mo and 114Cd nuclides. Chromatographic profiles of elements are generally analogous to those obtained with a Fractogel column, but better chromatographic resolution of separated species was achieved so that slight differences between samples were revealed. Estimated molecular weights of major phosphorus species in

  10. High-precision measurements of uranium and thorium isotopic ratios by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS)

    Science.gov (United States)

    Wang, Lisheng; Ma, Zhibang; Duan, Wuhui

    2015-04-01

    Isotopic compositions of U-Th and 230Th dating have been widely used in earth sciences, such as chronology, geochemistry, oceanography and hydrology. In this study, five ages of different carbonate samples were measured using 230Th dating technique with U-Th high-precision isotopic measurements by multi-collector inductively coupled plasma mass spectrometry, in Uranium-series Chronology Laboratory, Institute of Geology and Geophysics, Chinese Academy of Sciences.In this study, the precision and accuracy of uranium isotopic composition were estimated by measuring the uranium ratios of NBS-CRM 112A, NBS-CRM U500 and HU-1. The mean measured ratios, 234U/238U = 52.86 (±0.04) × 10-6 and δ234U = -38.36 (±0.77) × 10-3 for NBS-CRM 112A, 234U/238U = 10.4184 (±0.0001) × 10-3, 236U/238U = 15.43 (±0.01) × 10-4 and 238U/235U = 1.00021 (±0.00002) for NBS-CRM U500, 234U/238U = 54.911 (±0.007) and δ234U = -1.04 (±0.13) × 10-3 for HU-1 (95% confidence levels). The U isotope data for standard reference materials are in excellent agreement with previous studies, further highlighting the reliability and analytical capabilities of our technique. We measured the thorium isotopic ratios of three different thorium standards by MC-ICPMS. The three standards (Th-1, Th-2 and Th-3) were mixed by HU-1 and NBS 232Th standard, with the 230Th/232Th ratios from 10-4 to 10-6. The mean measured atomic ratios, 230Th/232Th = 2.1227 (±0.0024) × 10-6, 2.7246 (±0.0026) × 10-5, and 2.8358 (±0.0007) × 10-4 for Th-1, Th-2 and Th-3 (95% confidence levels), respectively. Using this technique, the following standard samples were dated by MC-ICPMS. Sample RKM-4, collected from Babardos Kendal Hill terrace, was used during the first stage of the Uranium-Series Intercomparison Project (USIP-I). Samples 76001, RKM-5 and RKM-6 were studied during the second stage of the USIP program (USIP-II). Sample 76001 is a laminated flowstone, collected from Sumidero Terejapa, Chiapas, Mexico, and samples

  11. Analytical evaluation of nebulizers for the introduction of acetic acid extracts aiming at the determination of trace elements by inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Gois, Jefferson S. de; Maranhao, Tatiane de A. [Departamento de Quimica, Universidade Federal de Santa Catarina, 88040-970, Florianopolis, SC (Brazil); Oliveira, Fernando J.S. [Petroleo Brasileiro S.A., Gerencia de Meio Ambiente, Rio de Janeiro, RJ (Brazil); Frescura, Vera L.A.; Curtius, Adilson J. [Departamento de Quimica, Universidade Federal de Santa Catarina, 88040-970, Florianopolis, SC (Brazil); Borges, Daniel L.G., E-mail: daniel.borges@ufsc.br [Departamento de Quimica, Universidade Federal de Santa Catarina, 88040-970, Florianopolis, SC (Brazil)

    2012-11-15

    Most of the official procedures aiming at classification of solid waste toxicity take into account metal solubility and bioavailability by means of extraction experiments using acetic acid solutions. Hence, the aim of this work was to investigate and optimize conditions to suppress the effect of acetic acid on the determination of trace elements using inductively coupled plasma mass spectrometry. The performance of four nebulizers (cross-flow (CFN), ultrasonic (USN), Meinhard (MN) and MicroMist (MMN)) were compared as to their efficiency in minimizing spectral and non-spectral effects on the determination of Ag, As, Ba, Cd, Cr, Hg, Pb and Se, with the ultimate goal to analyze acetic acid extracts obtained from solid waste residues. Operating conditions (desolvation temperatures for USN, RF power and nebulizer gas flow rates) were optimized individually for each nebulizer and for all analytes maintained in 0.14 mol L{sup -1} HNO{sub 3} solutions and in solutions prepared with acetic acid and acetic acid + NaOH, adjusted to pH 2.88 and 4.93, respectively. Pronounced non-spectral interferences for {sup 75}As and {sup 82}Se were observed in the presence of acetic acid for CF and MN, although to a less extent also for MMN and USN. Signal increase for blank solutions measured at m/z 208 ({sup 208}Pb) for CFN and MN, 107 ({sup 107}Ag) for USN and MN coupled to a cyclonic chamber and, m/z 82 ({sup 82}Se) for USN was observed, indicating an increased risk of spectral interference upon an increase in the concentration of acetic acid. Signal increase at specific m/z ratios, however, was not significant when the MMN was used, with the exception of m/z 52 ({sup 52}Cr) in acetic acid solutions, arising from the formation of {sup 40}Ar{sup 12}C{sup +}. This same effect was noticed for all nebulizers, although at noticeably different intensities. A signal stability study was performed, demonstrating that variations in the analytical signal were within a 20% range for all analytes

  12. Bayesian Integration and Classification of Composition C-4 Plastic Explosives Based on Time-of-Flight-Secondary Ion Mass Spectrometry and Laser Ablation-Inductively Coupled Plasma Mass Spectrometry.

    Science.gov (United States)

    Mahoney, Christine M; Kelly, Ryan T; Alexander, Liz; Newburn, Matt; Bader, Sydney; Ewing, Robert G; Fahey, Albert J; Atkinson, David A; Beagley, Nathaniel

    2016-04-05

    Time-of-flight-secondary ion mass spectrometry (TOF-SIMS) and laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) were used for characterization and identification of unique signatures from a series of 18 Composition C-4 plastic explosives. The samples were obtained from various commercial and military sources around the country. Positive and negative ion TOF-SIMS data were acquired directly from the C-4 residue on Si surfaces, where the positive ion mass spectra obtained were consistent with the major composition of organic additives, and the negative ion mass spectra were more consistent with explosive content in the C-4 samples. Each series of mass spectra was subjected to partial least squares-discriminant analysis (PLS-DA), a multivariate statistical analysis approach which serves to first find the areas of maximum variance within different classes of C-4 and subsequently to classify unknown samples based on correlations between the unknown data set and the original data set (often referred to as a training data set). This method was able to successfully classify test samples of C-4, though with a limited degree of certainty. The classification accuracy of the method was further improved by integrating the positive and negative ion data using a Bayesian approach. The TOF-SIMS data was combined with a second analytical method, LA-ICPMS, which was used to analyze elemental signatures in the C-4. The integrated data were able to classify test samples with a high degree of certainty. Results indicate that this Bayesian integrated approach constitutes a robust classification method that should be employable even in dirty samples collected in the field.

  13. Speciation of nickel in airborne particulate matter by means of sequential extraction in a micro flow system and determination by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Fuichtjohann, L; Jakubowski, N; Gladtke, D; Klocko, D; Broekaert, J A

    2001-12-01

    A four-stage sequential extraction procedure for the speciation of nickel has been applied to ambient aerosol samples. The determination of the soluble, sulfidic, metallic and oxidic Ni fractions in particulate matter was carried out by graphite furnace (electrothermal) atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICP-MS). An EDTA solution, a mixture of diammonium citrate and hydrogen peroxide, and a KCuCl3 solution were used as leaching agents for the determination of the soluble, sulfidic and metallic species, respectively, and nitric acid was used for the determination of oxidic compounds after microwave digestion of particulate matter sampled on filters. A new micro scale filter holder placed in a closed flow injection analysis (FIA) system for use in nickel speciation by means of sequential extraction, and the results of the optimisation of the extraction conditions are described. The temperature program for ETAAS was optimised for all extraction solutions with the aid of temperature curves. Pyrolysis temperatures of 900. 600 and 1,000 degrees C were found to be optimum for EDTA, hydrogen peroxide plus ammonium citrate and KCuCl3-containing solutions, respectively. Airborne dust was sampled on lilters at two locations near to a metallurgical plant in Dortmund, Germany. Concentrations in the low ng m(-3) range down to the detections limits (0.1-0.3 ng m(-3)) and various nickel species were found to be present in the collected dust. The mean fractions of total nickel (sampling period of one month) were found to contain 36+20% of soluble, 6 +/- 4% of sulfidic, 11 +/- 15% of metallic and 48 +/- 18% of oxidic nickel.

  14. Speciation analysis of orthophosphate and myo-inositol hexakisphosphate in soil- and plant-related samples by high-performance ion chromatography combined with inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Rugova, Ariana; Puschenreiter, Markus; Santner, Jakob; Fischer, Lisa; Neubauer, Stefan; Koellensperger, Gunda; Hann, Stephan

    2014-07-01

    A novel method based on high-performance ion chromatography inductively coupled plasma mass spectrometry employing strong anion exchange chromatography with HNO3 gradient elution for simultaneous analysis of orthophosphate and myo-inositol hexakisphosphate (IP6 ) in soil solution and plant extracts is presented. As inductively coupled plasma mass spectrometry analysis of phosphorus at m/z 31 is hampered by N-based interferences, (31)P was measured as (31)P(16)O(+) at m/z 47 employing dynamic reaction cell technique with O2 as reaction gas. Orthophosphate and IP6 were separated within a total chromatographic run-time of 12 min revealing a limit of detection of 0.3 μmol/L. The coefficients of determination obtained in a working range of 1-100 and 1-30 μmol/L were 0.9991 for orthophosphate and 0.9968 for IP6, respectively. The method was successfully applied to extracts from three different soils as well as root and shoot extracts of Brassica napus L. The precision of three independently prepared soil extracts was in the range of 4-10% relative standard deviation for PO4 (3-) and 3-8% relative standard deviation for IP6. Soil adsorption/desorption kinetics for IP6/orthophosphate were performed for investigating the sorption behavior of the two P species in the experimental soils.

  15. Current developments in laser ablation-inductively coupled plasma-mass spectrometry for use in geology, forensics, and nuclear nonproliferation research

    Energy Technology Data Exchange (ETDEWEB)

    Messerly, Joshua D. [Iowa State Univ., Ames, IA (United States)

    2008-08-26

    This dissertation focused on new applications of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The diverse fields that were investigated show the versatility of the technique. In Chapter 2, LA-ICP-MS was used to investigate the rare earth element (REE) profiles of garnets from the Broken Hill Deposit in New South Wales, Australia. The normalized REE profiles helped to shed new light on the formation of deposits of sulfide ores. This information may be helpful in identifying the location of sulfide ore deposits in other locations. New sources of metals such as Pg, Zn, and Ag, produced from these ores, are needed to sustain our current technological society. The application of LA-ICP-MS presented in Chapter 3 is the forensics analysis of automotive putty and caulking. The elemental analysis of these materials was combined with the use of Principal Components Analysis (PCA). The PCA comparison was able to differentiate the automotive putty samples by manufacturer and lot number. The analysis of caulk was able to show a differentiation based on manufacturer, but no clear differentiation was shown by lot number. This differentiation may allow matching of evidence in the future. This will require many more analyses and the construction of a database made up of many different samples. The 4th chapter was a study of the capabilities of LA-ICP-MS for fast and precise analysis of particle ensembles for nuclear nonproliferation applications. Laser ablation has the ability to spatially resolve particle ensembles which may contain uranium or other actinides from other particles present in a sample. This is of importance in samples obtained from air on filter media. The particle ensembles of interest may be mixed in amongst dust and other particulates. A problem arises when ablating these particle ensembles directly from the filter media. Dust particles other than ones of interest may be accidentally entrained in the aerosol of the ablated particle

  16. Current developments in laser ablation-inductively coupled plasma-mass spectrometry for use in geology, forensics, and nuclear nonproliferation research

    Energy Technology Data Exchange (ETDEWEB)

    Messerly, Joshua D. [Iowa State Univ., Ames, IA (United States)

    2008-08-26

    This dissertation focused on new applications of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The diverse fields that were investigated show the versatility of the technique. In Chapter 2, LA-ICP-MS was used to investigate the rare earth element (REE) profiles of garnets from the Broken Hill Deposit in New South Wales, Australia. The normalized REE profiles helped to shed new light on the formation of deposits of sulfide ores. This information may be helpful in identifying the location of sulfide ore deposits in other locations. New sources of metals such as Pg, Zn, and Ag, produced from these ores, are needed to sustain our current technological society. The application of LA-ICP-MS presented in Chapter 3 is the forensics analysis of automotive putty and caulking. The elemental analysis of these materials was combined with the use of Principal Components Analysis (PCA). The PCA comparison was able to differentiate the automotive putty samples by manufacturer and lot number. The analysis of caulk was able to show a differentiation based on manufacturer, but no clear differentiation was shown by lot number. This differentiation may allow matching of evidence in the future. This will require many more analyses and the construction of a database made up of many different samples. The 4th chapter was a study of the capabilities of LA-ICP-MS for fast and precise analysis of particle ensembles for nuclear nonproliferation applications. Laser ablation has the ability to spatially resolve particle ensembles which may contain uranium or other actinides from other particles present in a sample. This is of importance in samples obtained from air on filter media. The particle ensembles of interest may be mixed in amongst dust and other particulates. A problem arises when ablating these particle ensembles directly from the filter media. Dust particles other than ones of interest may be accidentally entrained in the aerosol of the ablated particle

  17. Analysis of Organic and Inorganic Arsenic in Waste Water of Agricultural Environment by High Performance Liquid Chromatography and Inductively Coupled Plasma Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    SHAN Hong

    2014-04-01

    Full Text Available A high performance liquid chromatography and inductively coupled plasma mass spectrometric method was established for analyz-ing 4 arsenic speciations in water of agricultural environment, including As(Ⅲ,MMA, DMA and As( V.The results showed that the method had a wide linear range(1~300 μg·L-1and the linear coefficients were more than 0.999 0. The detection limits were very low ( 0.7-0.9μg·L-1.All of the relative standard deviations(RSD were less than 5%. The recoveries were between 94% and 112%. The analysis results showed that As( Vand As(Ⅲwere the main arsenic speciations existed in the waste water of agricultural environment.

