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Sample records for ablation-inductively coupled plasma-mass

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  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. 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. 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.

  10. Strategies for the analysis of coal by laser ablation inductively coupled plasma mass spectroscopy.

    Science.gov (United States)

    Kleiber, L; Fink, H; Niessner, R; Panne, U

    2002-09-01

    The potential of laser ablation inductively coupled mass spectrometry (LA-ICP-MS) was investigated for the inorganic characterization of different coal samples pressed into pellets. Reference analysis was performed by microwave-assisted digestion of the ground samples followed by ICP-MS analysis of the resulting solutions. Two different laser ablation sampling procedures were compared. For continuous sampling, three sites of the pellet were sampled for approximately one minute, whereas for sequential sampling 15 sites were sampled for two seconds, respectively. The qualitative results of the two procedures were equivalent, but continuous sampling allowed faster analysis and better precision (RSD about 10%) than sequential sampling (RSD 10-20%). Different normalization procedures with internal and extrinsic standards were investigated and allowed a quantitative determination of Al, Ti, Zn, Ni, and V with measurement uncertainties below 10% and Fe, Si, and Sn with measurement uncertainties below 20%.

  11. Strategies for the analysis of coal by laser ablation inductively coupled plasma mass spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kleiber, L.; Fink, H.; Niessner, R.; Panne, U. [Institute of Hydrochemistry, Technical University of Munich, Marchioninistr. 17, 81377 Munich (Germany)

    2002-09-01

    The potential of laser ablation inductively coupled mass spectrometry (LA-ICP-MS) was investigated for the inorganic characterization of different coal samples pressed into pellets. Reference analysis was performed by microwave-assisted digestion of the ground samples followed by ICP-MS analysis of the resulting solutions. Two different laser ablation sampling procedures were compared. For continuous sampling, three sites of the pellet were sampled for approximately one minute, whereas for sequential sampling 15 sites were sampled for two seconds, respectively. The qualitative results of the two procedures were equivalent, but continuous sampling allowed faster analysis and better precision (RSD about 10%) than sequential sampling (RSD 10-20%). Different normalization procedures with internal and extrinsic standards were investigated and allowed a quantitative determination of Al, Ti, Zn, Ni, and V with measurement uncertainties below 10% and Fe, Si, and Sn with measurement uncertainties below 20%. (orig.)

  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. 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.

  14. 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.``

  15. 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.

  16. 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.

  17. 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.

  18. 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.

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

    Science.gov (United States)

    Bartle, Emma K; Watling, R John

    2007-03-01

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

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Multiplexed microRNA detection using lanthanide-labeled DNA probes and laser ablation inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    de Bang, Thomas Christian; Shah, Pratik; Cho, Seok Keun

    2014-01-01

    . The narrow size range of miRNAs (20-24 nucleotides) combined with the chemical properties of conventional reporter tags has hampered the development of multiplexed miRNA assays. In this study, we have used lanthanide-labeled DNA probes for the detection of miRNAs on membranes using laser ablation inductively...

  10. 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.

  11. 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.

  12. 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.

  13. Laser ablation inductively coupled plasma mass spectrometric analyses of base metals in arctic char (Salvelinus alpinus) otoliths collected from a flooded base metal mine.

    Science.gov (United States)

    Friedrich, Lisa A; Halden, Norman M

    2011-05-15

    Otoliths from arctic char recovered from the water body formed from an abandoned open-pit nickel-copper mine contain a trace element record related to the geology of the immediate watershed, past mining activity in the area, and the fish's diet. Laser ablation inductively coupled plasma mass spectrometric analyses across the annular structure of the otoliths detected trace amounts of nickel, copper, and chromium believed to be related to the metal-bearing, mafic-ultramafic minerals in the pit. Oscillatory strontium, barium, and zinc profiles may reflect changing water temperature, diet, or fish metabolism. Lead was detected in very low concentrations and may be related to anthropogenic influence. This closed lake system provides a unique opportunity to study an introduced exotic species in a setting where neither migration nor recruitment have been possible. The fish have successfully occupied the lake and continue to breed despite the influence of the surrounding rocks and local contamination. The chemical record retained within otoliths provides a method of monitoring trace elements affecting fish on a yearly basis and may be regarded as a useful assessment tool for examining the exposure of wild organisms to trace elements.

  14. 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%.

  15. 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.

  16. 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).

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Study on quantitative analysis of Ti, Al and V in clinical soft tissues after placing the dental implants by laser ablation inductively coupled plasma mass spectrometry

    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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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

  20. 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.