  18. Standard test method for analysis of total and isotopic uranium and total thorium in soils by inductively coupled plasma-mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2008-01-01

    1.1 This test method covers the measurement of total uranium (U) and thorium (Th) concentrations in soils, as well as the determination of the isotopic weight percentages of 234U, 235U, 236U, and 238U, thereby allowing for the calculation of individual isotopic uranium activity or total uranium activity. This inductively coupled plasma-mass spectroscopy (ICP-MS) method is intended as an alternative analysis to methods such as alpha spectroscopy or thermal ionization mass spectroscopy (TIMS). Also, while this test method covers only those isotopes listed above, the instrumental technique may be expanded to cover other long-lived radioisotopes since the preparation technique includes the preconcentration of the actinide series of elements. The resultant sample volume can be further reduced for introduction into the ICP-MS via an electrothermal vaporization (ETV) unit or other sample introduction device, even though the standard peristaltic pump introduction is applied for this test method. The sample preparatio...

  19. Comparison of optimised germanium gamma spectrometry and multicollector inductively coupled plasma mass spectrometry for the determination of 134Cs, 137Cs and 154Eu single ratios in highly burnt UO 2

    Science.gov (United States)

    Caruso, S.; Günther-Leopold, I.; Murphy, M. F.; Jatuff, F.; Chawla, R.

    2008-05-01

    Non-destructive and destructive methods have been compared to validate their corresponding assessed accuracies in the measurement of 134Cs/137Cs and 154Eu/137Cs isotopic concentration ratios in four spent UO2 fuel samples with very high (52 and 71 GWd/t) and ultra-high (91 and 126 GWd/t) burnup values, and about 10 (in the first three samples) and 4 years (in the latter sample) cooling time. The non-destructive technique tested was high-resolution gamma spectrometry using a high-purity germanium detector (HPGe) and a special tomographic station for the handling of highly radioactive 400 mm spent fuel segments that included a tungsten collimator, lead filter (to enhance the signal to Compton background ratio and reduce the dead time) and paraffin wax (to reduce neutron damage). The non-destructive determination of these isotopic concentration ratios has been particularly challenging for these segments because of the need to properly derive non-Gaussian gamma-peak areas and subtract the background from perturbing capture gammas produced by the intrinsic high-intensity neutron emissions from the spent fuel. Additionally, the activity distribution within each pin was determined tomographically to correct appropriately for self-attenuation and geometrical effects. The ratios obtained non-destructively showed a 1σ statistical error in the range 1.9-2.9%. The destructive technique used was a high-performance liquid chromatographic separation system, combined online to a multicollector inductively coupled plasma mass spectrometer (HPLC-MC-ICP-MS), for the analysis of dissolved fuel solutions. During the mass spectrometric analyses, special care was taken in the optimisation of the chromatographic separation for Eu and the interfering element Gd, as also in the mathematical correction of the 154Gd background from the 154Eu signal. The ratios obtained destructively are considerably more precise (1σ statistical error in the range 0.4-0.8% for most of the samples, but up to

  20. 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.

    Science.gov (United States)

    Krachler, Michael; Alvarez-Sarandes, Rafael; Rasmussen, Gert

    2016-09-06

    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 (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 spectrometric approach and thus effectively adds to the quality assurance of (234)U

  1. Spatial resolution in laser ablation inductively coupled plasma mass spectrometry; Resolucion espacial en la ablacion laser acoplada a la espectrometria de masas con fuente de plasm de acoplamiento inductivo

    Energy Technology Data Exchange (ETDEWEB)

    Coedo, A. G.; Dorado, M. T.

    2010-07-01

    Laser ablation as sampling system in inductively coupled plasma mass spectrometry (LA-ICP-MS) offers the possibility to know the spatial distribution of elements present in a solid sample. By varying the position of the laser beam on the sample surface, the profile of the lateral distribution of elements is obtained and, with successive pulses fired on a fixed point, profile in depth is achieved. After optimization of operating parameters the technique has been applied to samples with different compositions in both surface and depth.With regard to the lateral resolution has been found that in a length similar to the crater diameter of the laser beam, the signals of the elements appear mixed, making difficult to accurately establish the interface. Regarding the resolution in depth is clearly established the influence of the natural abundance of the measured isotopes. (Author)

  2. Simultaneous determination of Se, trace elements and major elements in Se-rich rice by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) after microwave digestion.

    Science.gov (United States)

    Wei, Yi Hua; Zhang, Jin Yan; Zhang, Da Wen; Luo, Lin Guang; Tu, Tian Hua

    2014-09-15

    A quick and accurate method was devised to determine Se, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr and Zn in Se-rich rice samples by microwave digestion and inductively coupled plasma-mass spectrometry (ICP-MS). Spectral interferences on Se were eliminated using methane as a reaction gas in the dynamic reaction cell (DRC). Rhodium was used as an internal standard to compensate for sample matrix effects. A rice-certified reference material (CRM) (GBW 10010) was used to verify the accuracy of the method. The method detection limits were 0.001-0.03 mg/kg, analyte recoveries were 85-108% and precisions (RSDs) ranged from 2.1% to 5.8%. Correlation analysis showed that the Se concentrations in the Se-rich rice samples correlated well with the Cu concentrations (r=0.53, p<0.05).

  3. A simple and practical control of the authenticity of organic sugarcane samples based on the use of machine-learning algorithms and trace elements determination by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Barbosa, Rommel M; Batista, Bruno L; Barião, Camila V; Varrique, Renan M; Coelho, Vinicius A; Campiglia, Andres D; Barbosa, Fernando

    2015-10-01

    A practical and easy control of the authenticity of organic sugarcane samples based on the use of machine-learning algorithms and trace elements determination by inductively coupled plasma mass spectrometry is proposed. Reference ranges for 32 chemical elements in 22 samples of sugarcane (13 organic and 9 non organic) were established and then two algorithms, Naive Bayes (NB) and Random Forest (RF), were evaluated to classify the samples. Accurate results (>90%) were obtained when using all variables (i.e., 32 elements). However, accuracy was improved (95.4% for NB) when only eight minerals (Rb, U, Al, Sr, Dy, Nb, Ta, Mo), chosen by a feature selection algorithm, were employed. Thus, the use of a fingerprint based on trace element levels associated with classification machine learning algorithms may be used as a simple alternative for authenticity evaluation of organic sugarcane samples.

  4. Gold upgrading in metamorphosed massive sulfide ore deposits: Direct evidence from laser-ablation-inductively coupled plasma-mass spectrometry analysis of invisible gold

    Science.gov (United States)

    Wagner, Thomas; Klemd, Reiner; Wenzel, Thomas; Mattsson, Benny

    2007-09-01

    The metamorphosed Boliden volcanic-hosted massive sulfide (VHMS) ore deposit, northern Sweden, is characterized by an abundance of massive arsenopyrite ore and unusually high gold enrichments (up to 300-600 g/t) in crosscutting veins and fracture zones. The ore textures observed record progressive recrystallization and porphyroblast growth during meta morphism. We conducted a systematic laser-ablation-inductively coupled plasma-mass spectrom etry (LA-ICP-MS) study on the gold distribution in fine-grained massive arseno-pyrite and pyrite ore, partially recrystallized arsenopyrite ore, and both arsenopyrite and pyrite porphyroblasts found in gold-rich veins. The gold concentrations in massive arseno-pyrite are highest (30-50 ppm on average) and systematically decrease to 0-2.7 ppm with increasing degree of recrystallization. By contrast, gold concentrations in pyrite ore are much lower and do not exceed 0.2 ppm. The LA-ICP-MS data, coupled with textural data, provide the first direct conclusive evidence that gold is progressively liberated from massive sulfide ores during metamorphism and reprecipitated in veins and other low-strain sites. We suggest that such upgrading is the principal mechanism responsible for significant gold enrichment observed in many metamorphosed VHMS deposits worldwide.

  5. Metal imaging on surface of micro- and nanoelectronic devices by laser ablation inductively coupled plasma mass spectrometry and possibility to measure at nanometer range.

    Science.gov (United States)

    Zoriy, Myroslav V; Mayer, Dirk; Becker, J Sabine

    2009-05-01

    An analytical mass spectrometric method for the elemental analysis of nano-bioelectronic devices involved in bioengineering research was developed and applied for measurements of selected metals (Au, Ti, Pt, Cr, etc.) on interdigitated electrode array chips (IDA-chip). An imaging laser ablation inductively coupled plasma mass spectrometric (LA-ICP-MS) procedure was used to map the elements of interest on the surface of the analyzed sample. The obtained images of metals were in a good agreement and corresponded to the micro- and nanofabricated metal electrode pattern. For the analysis at nanometer resolution scale a NF-LA-ICP-MS (NF-near-field) procedure was applied, which utilize thin Ag needle to enhance laser beam energy and improve spatial resolution of the method. The results show a approximately 100x enhancement of analyte signal, when the needle was positioned in the "near-field region" to the sample surface and the laser shot was performed. In addition, mass spectrometric studies of reproducibly for five separated NF-LA shots in different places of analyzed sample yielded an RSD of the measurement of 16%.

  6. Standard test method for analysis of isotopic composition of uranium in nuclear-grade fuel material by quadrupole inductively coupled plasma-mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2000-01-01

    1.1 This test method is applicable to the determination of the isotopic composition of uranium (U) in nuclear-grade fuel material. The following isotopic weight percentages are determined using a quadrupole inductively coupled plasma-mass spectrometer (Q-ICP-MS): 233U, 234U, 235U, 236U, and 238U. The analysis can be performed on various material matrices after acid dissolution and sample dilution into water or dilute nitric (HNO3) acid. These materials include: fuel product, uranium oxide, uranium oxide alloys, uranyl nitrate (UNH) crystals, and solutions. The sample preparation discussed in this test method focuses on fuel product material but may be used for uranium oxide or a uranium oxide alloy. Other preparation techniques may be used and some references are given. Purification of the uranium by anion-exchange extraction is not required for this test method, as it is required by other test methods such as radiochemistry and thermal ionization mass spectroscopy (TIMS). This test method is also described i...

  7. Determination of several elements in duplicate meals from catering establishments using closed vessel microwave digestion with inductively coupled plasma mass spectrometry detection: estimation of daily dietary intake.