  1. 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

  2. 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

  3. 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%.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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)

  13. Reproducibility of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) measurements in mussel shells and comparison with micro-drill sampling and solution ICP-MS.

    Science.gov (United States)

    Phung, Anh Tuan; Baeyens, Willy; Leermakers, Martine; Goderis, Steven; Vanhaecke, Frank; Gao, Yue

    2013-10-15

    The accumulation of trace elements (Mg, Mn, Sr, Ba) in Unio pictorum L. mussel shells from Lake Balaton has been assessed using a Laser Ablation (LA) system coupled to either a quadrupole-based or a sector-field inductively coupled plasma-mass spectrometer (ICP - MS), as well as by a combination of micro-drill sampling and solution ICP-MS. The LA-ICP-MS measurements were carried out in the holes made by the micro-drilling system. The longitudinal concentration profiles obtained with the different methods show similar patterns. However, the absolute concentrations determined at individual spots (holes) can be quite different. Especially Ba shows erratic peaks at a very small spatial scale. A paired, two-sample t-test between LA-ICP-MS longitudinal profiles and between LA-ICP-MS and micro-drill/solution ICP-MS profiles indicates that, in most cases, there is no significant difference between the concentration profiles of Ba, Mg, Mn and Sr. Average shell concentrations of Mg, Mn, Sr and Ba, as obtained by LA-ICP-MS and micro-drill/solution ICP-MS, compare well with bulk shell concentrations as obtained by acid digestion/ICP-MS of larger shell pieces. Next to the four elements mentioned above, also the concentrations of Cd, Co, Cr, Cu, Ni, Pb and Zn could be determined by bulk shell analysis. The element concentrations in 11 shells, all sampled at the same site, show a relative standard deviation (RSD) between 2% (Ni) and 46% (Zn). LA-ICP-MS and micro-drill solution ICP-MS are not sensitive enough for the determination of ultra-trace elements in Lake Balaton's mussel shells. We estimated the amount of shell material necessary to determine Ni, Pb, Cr and Cu by micro-drilling ICP-MS (for a concentration that equals 3 times their limit of detection) at, respectively, 0.04, 0.82, 2.7 and 0.4 mg, while the amount sampled by micro-drilling is about 0.06 mg.

  14. Study of near infra red femtosecond laser induced particles using transmission electron microscopy and low pressure impaction: Implications for laser ablation-inductively coupled plasma-mass spectrometry analysis of natural monazite

    Energy Technology Data Exchange (ETDEWEB)

    D' Abzac, Francois-Xavier, E-mail: dabzac@lmtg.obs-mip.fr [GET - UMR 5563 CNRS - Universite de Toulouse - IRD - OMP, 14 avenue Edouard Belin, 31400 Toulouse (France); Seydoux-Guillaume, Anne-Magali; Chmeleff, Jerome [GET - UMR 5563 CNRS - Universite de Toulouse - IRD - OMP, 14 avenue Edouard Belin, 31400 Toulouse (France); Datas, Lucien [TEMSCAN - CIRIMAT - Universite de Toulouse, 118 route de Narbonne, 31400 Toulouse (France); Poitrasson, Franck [GET - UMR 5563 CNRS - Universite de Toulouse - IRD - OMP, 14 avenue Edouard Belin, 31400 Toulouse (France)

    2011-09-15

    The characteristics of infra red femtosecond laser-induced aerosols are studied for monazite (LREE, Th(PO{sub 4})) ablation and correlations are established with inductively coupled plasma-mass spectrometry (ICP-MS) signals. Critical parameters are tested within wide ranges of values in order to cover the usual laser ablation -ICP-MS analysis conditions: pulse energy (0.15 < E{sub 0} < 1 mJ/pulse), pulse width (60 < {tau} < 3000 fs), ablation time (t {<=} 10 min) and transport length (l {<=} 6.3 m). Transmission electron microscopy reveals that aerosols are made of agglomerates of {approx} 10 nm particles and 20-300 nm phosphorus depleted condensed spherical particles. These structures are not affected by any laser ablation parameter. Particle counting is performed using electronic low pressure impaction. Small changes on particle size distribution are noticed. They may be induced either by a peak of ablation rate in the first 15 s at high fluence (larger particles) or the loss of small particles during transport. We found a positive correlation between I (ICP-MS mean signal intensity in cps) and N (particle density in cm{sup -3}) when varying E{sub 0} and t, suggesting that N is controlled by the irradiance (P{sub 0} in W{center_dot}cm{sup -2}). Elemental ratio measurements show a steady state signal after the initial high ablation rate (mass load effect in the plasma torch) and before a late chemical fractionation, induced by poor extraction of bigger, early condensed spherical particles from the deepening crater. Such chemical fractionation effects remain within uncertainties, however. These effects can be limited by monitoring E{sub 0} to shorten the initial transient state and delay the attainment of an unfavorable crater aspect ratio. Most adopted settings are for the first time deduced from aerosol characteristics, for infra red femtosecond laser ablation. A short transport (l < 4.0 m) limits the agglomeration of particles by collision process along the tube