    Science.gov (United States)

    Noël, L; Leblanc, J C; Guérin, T

    2003-01-01

    An estimation of the dietary exposure of French consumers to 21 essential and non-essential mineral elements using duplicate meals (breakfast and lunch) purchased from catering establishments was investigated after digestion by a closed vessel microwave procedure and quantification by ICP-MS. Daily dietary exposure estimates for metals and minerals were compared with the Provisional Tolerable Weekly Intakes (PTWI), the Tolerable Daily Intake (TDI) or the Acceptable Daily Intakes (ADI), as established by the FAO/WHO to estimate the risk of toxicity, and the US Recommended Daily Allowances (US RDA) or the Estimate Safe & Adequate Daily Dietary Intakes (ESADDI). Moreover, comparisons were made with those from previous French studies as well as those from other countries. The estimated mean daily intakes were 11 microgram for lithium, 3.42 g for sodium, 192 mg for magnesium, 2.03 mg for aluminium, 3.64 g for potassium, 642 mg for calcium, 154 microgram for chromium, 12.3 mg for iron, 2.15 mg for manganese, 4 microgram for cobalt, 74 microgram for nickel, 925 microgram for copper, 10.2 mg for zinc, 147 microgram for arsenic, 66 microgram for selenium, 112 microgram for molybdenum, 3.6 microgram for cadmium, 2.32 mg for tin, 3 microgram for antimony, 9 microgram for mercury and 34 microgram for lead. For the non-essential (toxic) elements, aluminium, tin, antimony, cadmium, arsenic, mercury and lead, the daily intake estimates were far below tolerable limits; and similar or somewhat lower than their respective PTWI, ADI, TDI, ESADDI and US RDA for individual minerals and essential trace elements, with good agreement with other country studies. The performance of the multi-elemental ICP-MS technique was also evaluated.

  8. Determination of tungsten in geochemical reference material basalt Columbia River 2 by radiochemical neutron activation analysis and inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Morrison, Samuel S.; Beck, Chelsie L.; Bowen, James M.; Eggemeyer, Tere A.; Hines, Corey C.; Liezers, Martin; Metz, Lori A.; Morley, Shannon M.; Restis, Kaitlyn R.; Snow, Mathew; Wall, Donald E.; Clark, Sue B.; Seiner, Brienne N.

    2017-01-02

    Environmental tungsten (W) analyses are inhibited by a lack of reference materials and practical methods to remove isobaric and radiometric interferences. We present a method that evaluates the potential use of commercially available sediment, Basalt Columbia River-2 (BCR-2), as a reference material using neutron activation analysis (NAA) and mass spectrometry. Tungsten concentrations using both methods are in statistical agreement at the 95% confidence interval (92 ± 4 ng/g for NAA and 100 ±7 ng/g for mass spectrometry) with recoveries greater than 95%. These results indicate that BCR-2 may be suitable as a reference material for future studies.

  9. 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.

    Science.gov (United States)

    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.

  10. Simultaneous quantification of 17 trace elements in blood by dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) equipped with a high-efficiency sample introduction system.

    Science.gov (United States)

    D'Ilio, S; Violante, N; Di Gregorio, M; Senofonte, O; Petrucci, F

    2006-10-10

    A quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) equipped with a dynamic reaction cell (DRC) and coupled with a desolvating nebulization system (APEX-IR) was employed to determine 17 elements (Al, As, Ba, Cd, Co, Cr, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Sr, V, and Zr) in blood samples. Ammonia (for Al, Cr, Mn, and V) and O2 (for As and Se) were used as reacting gases. Selection of the best flow rate of the gases and optimization of the quadrupole dynamic bandpass tuning parameter (RPq) were carried out, using digested blood diluted 1+9 with deionized water and spiked with 1 microg L(-1) of Al, Cr, Mn, V and 5 microgL(-1) of As and Se. Detection limits were determined in digested blood using the 3sigma criterion. The desolvating system allowed a sufficient sensitivity to be achieved to determine elements at levels of ng L(-1) without detriment of signal stability. The accuracy of the method was tested with the whole blood certified reference material (CRM), certified for Al, As, Cd, Co, Cr, Mn, Mo, Ni, Pb, Sb, Se, and V, and with indicative values for Ba, Li, Sn, Sr, and Zr. The addition calibration approach was chosen for analysis. In order to confirm the DRC data, samples were also analyzed by means of sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), operating in medium (m/Deltam=4000) and high (m/Deltam=10,000) resolution mode and achieving a good agreement between the two techniques.

  11. 等离子体质谱法测定高钠食品中微量铅的应用研究%Study on the Determination of Trace Lead in High Sodium Food by Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    张喜琦; 王骏; 陈晓媛

    2013-01-01

    The high content of sodium in high sodium food could interfere the determination of lead by Graphite Furnace Atomic Absorb Spectrometry,which will cause low determination result.At present,there is no method that could remove the matrix interference of sodium easily.The lead solution treated by microwave digestion can be determined by Inductively Coupled Plasma Mass Spectrometry.The test shows that this method has simple operation,high accuracy,high precision and low detection limit,it is a good method for the determination of trace lead in high sodium food.%高钠食品中微量铅用传统的石墨炉原子吸收光谱法直接测定时,样品中大量钠会对铅的信号产生很大的光谱干扰,导致测定结果偏低,没有简便易行的方法去除钠的基体干扰.经微波消解处理过的溶液可以直接用电感耦合等离子体质谱测定铅的含量,经验证该方法操作简便、结果准确、精密度高、检出限低,是测定高盐食品中微量铅的理想方法.

  12. Imaging of uranium on rat brain sections using laser ablation inductively coupled plasma mass spectrometry: a new tool for the study of critical substructures affined to heavy metals in tissues.

    Science.gov (United States)

    Becker, J Sabine; Dobrowolska, Justina; Zoriy, Miroslav; Matusch, Andreas

    2008-09-01

    The specific toxicity of trace metals and compounds largely depends on their bioavailability in different organs or compartments of the organism considered. Imaging mass spectrometry (IMS) using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) with a spatial resolution in the 100 microm range was developed and employed to study heavy metal distribution in brain tissues for toxicological screening. Rat brain post-mortem tissues were stained in an aqueous solution of either uranium or neodymium (metal concentration 100 microg g(-1)) for 3 h. The incubation of heavy metal in thin slices of brain tissue is followed by an imaging mass spectrometric LA-ICP-MS technique. Stained rat brain tissue (thickness 30 microm) were scanned with a focused laser beam (wavelength 266 nm, diameter of laser crater 100 microm and laser power density 3 x 10(9) W cm(-2)). The ion intensities of (235)U(+), (238)U(+), (145)Nd(+) and (146)Nd(+) were measured by LA-ICP-MS within the ablated area. For quantification purposes, matrix-matched laboratory standards were prepared by dosing each analyte to the pieces of homogenized brain tissue. Imaging LA-ICP-MS allows structures of interest to be identified and the relevant dose range to be estimated.

  13. Fractionation and Characterization of High Aspect Ratio Gold Nanorods Using Asymmetric-Flow Field Flow Fractionation and Single Particle Inductively Coupled Plasma Mass Spectrometry

    OpenAIRE

    Nguyen, Thao M; Jingyu Liu; Vincent A. Hackley

    2015-01-01

    Gold nanorods (GNRs) are of particular interest for biomedical applications due to their unique size-dependent longitudinal surface plasmon resonance band in the visible to near-infrared. Purified GNRs are essential for the advancement of technologies based on these materials. Used in concert, asymmetric-flow field flow fractionation (A4F) and single particle inductively coupled mass spectrometry (spICP-MS) provide unique advantages for fractionating and analyzing the typically complex mixtur...

  14. Testing the limits of micro-scale analyses of Si stable isotopes by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry with application to rock weathering

    Energy Technology Data Exchange (ETDEWEB)

    Schuessler, Jan A., E-mail: jan.schuessler@gfz-potsdam.de; Blanckenburg, Friedhelm von

    2014-08-01

    An analytical protocol for accurate in-situ Si stable isotope analysis has been established on a new second-generation custom-built femtosecond laser ablation system. The laser was coupled to a multicollector inductively coupled plasma mass spectrometer (fsLA-MC-ICP-MS). We investigated the influence of laser parameters such as spot size, laser focussing, energy density and repetition rate, and ICP-MS operating conditions such as ICP mass load, spectral and non-spectral matrix effects, signal intensities, and data processing on precision and accuracy of Si isotope ratios. We found that stable and reproducible ICP conditions were obtained by using He as aerosol carrier gas mixed with Ar/H{sub 2}O before entering the plasma. Precise δ{sup 29}Si and δ{sup 30}Si values (better than ± 0.23‰, 2SD) can be obtained if the area ablated is at least 50 × 50 μm; or, alternatively, for the analysis of geometric features down to the width of the laser spot (about 20 μm) if an equivalent area is covered. Larger areas can be analysed by rastering the laser beam, whereas small single spot analyses reduce the attainable precision of δ{sup 30}Si to ca. ± 0.6‰, 2SD, for < 30 μm diameter spots. It was found that focussing the laser beam beneath the sample surface with energy densities between 1 and 3.8 J/cm{sup 2} yields optimal analytical conditions for all materials investigated here. Using pure quartz (NIST 8546 aka. NBS-28) as measurement standard for calibration (standard-sample-bracketing) did result in accurate and precise data of international reference materials and samples covering a wide range in chemical compositions (Si single crystal IRMM-017, basaltic glasses KL2-G, BHVO-2G and BHVO-2, andesitic glass ML3B-G, rhyolitic glass ATHO-G, diopside glass JER, soda-lime glasses NIST SRM 612 and 610, San Carlos olivine). No composition-dependent matrix effect was discernible within uncertainties of the method. The method was applied to investigate the Si isotope

  15. Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Larsen, Erik Huusfeldt

    1998-01-01

    . The optimized anion and cation exchange HPLC-ICP-MS systems were used for arsenic speciation in contaminated ground water and in an in-house shrimp reference sample. For the purpose of verification, HPLC coupled with tandem mass spectrometry with electrospray ionization was additionally used for arsenic....... Anion and cation exchange HPLC systems, which meet these requirements, were used for the separation of selenium and arsenic species in crude extracts of biological samples. Furthermore, the signal-to-noise ratios obtained for these incompletely ionized elements in the argon ICP were further enhanced...

  16. Standard test method for isotopic abundance analysis of uranium hexafluoride and uranyl nitrate solutions by multi-collector, inductively coupled plasma-mass spectrometry

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2014-01-01

    1.1 This test method covers the isotopic abundance analysis of 234U, 235U, 236U and 238U in samples of hydrolysed uranium hexafluoride (UF6) by inductively coupled plasma source, multicollector, mass spectrometry (ICP-MC-MS). The method applies to material with 235U abundance in the range of 0.2 to 6 % mass. This test method is also described in ASTM STP 1344. 1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard. 1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

  17. Biomonitoring of metal contamination in a marine prosobranch snail (Nassarius reticulatus) by imaging laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    Science.gov (United States)

    Santos, Mirian C; Wagner, Martin; Wu, Bei; Scheider, Jessica; Oehlmann, Jörg; Cadore, Solange; Becker, J Sabine

    2009-12-15

    An imaging mass spectrometric method using laser ablation inductively coupled plasma spectrometry (LA-ICP-MS) was developed to determine Cu, Zn, Cd, Hg and Pb and metal distribution in longitudinal tissue sections of the marine snail Nassarius reticulatus (Gastropoda, Prosobranchia). Snails were sampled in northern Brittany (France) at three stations with different contamination levels. The quantification of metal distribution (imaging or mapping) in a thin slice of the snail tissue was carried out using different strategies: by one-point calibration and via matrix-matched laboratory standards using different biological materials (BCR 278, snail tissue, and rat brain). Together with the imaging of metals the distribution of two non-metals (carbon and sulfur) was analyzed. The imaging LA-ICP-MS analysis yielded an inhomogeneous distribution for all elements investigated. The detection limits for the distribution analysis of Cu, Zn, Cd, Hg and Pb measured by LA-ICP-MS were in the low microg g(-1) range.

  18. MSI.R scripts reveal volatile and semi-volatile features in low-temperature plasma mass spectrometry imaging (LTP-MSI) of chilli (Capsicum annuum).

    Science.gov (United States)

    Gamboa-Becerra, Roberto; Ramírez-Chávez, Enrique; Molina-Torres, Jorge; Winkler, Robert

    2015-07-01

    In cartography, the combination of colour and contour lines is used to express a three-dimensional landscape on a two-dimensional map. We transferred this concept to the analysis of mass spectrometry imaging (MSI) data and developed a collection of R scripts for the efficient evaluation of .imzML archives in a four-step strategy: (1) calculation of the density distribution of mass-to-charge ratio (m/z) signals in the .imzML file and assembling of a pseudo-master spectrum with peak list, (2) automated generation of mass images for a defined scan range and subsequent visual inspection, (3) visualisation of individual ion distributions and export of relevant .mzML spectra and (4) creation of overlay graphics of ion images and photographies. The use of a Hue-Chroma-Luminance (HCL) colour model in MSI graphics takes into account the human perception for colours and supports the correct evaluation of signal intensities. Further, readers with colour blindness are supported. Contour maps promote the visual recognition of patterns in MSI data, which is particularly useful for noisy data sets. We demonstrate the scalability of MSI.R scripts by running them on different systems: on a personal computer, on Amazon Web Services (AWS) instances and on an institutional cluster. By implementing a parallel computing strategy, the execution speed for .imzML data scanning with image generation could be improved by more than an order of magnitude. Applying our MSI.R scripts ( http://www.bioprocess.org/MSI.R ) to low-temperature plasma (LTP)-MSI data shows the localisation of volatile and semi-volatile compounds in the cross-cut of a chilli (Capsicum annuum) fruit. The subsequent identification of compounds by gas and liquid chromatography coupled to mass spectrometry (GC-MS, LC-MS) proves that LTP-MSI enables the direct measurement of volatile organic compound (VOC) distributions from biological tissues.

  19. Solid Matrix Transformation and Tracer Addition using Molten Ammonium Bifluoride Salt as a Sample Preparation Method for Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Grate, Jay W.; Gonzalez, Jhanis J.; O' Hara, Matthew J.; Kellogg, Cynthia M.; Morrison, Samuel S.; Koppenaal, David W.; Chan, George C.; Mao, Xianglei; Zorba, Vassilia; Russo, Richard

    2017-09-08

    Laser ablation (LA) is a means of sample introduction to inductively coupled plasma (ICP) mass spectrometry (MS) that avoids acid dissolution and chemical separation steps conventionally associated with solid sample analysis. At the same time, certain features of LA-ICP-MS are often mentioned in critical reviews including solid matrix variability and its influence on the ablation process, matrix dependent elemental fractionation, lack of matrix matched standards for external calibration, and limitations to internal calibration because it is challenging to add and distribute spikes into solid samples. In this paper we introduce the concept of a synergistic minimal sample preparation method that is used in combination with LA-ICP-MS as a means to overcome these limitations. The aim of this minimal sample preparation procedure is to reactively transform the original matrix to a more consistent matrix for LA-based analysis, thus reducing the effects of matrix variability, while enabling the addition of tracers. In conjunction with ICP-MS, we call this MTR-LA-ICP-MS, where MTR is derived from matrix transformation including the option to add tracers

  20. Pure cerium dioxide preparation for use as spectrochemical standard and analysed by inductively coupled plasma mass spectrometry (SF ICP-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Queiroz, Carlos A. da S.; Abrao, Alcidio; Rocha, Soraya M.R. da; Vasconcellos, Mari E. de; Seneda, Jose A.; Forbicini, Christina A.L.G. de O. [Instituto de Pesquisas Energeticas e Nucleares (IPEN), Sao Paulo, SP (Brazil)]. E-mail: cqueiroz@ipen.br; Pedreira, Walter R.; Boaventura, Geraldo R. [Brasilia Univ., DF (Brazil). Dept. de Geociencias; Pimentel, Marcio M. [Fundacao Jorge Duprat Figueiredo de Seguranca e Medicina do Trabalho (FUNDACENTRO), Sao Paulo, SP (Brazil)]. E-mail: walter.pedreira@fundacentro.gov.br

    2005-11-15

    several years, IPEN/CNEN-SP has been working in the separation of the Rare Earth (RE) elements. A simple and economic procedure for the purification of technical grade cerium concentrate is described. The highly pure cerium dioxide is designed to be used as spectrochemical standard. It is obtained by association of the fractional precipitation technique, in the system RECl{sub 3}/NH{sub 4}OH/ Air/H{sub 2}O{sub 2}, to enrich the cerium up to 90% and then it is upgraded by ion exchange technique to 99.99% CeO{sub 2}. The quality control warranty was accomplished by inductively coupled mass spectrometry (ICP-MS) and neutron activation analysis. The collected values for the accompanying Rare Earth elements in a CeO{sub 2} sample are the following (ppm): La(36), Pr(19), Nd(161), Sm(11), Eu(5.3), Gd(113), Tb(89), Dy(2), Ho(0.05), Er(1), Tm(<0.05), Yb(11), Lu(19) and Y(2.1), respectively. The purity of this cerium oxide is comparable to the international spectrographic standards. (author)

  1. Fractionation and Characterization of High Aspect Ratio Gold Nanorods Using Asymmetric-Flow Field Flow Fractionation and Single Particle Inductively Coupled Plasma Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Thao M. Nguyen

    2015-07-01

    Full Text Available Gold nanorods (GNRs are of particular interest for biomedical applications due to their unique size-dependent longitudinal surface plasmon resonance band in the visible to near-infrared. Purified GNRs are essential for the advancement of technologies based on these materials. Used in concert, asymmetric-flow field flow fractionation (A4F and single particle inductively coupled mass spectrometry (spICP-MS provide unique advantages for fractionating and analyzing the typically complex mixtures produced by common synthetic procedures. A4F fractions collected at specific elution times were analyzed off-line by spICP-MS. The individual particle masses were obtained by conversion of the ICP-MS pulse intensity for each detected particle event, using a defined calibration procedure. Size distributions were then derived by transforming particle mass to length assuming a fixed diameter. The resulting particle lengths correlated closely with ex situ transmission electron microscopy. In contrast to our previously reported observations on the fractionation of low-aspect ratio (AR GNRs (AR < 4, under optimal A4F separation conditions the results for high-AR GNRs of fixed diameter (≈20 nm suggest normal, rather than steric, mode elution (i.e., shorter rods with lower AR generally elute first. The relatively narrow populations in late eluting fractions suggest the method can be used to collect and analyze specific length fractions; it is feasible that A4F could be appropriately modified for industrial scale purification of GNRs.

  2. In vivo monitoring of quantum dots in the extracellular space using push-pull perfusion sampling, online in-tube solid phase extraction, and inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Su, C K; Huang, C W; Yang, C S; Wang, Y J; Sun, Y C

    2010-09-01

    To monitor the dynamic changes of extracellular quantum dots (QDs) in vivo in the livers of anesthetized rats, we developed an automatic online analytical system comprising push-pull perfusion (PPP) sampling, the established in-tube solid phase extraction (SPE) procedure, and inductively coupled plasma mass spectrometry (ICPMS). The method takes advantage of the retention of QDs onto the interior surface of a polytetrafluoroethylene (PTFE) tube as a means of extracting the QDs from complicated push-pull perfusates. For the injected QDs present in the liver extracellular fluid (ECF) at low picomolar levels, a temporal resolution of 10 min was required to collect sufficient amounts of QDs to meet the sensitivity requirements of the ICPMS system. To the best of our knowledge, this study is the first to exploit the PPP technique for the collection of QDs from living animals and PTFE tubing as a SPE adsorbent for the online extraction of QDs and the removal of biological matrix prior to ICPMS analysis of cadmium-containing inorganic nanocrystal. We confirmed the analytical reliability of this method from measurements of the spike recoveries of saline samples; in addition, we demonstrated the systems' applicability through in vivo monitoring of the time-dependent concentration profile of liver extracellular QDs in living rats after intravenous administration.

  3. 微波消解-电感耦合等离子体质谱法检测虾中铅含量%Determination of lead in shrimps by microwave digestion and inductively coupled plasma mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    李倩云; 周国燕; 曹蕾

    2016-01-01

    建立微波消解-电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry,ICP-MS)测定虾中铅的方法.在单因素试验基础上,通过正交试验分析研究H2O2量、HNO3量、微波消解时间对虾中铅提取量的影响,优选虾中铅的提取条件.结果表明:在H2O2量为1.0 mL、HNO3量为5 mL、微波消解时间为13 min条件下,虾中铅含量可达到0.497 mg/kg.检测国家标准物质GBW10050(大虾)进行方法验证,结果与标准值一致.方法检出限为0.01μ g/kg,平行测定RSD(n =6)小于5%.该方法能够简单、快速、灵敏和准确地测定虾中的重金属铅元素.

  4. Elemental ratios for characterization of quantum-dots populations in complex mixtures by asymmetrical flow field-flow fractionation on-line coupled to fluorescence and inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Menendez-Miranda, Mario; Fernandez-Arguelles, Maria T.; Costa-Fernandez, Jose M., E-mail: jcostafe@uniovi.es; Encinar, Jorge Ruiz; Sanz-Medel, Alfredo, E-mail: asm@uniovi.es

    2014-08-11

    Highlights: • The hyphenated system allows unequivocal identification of nanoparticle populations. • AF4 separation permitted detection of unexpected nanosized species in a sample. • ICP-QQQ provides elemental ratios with adequate accuracy in every nanoparticle. • Purity and chemical composition of different quantum dot samples were assessed. - Abstract: Separation and identification of nanoparticles of different composition, with similar particle diameter, coexisting in heterogeneous suspensions of polymer-coated CdSe/ZnS quantum dots (QDs) have been thoroughly assessed by asymmetric flow field-flow fractionation (AF4) coupled on-line to fluorescence and inductively coupled plasma mass spectrometry (ICPMS) detectors. Chemical characterization of any previously on-line separated nanosized species was achieved by the measurement of the elemental molar ratios of every element involved in the synthesis of the QDs, using inorganic standards and external calibration by flow injection analysis (FIA). Such elemental molar ratios, strongly limited so far to pure single nanoparticles suspensions, have been achieved with adequate accuracy by coupling for the first time an ICP-QQQ instrument to an AF4 system. This hyphenation turned out to be instrumental to assess the chemical composition of the different populations of nanoparticles coexisting in the relatively complex mixtures, due to its capabilities to detect the hardly detectable elements involved in the synthesis. Interestingly such information, complementary to that obtained by fluorescence, was very valuable to detect and identify unexpected nanosized species, present at significant level, produced during QDs synthesis and hardly detectable by standard approaches.

  5. Determination of thorium and light rare-earth elements in soil water and its high molecular mass organic fractions by inductively coupled plasma mass spectrometry and on-line-coupled size-exclusion chromatography.

    Science.gov (United States)

    Casartelli, Evelton A; Miekeley, Norbert

    2003-09-01

    Inductively coupled plasma mass spectrometry (ICP-MS) has been used for the determination of thorium and light rare-earth elements (LREEs) in soil and soil water samples from a mineral deposit (Morro do Ferro, Minas Gerais, Brazil). Size-exclusion chromatography (SEC) on-line coupled to ICP-MS and UV-detection was applied to verify possible association/complexation of these elements with organic matter in soil water separated by a centrifugation technique. Concentrations of DOC in soil waters are in the range of 10 to 500 mg L(-1) and correlate with the organic carbon content of the soil (r=0.950; p10,000 Da, with a retention time of about 10 min; 7000 to 8000 Da with retention times of 13 to 15 min; and 2000 to 4000 Da with retention times around 23 min. Elemental peaks associated with dissolved organic matter below 1000 Da were not observed, suggesting that complexation with simple plant organic acids or inorganic ligands is of minor importance in the environment studied in this work.

  6. Differentiating the Bishop ash bed and related tephra layers by elemental-based similarity coefficients of volcanic glass shards using solution inductively coupled plasma-mass spectrometry (S-ICP-MS)

    Science.gov (United States)

    Knott, J.R.; Sarna-Wojcicki, A. M.; Montanez, I.P.; Wan, E.

    2007-01-01

    Volcanic glass samples from the same volcanic center (intra-source) often have a similar major-element composition. Thus, it can be difficult to distinguish between individual tephra layers, particularly when using similarity coefficients calculated from electron microprobe major-element measurements. Minor/trace element concentrations in glass can be determined by solution inductively coupled plasma mass spectrometry (S-ICP-MS), but have not been shown as suitable for use in large tephrochronologic databases. Here, we present minor/trace-element concentrations measured by S-ICP-MS and compare these data by similarity coefficients, the method commonly used in large databases. Trial samples from the Bishop Tuff, the upper and lower tuffs of Glass Mountain and the tuffs of Mesquite Spring suites from eastern California, USA, which have an indistinguishable major-element composition, were analyzed using S-ICP-MS. The resulting minor/trace element similarity coefficients clearly separated the suites of tephra layers and, in most cases, individual tephra layers within each suite. Comparisons with previous instrumental neutron activation analysis (INAA) elemental measurements were marginally successful. This is important step toward quantitative correlation in large tephrochronologic databases to achieve definitive identification of volcanic glass samples and for high-resolution age determinations. ?? 2007 Elsevier Ltd and INQUA.

  7. Determination of trace Cd, Cu, Fe, Pb and Zn in diesel and gasoline by inductively coupled plasma mass spectrometry after sample clean up with hollow fiber solid phase microextraction system

    Energy Technology Data Exchange (ETDEWEB)

    Nomngongo, Philiswa N.; Ngila, J. Catherine, E-mail: jcngila@uj.ac.za

    2014-08-01

    This study reports a simple and efficient method for the determination of trace Cd, Cu, Fe, Pb and Zn in diesel and gasoline samples by inductively coupled plasma mass spectrometry after matrix removal and analyte pre-concentration using hollow fiber-solid phase microextraction (HF–SPME). The optimization of HF-SPME procedure was carried out using two-level full factorial and central composite designs. Four factors (variables), that are, sample solution pH, acceptor phase amount, extraction time and eluent concentration were optimized. Under the optimized experimental conditions, the precision was ≤ 3% (C = 10 μg L{sup −1}, n = 15), limits of detection and quantification ranged from 0.1 to 0.3 μg L{sup −1} and 0.3–0.9 μg L{sup −1}, respectively, and the maximum preconcentration factor was 30. The HF-SPME method was applied for the determination of trace metals in real gasoline and diesel samples. - Highlights: • Hollow fiber solid phase microextraction of metal ions in diesel and gasoline • Use of hollow fiber-supported sol–gel combined with cation exchange resin • Optimization of HF-SPME using multivariate techniques • Determination of Cd, Cu, Fe, Pb and Zn using ICP–MS • Relatively low LOD and LOQ.

  8. Determination of ultra-trace amount methyl-, phenyl- and inorganic mercury in environmental and biological samples by liquid chromatography with inductively coupled plasma mass spectrometry after cloud point extraction preconcentration.

    Science.gov (United States)

    Chen, Jianguo; Chen, Hengwu; Jin, Xianzhong; Chen, Haiting

    2009-02-15

    The cloud point extraction (CPE) preconcentration of ultra-trace amount of mercury species prior to reverse-phase high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS) detection was studied. Mercury species including methyl-, ethyl-, phenyl- and inorganic mercury were transformed into hydrophobic chelates by reaction with sodium diethyldithiocarbamate, and the hydrophobic chelates were extracted into a surfactant-rich phase of Triton X-114 upon heating in a water bath at 40 degrees C. Ethylmercury was found partially decomposed during the CPE process, and was not included in the developed method. Various experimental conditions affecting the CPE preconcentration, HPLC separation, and ICP-MS determination were optimized. Under the optimized conditions, detection limits of 13, 8 and 6 ng l(-1) (as Hg) were achieved for MeHg(+), PhHg(+) and Hg(2+), respectively. Seven determinations of a standard solution containing the three mercury species each at 0.5 ng ml(-1) level produced relative standard deviations of 5.3, 2.3 and 4.4% for MeHg(+), PhHg(+) and Hg(2+), respectively. The developed method was successfully applied for the determination of the three mercury species in environmental water samples and biological samples of human hair and ocean fish.

  9. On-line speciation of inorganic and methyl mercury in waters and fish tissues using polyaniline micro-column and flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS).

    Science.gov (United States)

    Krishna, M V Balarama; Chandrasekaran, K; Karunasagar, D

    2010-04-15

    A simple and efficient method for the determination of ultra-trace amounts of inorganic mercury (iHg) and methylmercury (MeHg) in waters and fish tissues was developed using a micro-column filled with polyaniline (PANI) coupled online to flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS) system. Preliminary studies indicated that inorganic and methyl mercury species could be separated on PANI column in two different speciation approaches. At pH extraction of the mercury species from biological samples, was used directly to separate MeHg from iHg in the fish tissues (tuna fish ERM-CE 463, ERM-CE 464 and IAEA-350) by PANI column using speciation procedure 1. The determined values were in good agreement with certified values. Under optimal conditions, the limits of detection (LODs) were 2.52 pg and 3.24 pg for iHg and MeHg (as Hg) respectively. The developed method was applied successfully to the direct determination of iHg and MeHg in various waters (tap water, lake water, ground water and sea-water) and the recoveries for the spiked samples were in the range of 96-102% for both the Hg species.

  10. Implementation of Online Preconcentration and Microsecond Time Resolution to Capillary Electrophoresis Single Particle Inductively Coupled Plasma Mass Spectrometry (CE-SP-ICP-MS) and Its Application in Silver Nanoparticle Analysis.

    Science.gov (United States)

    Mozhayeva, Darya; Strenge, Ingo; Engelhard, Carsten

    2017-07-05

    Capillary electrophoresis (CE) coupled to single particle inductively coupled plasma mass-spectrometry (SP-ICP-MS) was used for the first time with a prototype data acquisition (μsDAQ) system that features 5 μs time resolution (100% duty cycle) to separate and quantify mixtures of silver nanoparticles (Ag NPs). Additionally, an online preconcentration technique, reversed electrode polarity stacking mode (REPSM), was applied for Ag NPs analysis with CE-SP-ICP-MS for the first time. After optimization, best results were achieved using a injection time of 110 s and a constant pressure of 50 mbar in hydrodynamic injection mode. It was possible to detect 14.3 ± 1.5× more 20 nm sized, 21.0 ± 4.2× more 40 nm sized, and 27.7 ± 4.9× more 60 nm sized Ag NPs compared to the standard injection time of only 3 s. The effect of applied voltage on the NPs separation was studied, and a CE separation at 20 kV was found to be optimal for the present setup. The capability of CE-SP-ICP-MS for quantification of particle number concentration was investigated, and detection limits in the submicrogram-per-liter range were achieved. The possibility to separate 20, 40, and 60 nm sized Ag NPs simultaneously present in a mixture was demonstrated over a broad concentration range.

  11. Results of an interlaboratory method performance study for the size determination and quantification of silver nanoparticles in chicken meat by single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS).

    Science.gov (United States)

    Weigel, Stefan; Peters, Ruud; Loeschner, Katrin; Grombe, Ringo; Linsinger, Thomas P J

    2017-08-01

    Single-particle inductively coupled plasma mass spectrometry (sp-ICP-MS) promises fast and selective determination of nanoparticle size and number concentrations. While several studies on practical applications have been published, data on formal, especially interlaboratory validation of sp-ICP-MS, is sparse. An international interlaboratory study was organized to determine repeatability and reproducibility of the determination of the median particle size and particle number concentration of Ag nanoparticles (AgNPs) in chicken meat. Ten laboratories from the European Union, the USA, and Canada determined particle size and particle number concentration of two chicken meat homogenates spiked with polyvinylpyrrolidone (PVP)-stabilized AgNPs. For the determination of the median particle diameter, repeatability standard deviations of 2 and 5% were determined, and reproducibility standard deviations were 15 and 25%, respectively. The equivalent median diameter itself was approximately 60% larger than the diameter of the particles in the spiking solution. Determination of the particle number concentration was significantly less precise, with repeatability standard deviations of 7 and 18% and reproducibility standard deviations of 70 and 90%.

  12. Determination of Trace Elements in Water by Inductively Coupled Plasma Mass Spectrometry%电感耦合等离子体质谱法测定水中痕量元素

    Institute of Scientific and Technical Information of China (English)

    王霞; 陈素兰; 王经顺

    2012-01-01

    应用电感耦合等离子体质谱法对水样(地表水、饮用水等)中铜、锌、硒、砷、镉、铬、铅、铁、锰等痕量元素进行分析测定。结果表明,方法检出限为0.01~0.78μg/L,平行测定的相对标准偏差为0.6%~7.9%,实际水样加标回收率为90.5%~103%。该方法快速、简便、线性范围大,具有良好的检出限和准确度。%The application of inductively coupled plasma mass spectrometry for water samples (surface water, drinking water, etc. ) , copper, zinc, selenium, arsenic, cadmium, chromium, lead, iron, manganese and other trace dements were analyzed. The results showed that the detection limit was 0.01-0.78μg/L, the relative standard deviation of parallel samples was 0.6% to 7.9%, and the recovery of added standards in water samples ranged from 90.5% to 103%. The method was rapid, simple, linear range and good detection limits and accuracy.

  13. Methodology for monitoring gold nanoparticles and dissolved gold species in culture medium and cells used for nanotoxicity tests by liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    López-Sanz, Sara; Fariñas, Nuria Rodríguez; Vargas, Rosario Serrano; Martín-Doimeadios, Rosa Del Carmen Rodríguez; Ríos, Ángel

    2017-03-01

    An analytical methodology based on coupling reversed-phase liquid chromatography (HPLC) to an inductively coupled plasma mass spectrometry (ICP-MS) has been developed for the characterization and identification of gold nanoparticles (AuNPs) and gold dissolved species (Au(3+)) in culture medium (Dulbecco's Modified Eagle Medium, DMEM) and HeLa cells (a human cervical adenocarcinoma cell line) used in nanotoxicity tests. The influence of the culture medium was also studied and the method applied for nanotoxicity tests. It was also observed that AuNPs can undergo an oxidation process in the supernatants and only a small amount of AuNPs and dissolved Au(3+) was associated with cells. To evaluate the biological impact of AuNPs, a classical viability assay onto HeLa cells was performed using cellular media DMEM in the presence of increasing dosage of 10nm AuNPs. The results showed that 10nm AuNPs exhibit a slight toxic effect.

  14. 高分辨电感耦合等离子体质谱法测定地下水中稀土元素%Determination of Rare Earth Elements in Groundwater by High Resolution Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    程青; 蔡述伟; 李华玲; 蔡小虎; 白晓

    2015-01-01

    采用高分辨电感耦合等离子体质谱法测定地下水中14种稀土元素,并选择Rh作内标,可消除测定中的质谱干扰和非质谱干扰,使方法在0μg/L~100μg/L范围内线性良好。方法检出限为0.002μg/L~0.005μg/L,实际水样的加标回收率为80.0%~117%,RSD为2.1%~3.8%。%14 rare earth elements were detected by high resolution inductively coupled plasma mass spec-trometry (HR-ICP-MS),by choosing Rh as a internal standard,the mass spectral interference and non-interfer-ence in the detection could be eliminated and the result showed a good linearity in the range of 0 μg/L ~100 μg/L.The detection limits of this method were 0.002 μg/L~0.005 μg/L,the recoveries of actual water samples ranged from 80.0%to 117%,and the RSDs were 2.1%~3.8%.

  15. DETERMINATION OF URANIUM IN SOFT DRINK BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY%电感耦合等离子体质谱法测定饮料中的铀

    Institute of Scientific and Technical Information of China (English)

    杨彦丽; 周谙非; 陈光

    2009-01-01

    The method for determination of uranium in soft drinking by inductively coupled plasma mass spectrometry (ICP-MS) was established. Sample preparation for different soft drink was investigated and precision and recovery results were evaluated. The relative standard deviations (RSDs) were 1.67%-8.21% (n =6), the spiked recovery were 96.0%-109.0% and the detection limit was 0.010μg ·l~(-1). The method was accurate and reliable.%建立了电感耦合等离子体质谱法(ICP-MS)测定饮料中的铀.对不同基质的饮料进行了前处理方法的摸索,从精密度和回收率考察了方法的准确性,相对标准偏差(RSD)为1.67%-8.21%(n=6),加标回收率为96.0%-109.0%,方法检出限为0.010μg·l~(-1),方法准确可靠.

  16. 电感耦合等离子体法测定地质样品中的铷%Determination of Rubidium in Geological Samples by Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    高静; 陈述

    2011-01-01

    建立了电感耦合等离子体质谱法测定地质化探样品中铷的方法.样品经HCl-HNO3-HF-HClO4敞口酸溶后,用电感耦合等离子体质谱仪测定其中的铷含量.该法用于土壤、岩石中铷的测定,检出限为3.2ng/g,相对标准偏差小于3%,加标回收率在90%~120%之间.%A method was established for determinating rubidium in geological samples by inductively coupled plasma mass spectrometry(ICP-MS) , with which the content of rubidium was measured by ICP-MS after the samples were dissolved with a mixed acid of HC1-HNO3-HF-HC1O4 in an open container. The method was applied to the determination of rubidium in soil or rock, with a detection limit of 3.2 ng/g, relative standard deviation less than 3% and the recovery by standard addition method ranging from 90% to 120%.

  17. Analysis of iron, zinc, selenium and cadmium in paraffin-embedded prostate tissue specimens using inductively coupled plasma mass-spectrometry

    Science.gov (United States)

    Sarafanov, A.G.; Todorov, T.I.; Kajdacsy-Balla, A.; Gray, Michael A.; MacIas, V.; Centeno, J.A.

    2008-01-01

    Formalin-fixed paraffin-embedded (FFPE) tissue specimens represent a valuable and abundant resource of pathologic material for various biomedical studies. In the present study, we report the application of high-resolution inductively coupled mass-spectrometry (ICP-MS) for quantification of Fe, Zn, Se and Cd in FFPE prostate tissue. These elements have a possible role in the development of prostate diseases: while Zn and Se are needed for a healthy prostate, Cd shows multiple toxic and carcinogenic effects. Excessive accumulation of Fe induces the production of highly reactive hydroxyl radical species, which may play a role in cancer etiopathogenesis. To assess whether the levels of these metals in the FFPE prostate tissue represent their original content, we compared their levels with those in the fresh tissue (on dry weight basis) in samples obtained from 15 patients. We found that in FFPE tissue, the recoveries of Se, Fe, Cd and Zn were progressively decreased, 97??11% (r=0.88), 82??22% (r=0.86), 59??23% (r=0.69) and 24??11% (r=0.38), respectively. Thus, the use of correction factors, determined as k=0.16 for Se, k=0.20 for Fe, k=0.27 for Cd and k=0.67 for Zn, is required to estimate the retrospective levels of these elements in the parental non-processed fresh (wet) prostate tissue. The technique used in this study enables the analysis of archival FFPE prostate tissue for the concentrations of Fe, Zn, Se and Cd to study association between the levels of these metals and prostate disease. ?? 2008.

  18. Determination of copper in coal fly ash in the presence of excess titanium by dynamic reaction cell inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Liu, Hui-Tao; Jiang, Shiuh-Jen

    2003-01-01

    Inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) was used for the accurate determination of copper in coal fly ash samples in the presence of excess titanium, using the reaction of Cu(+) ions with NH(3) in the cell. The method eliminated the effect of polyatomic isobaric interferences at m/z 63 and 65 caused by the formation of (47)Ti(16)O(+), (49)Ti(16)O(+) and (47)Ti(18)O(+) on (63)Cu(+) and (65)Cu(+) by detecting Cu(+) as the product cluster ion Cu(NH(3))(2)(+). As the signal of (63)Cu(NH(3))(2)(+) overlapped with that of (97)Mo(+) which existed in the samples, (65)Cu(NH(3))(2)(+) was detected at m/z 99. The effect of the operating conditions of DRC system was studied in order to obtain the best signal to noise ratio for Cu(NH(3))(2)(+) at m/z 99. The formation of Cu(NH(3))(2)(+) was through the clustering reaction Cu(+)+2NH(3)-->Cu(NH(3))(2)(+) which resulted in the separation of analyte from the interfering oxide. The detection limit for Cu(NH(3))(2)(+) was 0.015 ng mL(-1) as Cu. The method was applied to the determination of copper in NIST SRM 1633a and 1633b coal fly ash reference materials. The precision between sample replicates was better than 2.0% and the analysis results were in good agreement with the certified values.

  19. Determination of copper in coal fly ash in the presence of excess titanium by dynamic reaction cell inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hui-Tao [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Jiang, Shiuh-Jen [Department of Chemistry, National Sun Yat-sen University, Kaohsiung 80424 (Taiwan)

    2003-01-01

    Inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) was used for the accurate determination of copper in coal fly ash samples in the presence of excess titanium, using the reaction of Cu{sup +} ions with NH{sub 3} in the cell. The method eliminated the effect of polyatomic isobaric interferences at m/z 63 and 65 caused by the formation of {sup 47}Ti{sup 16}O{sup +}, {sup 49}Ti{sup 16}O{sup +} and {sup 47}Ti{sup 18}O{sup +} on {sup 63}Cu{sup +} and {sup 65}Cu{sup +} by detecting Cu{sup +} as the product cluster ion Cu(NH{sub 3}){sub 2}{sup +}. As the signal of {sup 63}Cu(NH{sub 3}){sub 2}{sup +} overlapped with that of {sup 97}Mo{sup +} which existed in the samples, {sup 65}Cu(NH{sub 3}){sub 2}{sup +} was detected at m/z 99. The effect of the operating conditions of DRC system was studied in order to obtain the best signal to noise ratio for Cu(NH{sub 3}){sub 2}{sup +} at m/z 99. The formation of Cu(NH{sub 3}){sub 2}{sup +} was through the clustering reaction Cu{sup +}+2NH{sub 3}{yields}Cu(NH{sub 3}){sub 2}{sup +} which resulted in the separation of analyte from the interfering oxide. The detection limit for Cu(NH{sub 3}){sub 2}{sup +} was 0.015 ng mL{sup -1} as Cu. The method was applied to the determination of copper in NIST SRM 1633a and 1633b coal fly ash reference materials. The precision between sample replicates was better than 2.0% and the analysis results were in good agreement with the certified values. (orig.)

  20. Influence of relative abundance of isotopes on depth resolution for depth profiling of metal coatings by laser ablation inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Fariñas, Juan C; Coedo, Aurora G; Dorado, Teresa

    2010-04-15

    A systematic study on the influence of relative abundance of isotopes of elements in the coating (A(c)) and in the substrate (A(s)) on both shape of time-resolved signals and depth resolution (Delta z) was performed for depth profile analysis of metal coatings on metal substrates by ultraviolet (266 nm) nanosecond laser ablation inductively coupled plasma quadrupole mass spectrometry. Five coated samples with coating thicknesses of the same order of magnitude (20-30 microm) were tested: nickel coating on aluminium, chromium and copper, and steel coated with copper and zinc. A laser repetition rate of 1 Hz and a laser fluence of 21 J cm(-2) were used. Five different depth profile types were established, which showed a clear dependence on A(c)/A(s) ratio. In general, depth profiles obtained for ratios above 1-10 could not be used to determine Delta z. We found that Delta z increased non-linearly with A(c)/A(s) ratio. The best depth profile types, leading to highest depth resolution and reproducibility, were attained in all cases by using the isotopes with low/medium A(c) values and with the highest A(s) values. In these conditions, an improvement of up to 4 times in Delta z values was achieved. The average ablation rates were in the range from 0.55 microm pulse(-1) for copper coating on steel to 0.83 microm pulse(-1) for zinc coating on steel, and the Delta z values were between 2.74 microm for nickel coating on chromium and 5.91 microm for nickel coating on copper, with RSD values about 5-8%.

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

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, Sergei F. [Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University Mainz, Duesbergweg 10-14, 55099 Mainz (Germany)]. E-mail: sergei.boulyga@univie.ac.at; Heumann, Klaus G. [Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University Mainz, Duesbergweg 10-14, 55099 Mainz (Germany)

    2006-07-01

    A method by inductively coupled plasma mass spectrometry (Icp-Ms) was developed which allows the measurement of {sup 236}U at concentration ranges down to 3 x 10{sup -14} g g{sup -1} and extremely low {sup 236}U/{sup 238}U isotope ratios in soil samples of 10{sup -7}. By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5000 counts fg{sup -1} uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH{sup +}/U{sup +} down to a level of 10{sup -6}. An abundance sensitivity of 3 x 10{sup -7} was observed for {sup 236}U/{sup 238}U isotope ratio measurements at mass resolution 4000. The detection limit for {sup 236}U and the lowest detectable {sup 236}U/{sup 238}U isotope ratio were improved by more than two orders of magnitude compared with corresponding values by alpha spectrometry. Determination of uranium in soil samples collected in the vicinity of Chernobyl nuclear power plant (NPP) resulted in that the {sup 236}U/{sup 238}U isotope ratio is a much more sensitive and accurate marker for environmental contamination by spent uranium in comparison to the {sup 235}U/{sup 238}U isotope ratio. The ICP-MS technique allowed for the first time detection of irradiated uranium in soil samples even at distances more than 200 km to the north of Chernobyl NPP (Mogilev region). The concentration of {sup 236}U in the upper 0-10 cm soil layers varied from 2 x 10{sup -9} g g{sup -1} within radioactive spots close to the Chernobyl NPP to 3 x 10{sup -13} g g{sup -1} on a sampling site located by >200 km from Chernobyl.

  2. A novel quantification strategy of transferrin and albumin in human serum by species-unspecific isotope dilution laser ablation inductively coupled plasma mass spectrometry (ICP-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Liuxing, E-mail: fenglx@nim.ac.cn; Zhang, Dan; Wang, Jun; Shen, Dairui; Li, Hongmei

    2015-07-16

    Highlights: • Species-unspecific ID-PAGE-LA-ICP-MS was used to quantify Alb and Tf in human serum. • Addition methods of species-unspecific {sup 34}S spike were evaluated. • Isotope change conditions were investigated to reach satisfactory “isotope equilibration”. • Human serum CRM (ERM-DA470k/IFCC) was used to validate the new arrangements. • The developed method offers potential for accurate quantification of protein by ID-PAGE-LA-ICP-MS. - Abstract: Species-specific (SS) isotope dilution analysis with gel electrophoresis (GE)-laser ablation (LA)-ICP-MS is a promising technique for the quantification of particular metal-binding proteins in biological samples. However, unavailable isotopically enriched spike and metal losses in GE separation are main limitations for SS-isotope dilution PAGE-LA-ICP-MS. In this study, we report for the first time the absolute quantification of transferrin (Tf) and albumin (Alb) in human serum by non-denaturing (native) GE combined with species-unspecific isotope dilution mass spectrometry (IDMS). In order to achieve a homogeneous distribution of both protein and isotope-enriched spike (simulated isotope equilibration), immersing the protein strips with {sup 34}S spike solution after gel electrophoresis was demonstrated to be an effective way of spike addition. Furthermore, effects of immersion time and {sup 34}S spike concentration were investigated to obtain optimal conditions of the post-electrophoresis isotope dilution method. The relative mass of spike and ablated sample (m{sub sp}/m{sub sam}) in IDMS equation was calculated by standard Tf and Alb proteins, which could be applied to the quantification of Tf and Alb in ERM-DA470k/IFCC for method confirmation. The results were in agreement with the certified value with good precision and small uncertainty (1.5–3%). In this method, species-specific spike protein is not necessary and the integrity of the heteroatom-protein could be maintained in sample preparation

  3. Gas-flow optimization studies on brass samples using closed and open types of laser ablation cells in inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kantor, Tibor, E-mail: kantort@mafi.hu; Kiraly, Edit; Bertalan, Eva; Bartha, Andras

    2012-02-15

    The effect of the carrier gas flow rate on laser ablation inductively coupled mass spectrometry (LA-ICP-MS) signals of brass components (Cu, Zn, and Ni) were studied primarily with the use of a conventional closed ablation cell (UP-213) and with the use of an open ablation cell of our own construction. In the closed ablation cell configuration with the carrier gas flow rate in the range of 0.40-1.3 L min{sup -1} Ar, the MS signals increased significantly (an 8.2-fold increase for a Cu signal), and the Zn/Cu signal ratio increased 3.2 times. To identify the degree of fractionation, the conventional solution sample introduction method was selected as the reference method because it is expected free from fractionation for Cu and Zn. To obtain a theoretical value, calculations were made based on Saha's relationship of ionization, which resulted in fair agreement with the experimental results of the solution method. By comparing the Zn/Cu signal ratios obtained from both the LA and the solution method, a fractionation factor of 2.26 was deduced for these two components. To explain the increased signals described above, the transport efficiency as a function of the carrier gas flow rate was calculated for different particle size fractions based on existing theories. It was demonstrated that the large increase in the signals with carrier gas flow rate is predominantly due to processes taking place in the ablation cell (i.e., neither during the transportation nor in the ICP). The results of the novel fundamental works on aerosol formation under LA conditions were considered and complemented with the application of the Kelvin (Gibbs-Thomson) equation to calculate critical sizes of aerosol particles in the nucleating vapors of Cu, Zn, Ni and Pb elements. It was concluded that the noted increase of signals was due to the intensification of mixing of the expanding vapor-cloud with cold gas when applying an increasing carrier gas flow rate. It was also concluded that the

  4. Development of an inductively coupled plasma mass spectrometry method for quantification of extracted tungsten from glass prefilled syringes used as a primary packaging for pharmaceutical and therapeutic protein products.

    Science.gov (United States)

    Fujimori, Kiyoshi; Lee, Hans; Phillips, Joseph; Nashed-Samuel, Yasser

    2013-01-01

    Leachable tungsten is associated with protein aggregation and precipitation in glass prefilled syringes, and this may trigger immunogenicity concerns. Determining the level of leachable tungsten from glass prefilled syringes is critical for assuring quality of certain biopharmaceutical drug products. An inductively coupled plasma mass spectrometry (ICP/MS) quantification method was developed to determine elemental tungsten in syringe extracts. The syringe was extracted using 0.5% ammonium hydroxide (pH 11), heat (75 °C), and sonication. The resulting extraction solution was diluted 10 fold prior to ICP/MS analysis. Syringes from three syringe lots containing known low (average 28.0 ng), medium (average 189.4 ng), and high (average 631.9 ng) levels of tungsten were extracted three times each. All syringes with total tungsten greater than 14 ng had extraction efficiency greater than 90% with the first two extractions combined. The calibration curve range was 0.1-200 μg/L tungsten with iridium as the internal standard, and the correlation coefficient was ≥1.0000. The limit of detection at 0.05 μg/L tungsten and limit of quantification at 0.1 μg/L tungsten were determined as having a signal-to-noise ratio greater than 40 and 80 times compared with the blank, respectively. The ICP/MS method was selective for tungsten and iridium in the presence of other metals. Accuracies of spiked tungsten, at three different levels, in syringe extracts were >99% with precision relative standard deviation (RSD) (n = 5) of ≤1%. The matrix effect of the syringe extract media and carryover of tungsten and internal standard were negligible. Onboard stability of the syringe extracts over three days had a tungsten concentration RSD (n = 3) of ≤1%. Syringe extractions performed with 0.45-0.55% ammonium hydroxide had spike recoveries ≥99% and demonstrated extraction solution robustness. Quantified residual tungsten in syringes extract by ammonium hydroxide and analyzed by ICP

  5. Selenium speciation in radix puerariae using ultrasonic assisted extraction combined with reversed phase high performance liquid chromatography-inductively coupled plasma-mass spectrometry after magnetic solid-phase extraction with 5-sulfosalicylic acid functionalized magnetic nanoparticles

    Science.gov (United States)

    Cao, Yupin; Yan, Lizhen; Huang, Hongli; Deng, Biyang

    2016-08-01

    A new method for determination of selenium species in radix puerariae was described. The method consists of sample enrichment with 5-sulfosalicylic acid (SSA)-functionalized silica-coated magnetic nanoparticles (SMNPs), high performance liquid chromatography (HPLC) separation, and online detection using inductively coupled plasma mass spectrometry (ICP-MS). The selenium species were extracted using ultrasonic extraction system with a mixture of protease K and lipase. The SSA-SMNPs were used to enrich trace amounts of selenite [Se(IV)], selenate [Se(VI)], selenomethionine (SeMet), and selenocystine (SeCys2) from lower selenium containing samples. Under the optimal conditions, the limits of detection (3σ) for SeCys2, Se(IV), SeMet and Se(VI) were observed as 0.0023, 0.0015, 0.0043, and 0.0016 ng mL- 1, respectively. The RSD values (n = 6) of method for intraday were observed between 0.5% and 0.9%. The RSD values of method for interday were less than 1.3%. The linear concentration ranges for SeCys2, Se(IV), SeMet and Se(VI) were 0.008-1000, 0.005-200, 0.015-500 and 0.006-200 ng mL- 1, respectively. The detection limits of this method were improved by 10 times due to the enrichment with the SSA-SMNP extraction. The contents of SeCys2, Se(IV), SeMet, and Se(VI) in radix puerariae were determined as 0.0140, 0.171, 0.0178, and 0.0344 μg g- 1, respectively. The recoveries were in the range of 95.6%-99.4% and the RSDs (n = 6) of recoveries were less than 1.5%.

  6. Optimization of capillary electrophoresis-inductively coupled plasma mass spectrometry for species analysis of metallothionein-like proteins extracted from liver tissues of Elbe-bream and Roe deer

    Energy Technology Data Exchange (ETDEWEB)

    Proefrock, Daniel; Prange, Andreas E-mail: andreas.prange@gkss.de; Schaumloeffel, Dirk; Ruck, Wolfgang

    2003-08-15

    Species analysis of metallothionein-like proteins (MLP) in liver tissues from Elbe-Bream (Abramis brama L.) and Roe Deer (Capreolus capreolus L.) using capillary electrophoresis (CE) combined with inductively coupled plasma mass spectrometry detection is described. In order to allow systematic development of the method, commercially available metallothionein (MT) preparations of rabbit liver were used. Optimum separation efficiency was obtained by investigating the influence of parameters such as voltage, capillary temperature, buffer concentration, buffer pH and the use of different buffer systems. Instrumental parameters such as CE capillary position, interface adjustment and contamination problems are also discussed. Separation was performed using uncoated fused silica capillaries with 75 {mu}m i.d. and 70 cm length. The optimum conditions were found to be: Separation voltage 30 kV, positive polarity, capillary temperature 288.15 K and a buffer concentration of 100 mmol l{sup -1} Tricine-NH{sub 3} adjusted to pH 7.2. Sample preparation was performed so as to minimize oxidation and heavy metal contamination of the samples. The high molecular mass protein matrix was reduced by acetonitrile precipitation. For commercial MT preparations the relative standard deviations (R.S.D) in the retention times were 0.9% for MT-1 and 1.9% for MT-2; the R.S.D.'s in the peak areas were less than 6% for MT-1 and 16% for MT-2, respectively. Under optimized conditions the MLPs in the real samples could be separated efficiently in less than 10 min. By comparison with the migration times of commercially available MT preparations, two of the observed peaks could be assigned to MT-1 and MT-2.

  7. Estimation of the bio-accessible fraction of Cr, As, Cd and Pb in locally available bread using on-line continuous leaching method coupled to inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Lamsal, Ram P; Beauchemin, Diane

    2015-03-31

    A previously developed, efficient and simple on-line leaching method was used to assess the maximum bio-accessible fraction (assuming no synergistic effect from other food and beverage) of potentially toxic elements (Cr, As, Cd and Pb) in whole wheat brown and white bread samples. Artificial saliva, gastric juice and intestinal juice were successively pumped into a mini-column, packed with bread (maintained at 37 °C) connected on-line to the nebulizer of an inductively coupled plasma mass spectrometry (ICP-MS) instrument equipped with a collision-reaction interface (CRI) using hydrogen as reaction gas to minimize carbon- and chlorine-based polyatomic interferences. In contrast to the conventional batch method to which it was compared, this approach provides real-time monitoring of potentially toxic elements that are continuously released during leaching. Mass balance for both methods was verified at the 95% confidence level. Results obtained from the whole wheat brown and white bread showed that the majority of Cr, Cd and Pb was leached by gastric juice but, in contrast, the majority of As was leached by saliva. While there was higher total content for elements in whole wheat bread than in white bread, a higher percentage of elements were bio-accessible in white bread than in whole wheat bread. Both the on-line and batch methods indicate that 40-98% of toxic elements in bread samples are bio-accessible. While comparison of total analyte concentrations with provisional tolerable daily intake values may indicate some serious health concern for children, when accounting for the bio-accessibility of these elements, bread consumption is found to be safe for all ages. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Triple-Quadrupole Inductively Coupled Plasma-Mass Spectrometry with a High-Efficiency Sample Introduction System for Ultratrace Determination of (135)Cs and (137)Cs in Environmental Samples at Femtogram Levels.

    Science.gov (United States)

    Zheng, Jian; Cao, Liguo; Tagami, Keiko; Uchida, Shigeo

    2016-09-06

    High yield fission products, (135)Cs and (137)Cs, have entered the environment as a result of anthropogenic nuclear activities. Analytical methods for ultratrace measurement of (135)Cs and (137)Cs are required for environmental geochemical and nuclear forensics studies. Here we report a highly sensitive method combining a desolvation sample introduction system (APEX-Q) with triple-quadrupole inductively coupled plasma mass spectrometry (AEPX-ICPMS/MS) for the determination of (135)Cs and (135)Cs/(137)Cs isotope ratio at femtogram levels. Using this system, we introduced only selected ions into the collision/reaction cell to react with N2O, significantly reducing the isobaric interferences ((135)Ba(+) and (137)Ba(+)) and polyatomic interferences ((95,97)Mo(40)Ar(+), (119)Sn(16)O(+), and (121)Sb(16)O(+)). Compared to the instrument setup of ICPMS/MS, the APEX-ICPMS/MS enables a 10-fold sensitivity increase. In addition, an effective chemical separation scheme consisting of ammonium molybdophosphate (AMP) Cs-selective adsorption and two-stage ion-exchange chromatographic separation was developed to remove major matrix and interfering elements from environmental samples (10-40 g). This separation method showed high decontamination factors (10(4)-10(7)) for major matrix elements (Al, Ca, K, Mg, Na, and Si) and interfering elements (Ba, Mo, Sb, and Sn). The high sensitivity of APEX-ICPMS/MS and the effective removal sample matrix allowed reliable analysis of (135)Cs and (137)Cs with extremely low detection limits (0.002 pg mL(-1), corresponding to 0.006 Bq mL(-1) (137)Cs). The accuracy and applicability of the APEX-ICPMS/MS method was validated by analysis of seven standard reference materials (soils, sediment, and plants). For the first time, ultratrace determination of (135)Cs and (135)Cs/(137)Cs isotope ratio at global fallout source environmental samples was achieved with the ICPMS technique.

  9. Rapid determination of {sup 135}Cs and precise {sup 135}Cs/{sup 137}Cs atomic ratio in environmental samples by single-column chromatography coupled to triple-quadrupole inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Guosheng [Department of Radiation Chemistry, Institute of Radiation Emergency Medicine, Hirosaki University, 66-1 Hon-cho, Hirosaki, Aomori 036-8564 (Japan); Division of Nuclear Technology and Applications, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China); Beijing Engineering Research Center of Radiographic Techniques and Equipment, Beijing 100049 (China); Tazoe, Hirofumi [Department of Radiation Chemistry, Institute of Radiation Emergency Medicine, Hirosaki University, 66-1 Hon-cho, Hirosaki, Aomori 036-8564 (Japan); Yamada, Masatoshi, E-mail: myamada@hirosaki-u.ac.jp [Department of Radiation Chemistry, Institute of Radiation Emergency Medicine, Hirosaki University, 66-1 Hon-cho, Hirosaki, Aomori 036-8564 (Japan)

    2016-02-18

    For source identification, measurement of {sup 135}Cs/{sup 137}Cs atomic ratio not only provides information apart from the detection of {sup 134}Cs and {sup 137}Cs, but it can also overcome the application limit that measurement of the {sup 134}Cs/{sup 137}Cs ratio has due to the short half-life of {sup 134}Cs (2.06 y). With the recent advancement of ICP-MS, it is necessary to improve the corresponding separation method for rapid and precise {sup 135}Cs/{sup 137}Cs atomic ratio analysis. A novel separation and purification technique was developed for the new generation of triple-quadrupole inductively coupled plasma-mass spectrometry (ICP-MS/MS). The simple chemical separation, incorporating ammonium molybdophosphate selective adsorption of Cs and subsequent single cation-exchange chromatography, removes the majority of isobaric and polyatomic interference elements. Subsequently, the ICP-MS/MS removes residual interference elements and eliminates the peak tailing effect of stable {sup 133}Cs, at m/z 134, 135, and 137. The developed analytical method was successfully applied to measure {sup 135}Cs/{sup 137}Cs atomic ratios and {sup 135}Cs activities in environmental samples (soil and sediment) for radiocesium source identification. - Highlights: • A simple {sup 135}Cs/{sup 137}Cs analytical method was developed. • The separation procedure was based on AMP adsorption and one column chromatography. • {sup 135}Cs/{sup 137}Cs was measured by ICP-MS/MS. • Decontamination factors for Ba, Mo, Sb, and Sn were improved. • {sup 135}Cs/{sup 137}Cs atomic ratios of 0.341–0.351 were found in Japanese soil samples.

  10. Direct comparison of capillary electrophoresis and capillary liquid chromatography hyphenated to collision-cell inductively coupled plasma mass spectrometry for the investigation of Cd-, Cu- and Zn-containing metalloproteins.

    Science.gov (United States)

    Montes-Bayon, Maria; Pröfrock, Daniel; Sanz-Medel, Alfredo; Prange, Andreas

    2006-05-05

    Capillary liquid chromatography (cLC) and capillary electrophoresis (CE) have been critically compared for the separation of metalloproteins when using collision-cell inductively coupled plasma mass spectrometry (ICP-CC-MS) as detection system. For cLC separation, the selected column was a C8 (0.3 mm I.D.) and the separation conditions involved a gradient up to 80% methanol in 10mM ammonium acetate buffer (pH 7.4). The low flow rate used (3 microL min(-1)) permitted the utilization of a high methanol content maintaining the sensitivity along the whole chromatographic run. For this purpose, a new low-flow interface has been developed based on a total consumption nebulizer. Similarly, CE has been studied as separation technique using a 75 microm I.D. fused silica capillary and a running buffer of 20 mM Tris-HNO3 (pH 7.4) and working at 30 kV. Metallothionein (mixture of MT-I and -II) and superoxide dismutase (SOD) have been used as protein models in order to evaluate the separation/detection capabilities using the same injection volumes in both systems (20 nL). For both hybrid systems, separation parameters such as retention factor, numbers of theoretical plates, tailing factor and resolution have been critically compared. Also, the analytical performance characteristics of both hybrid systems have been evaluated and tested by analyzing the Cu-, Zn-species present in red blood cell extracts in order to explore more adequate separation methodology for the analysis of metalloproteins in complex matrices.

  11. Development of a novel method for unraveling the origin of natron flux used in Roman glass production based on B isotopic analysis via multicollector inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Devulder, Veerle; Degryse, Patrick; Vanhaecke, Frank

    2013-12-17

    The provenance of the flux raw material used in the manufacturing of Roman glass is an understudied topic in archaeology. Whether one or multiple sources of natron mineral salts were exploited during this period is still open for debate, largely because of the lack of a good provenance indicator. The flux is the major source of B in Roman glass. Therefore, B isotopic analysis of a sufficiently large collection and variety (origin and age) of such glass samples might give an indication of the number of flux sources used. For this purpose, a method based on acid digestion, chromatographic B isolation and B isotopic analysis using multicollector inductively coupled plasma mass spectrometry was developed. B isolation was accomplished using a combination of strong cation exchange and strong anion exchange chromatography. Although the B fraction was not completely matrix-free, the remaining Sb was shown not to affect the δ(11)B result. The method was validated using obsidian and archaeological glass samples that were stripped of their B content, after which an isotopic reference material with known B isotopic composition was added. Absence of artificial B isotope fractionation was demonstrated, and the total uncertainty was shown to be <2‰. A proof-of-concept application to natron glass samples showed a narrow range of δ(11)B, whereas first results for natron salt samples do show a larger difference in δ(11)B. These results suggest the use of only one natron source or of several sources with similar δ(11)B. This indicates that B isotopic analysis is a promising tool for the provenance determination of this flux raw material.

  12. Using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to explore geochemical taphonomy of vertebrate fossils in the upper cretaceous two medicine and Judith River formations of Montana

    Science.gov (United States)

    Rogers, R.R.; Fricke, H.C.; Addona, V.; Canavan, R.R.; Dwyer, C.N.; Harwood, C.L.; Koenig, A.E.; Murray, R.; Thole, J.T.; Williams, J.

    2010-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine rare earth element (REE) content of 76 fossil bones collected from the Upper Cretaceous (Campanian) Two Medicine (TMF) and Judith River (JRF) Formations of Montana. REE content is distinctive at the formation scale, with TMF samples exhibiting generally higher overall REE content and greater variability in REE enrichment than JRF samples. Moreover, JRF bones exhibit relative enrichment in heavy REE, whereas TMF bones span heavy and light enrichment fields in roughly equal proportions. TMF bones are also characterized by more negative Ce anomalies and greater U enrichment than JRF bones, which is consistent with more oxidizing diagenetic conditions in the TMF. Bonebeds in both formations show general consistency in REE content, with no indication of spatial or temporal mixing within sites. Previous studies, however, suggest that the bonebeds in question are attritional assemblages that accumulated over considerable time spans. The absence of geochemical evidence for mixing is consistent with diagenesis transpiring in settings that remained chemically and hydrologically stable during recrystallization. Lithology-related patterns in REE content were also compared, and TMF bones recovered from fluvial sandstones show relative enrichment in heavy REE when compared with bones recovered from fine-grained floodplain deposits. In contrast, JRF bones, regardless of lithologic context (sandstone versus mudstone), exhibit similar patterns of REE uptake. This result is consistent with previous reconstructions that suggest that channel-hosted microfossil bonebeds of the JRF developed via the reworking of preexisting concentrations embedded in the interfluve. Geochemical data further indicate that reworked elements were potentially delivered to channels in a recrystallized condition, which is consistent with rapid adsorption of REE postmortem. Copyright ?? 2010, SEPM (Society for

  13. 微波辅助萃取-电感耦合等离子体质谱法检测食品中的硼砂%Microwave-assisted extraction-inductively coupled plasma mass spectrometry in food borax

    Institute of Scientific and Technical Information of China (English)

    童成豹

    2012-01-01

      The establishment of a microwave-assisted extraction-inductively coupled plasma mass spectrometry detection of food in the borax method. To 0.1 moL/L ammonia to eliminate the memory effect of boron. Boron content of(0~2.0)μg/mL range a good linear relationship, R=1.0000. Borax detection limit of 2.0ng/mL(σ=3), RSD less than 5%, and 95.2%recoveries of 103.4%. The law was compled with GB/T21918-2008 in the three test methods, simple, rapid, reagent pollution characteristics. Boric acid as a food in one of the detection method.%  建立了一种应用微波辅助萃取-电感耦合等离子体质谱法检测食品中的硼砂的方法.以0.1 mol/L氨水来消除硼的记忆效应.硼含量在0~2.0μg/mL范围内线性关系良好,R=1.0000.硼砂检测限为2.0 ng/mL(σ=3),RSD小于5%,方法回收率为95.2%~103.4%.该法与GB/T21918-2008中的三种检测方法相比,具有操作简单、快速、试剂污染少的特点.可作为食品中硼砂含量的检测方法之一.

  14. Bayesian Integration and Characterization of Composition C-4 Plastic Explosives Based on Time-of-Flight Secondary Ion Mass Spectrometry and Laser Ablation-Inductively Coupled Plasma Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Mahoney, Christine M.; Kelly, Ryan T.; Alexander, M. L.; Newburn, Matthew K.; Bader, Sydney P.; Ewing, Robert G.; Fahey, Albert J.; Atkinson, David A.; Beagley, Nathaniel

    2016-02-25

    Key elements regarding the use of non-radioactive ionization sources will be presented as related to explosives detection by mass spectrometry and ion mobility spectrometry. Various non-radioactive ionization sources will be discussed along with associated ionization mechanisms pertaining to specific sample types.

  15. Simultaneous Determination of 7 Trace Elements in Meat and Meat Products by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) with Microwave Digestion%微波消解-电感耦合等离子体质谱法同时测定肉及肉制品中7种痕量元素

    Institute of Scientific and Technical Information of China (English)

    吴春敏; 夏静; 李强; 张岩

    2015-01-01

    A method for the simultaneous determination of 7 trace elements (lead, arsenic, cadmium, chromium, selenium, mercury, and nickel) in meat and meat products by inductively coupled plasma mass spectrometry (ICP-MS) with microwave digestion was established. Samples were pretreated by microwave digestion and determined by ICP-MS with rhodium (Rh) as the internal standard. The microwave digestion conditions and the instrumental parameters were optimized. It was found that the instrumental signal drift and matrix effect could be overcome by using the internal standard method. The developed standard curve was linear in the range of 0 to 20 ng/mL, with a correlation coefficient of more than 0.999. The recoveries of the analytes in spiked samples ranged from 89.4% to 98.9% and the precision expressed as relative standard deviation was less than 5%. The limits of detection for the trace elements were all lower than those stipulated in the Chinese national standards. The proposed method was rapid, accurate, reliable, sensitive and suitable for simultaneous multi-element analysis of meat and meat products.%建立采用电感耦合等离子体质谱法对肉及肉制品中铅、砷、镉、铬、硒、汞、镍7种痕量元素同时检测的方法。用微波消解仪对肉及肉制品进行前处理,以铑作为内标,经电感耦合等离子体质谱仪针对7种痕量元素进行测定。优化微波消解条件以及电感耦合等离子体质谱仪器测定条件。结果表明:内标法能克服仪器信号漂移及样品基体效应的影响。标准曲线的线性范围在0~20 ng/mL,回归方程的相关系数均大于0.999,各元素的加标回收率在89.4%~98.9%之间,相对标准偏差小于5%,检出限均低于国标方法中所规定的方法检出限。该方法具有快速、准确、可靠、灵敏度高及多元素同时分析等优点,可以满足批量肉及肉制品中铅、砷、铬、镉、硒、镍、汞检验和测定。

  16. High-accuracy determination of iron in seawater by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using nitrilotriacetic acid chelating resin for pre-concentration and matrix separation

    Energy Technology Data Exchange (ETDEWEB)

    Jong, Jeroen de [Universite Libre de Bruxelles (ULB), Departement des Sciences de la Terre et de l' Environnement (DSTE), Unite Isotopes: Petrologie et Environnement - IPE CP 160/02, Avenue F.D. Roosevelt 50, B-1050 Brussels (Belgium)], E-mail: jdejong@ulb.ac.be; Schoemann, Veronique [Universite Libre de Bruxelles (ULB), Ecologie des Systemes Aquatiques (ESA) CP 221, Avenue F.D. Roosevelt 50, B-1050 Brussels (Belgium); Lannuzel, Delphine [Universite Libre de Bruxelles (ULB), Departement des Sciences de la Terre et de l' Environnement (DSTE), Laboratoire d' Oceanographie Chimique et Geochimie des Eaux - LOCGE CP 208, Avenue F.D. Roosevelt 50, B-1050 Brussels (Belgium); Tison, Jean-Louis [Universite Libre de Bruxelles (ULB), Departement des Sciences de la Terre et de l' Environnement (DSTE), Laboratoire de Glaciologie - GLACIOL CP 160/03, Avenue F.D. Roosevelt 50, B-1050 Brussels (Belgium); Mattielli, Nadine [Universite Libre de Bruxelles (ULB), Departement des Sciences de la Terre et de l' Environnement (DSTE), Unite Isotopes: Petrologie et Environnement - IPE CP 160/02, Avenue F.D. Roosevelt 50, B-1050 Brussels (Belgium)

    2008-08-15

    In the present paper we describe a robust and simple method to measure dissolved iron (DFe) concentrations in seawater down to <0.1 nmol L{sup -1} level, by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using a {sup 54}Fe spike and measuring the {sup 57}Fe/{sup 54}Fe ratio. The method provides for a pre-concentration step (100:1) by micro-columns filled with the resin NTA Superflow of 50 mL seawater samples acidified to pH 1.9. NTA Superflow is demonstrated to quantitatively extract Fe from acidified seawater samples at this pH. Blanks are kept low (grand mean 0.045 {+-} 0.020 nmol L{sup -1}, n = 21, 3x S.D. limit of detection per session 0.020-0.069 nmol L{sup -1} range), as no buffer is required to adjust the sample pH for optimal extraction, and no other reagents are needed than ultrapure nitric acid, 12 mM H{sub 2}O{sub 2}, and acidified (pH 1.9) ultra-high purity (UHP) water. We measured SAFe (sampling and analysis of Fe) reference seawater samples Surface-1 (0.097 {+-} 0.043 nmol L{sup -1}) and Deep-2 (0.91 {+-} 0.17 nmol L{sup -1}) and obtained results that were in excellent agreement with their DFe consensus values: 0.118 {+-} 0.028 nmol L{sup -1} (n = 7) for Surface-1 and 0.932 {+-} 0.059 nmol L{sup -1} (n = 9) for Deep-2. We also present a vertical DFe profile from the western Weddell Sea collected during the Ice Station Polarstern (ISPOL) ice drift experiment (ANT XXII-2, RV Polarstern) in November 2004-January 2005. The profile shows near-surface DFe concentrations of {approx}0.6 nmol L{sup -1} and bottom water enrichment up to 23 nmol L{sup -1} DFe.

  17. 电感耦合等离子体质谱法测定多晶硅中18个痕量元素%Determination of eighteen trace elements in multicrystal silicon by inductively coupled plasma mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    杨毅; 刘英波; 王劲榕; 李菁菁

    2009-01-01

    A method was established for simultaneous and quantitative determination of trace B, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, W, Cd and Pb in multicrystal silicon by inductively coupled plasma mass spectrometry(ICP-MS).The samples were decomposed with nitric acid and hydrofluoric acid, and the adding amount of reagents was obtained by weighing method.The mass spectral interference was eliminated by introducing ammonia gas as reaction gas in the dynamic reaction cell system(DRC).Under the optimal conditions, the detection limit was 0.8-6.9 pg/g (3σ).The recovery of standard addition was in the range of 83.0%-106%, and the relative standard deviation(RSD)was 0.27%-2.7%(n=11).The proposed method has been used for complete analysis of photovohaic muliticrystal silicon samples, and the results were in good accordance with the reference values.