  15. 激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)定量分析小麦籽粒锌元素的空间分布%Quantification and spatial distribution of zinc in wheat grains by laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS)

    Institute of Scientific and Technical Information of China (English)

    王云霞; 杨连新; W.J.Horst

    2011-01-01

    激光剥蚀电感耦合等离子体质谱(laser ablation inductively coupled plasma mass spectrometry,LA-ICP-MS)是用于测定植物组织中元素分布的最新技术.采用LA-ICP-Ms技术对小麦成熟籽粒中锌的空间分布进行了定量分析.结果表明:成熟小麦籽粒锌浓度的空间分布差异明显.从浓度分布看,种皮、糊粉层和胚中的锌分别为192、432和292 mg·kg-1,而胚乳中的锌只有14 mg·kg-1;从积累量分布看,种皮、糊粉层、胚和胚乳中的锌积累量分别占籽粒总积累量的24%、47%、11%和18%,说明小麦籽粒经加工后锌含量锐减(下降约80%).分别采用LA-ICP-MS和酸消解溶液雾化进样ICP-MS法测定了自制校正标准样和小麦整粒种子的锌浓度,结果两种方法的测定值很接近且重复间变异较小,证实了LA-ICP-MS这一空间分布定量分析方法的可靠性.%Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)is a recently developed technology for examining mineral elements distribution in plant tissue. In this paper, the spatial distribution of zinc in wheat grains was quantified by LA-ICP-MS. Results indicated large spatial variation of zinc concentration in wheat grains. Zinc concentration in seed coat, aleurone layer and ambryo is 192,432 and 292 mg-kg-1, respectively, only 14 mg·kg-1 in endosperm. As for zinc accumulation, zinc amount in seed coat,aleurone layer,ambryo and endosperm account for 24% ,47%, 11% and 18% of total zinc in grain, which implied that zinc content in grains decreased sharply after seed processing (polished). By comparing the measured zinc value of two different methods (i. e. , LA-1CP-MS and ICP-MS after digestion), we also found that the variation of measured zinc concentration between two methods as well as among replications were small, which suggested that LA-ICP-MS is a reliable method for quantifying the spatial distribution of elements in grains.

  16. Element Colocalization in Wheat Seed Revealed by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)%用激光剥蚀电感耦合等离子体质谱研究小麦籽粒元素的共分布

    Institute of Scientific and Technical Information of China (English)

    王云霞; 杨连新; WalterJ.HORST

    2012-01-01

    For enhancement of micronutrient concentrations in edible parts of food crops, element uptake and partition in plants, especially in seeds, should be better understanded. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a recently developed technology for examining mineral elements distribution in plant tissues. By using this technique, we quantitatively measured distributions of manganese (Mn), copper (Cu), zinc (Zn), and phosphorus (P) in different parts of wheat seeds. The concentrations of Cu, Zn, and P were the highest in aleurone layer and the lowest in endosperm with the difference of 15, 42, and 33 folds, respectively. The Mn concentration was the highest in embryo, which was 9-fold higher than the lowest concentration in endosperm. The concentration gradients of measured elements were also found in same parts of wheat grain. The concentrations of P, Mn, Cu, and Zn in endosperm close to aleurone layer were higher than those in the middle of wheat seed. Similarly, the element concentrations in scutellum were higher than those in embryo axis. The four elements had similar distribution pattern in wheat seed with a clear synchronization. This phenomenon suggested the colocalization of these elements in wheat seeds. Therefore, the translocations and accumulations of P, Mn, Cu, and Zn in wheat seeds might be closely related to each other, and the finding is useful for wheat biofortification programs in the future.%增加粮食可食用部分微量营养元素的浓度,需要更好地了解其在植株,特别是籽粒内的运输和分布规律.激光剥蚀电感耦合等离子体质谱(laser ablation inductively coupled plasma mass spectrometry,LA-ICP-MS)是一种测定植物组织中元素空间分布的新技术.采用该技术对成熟小麦籽粒中锰(Mn)、铜(Cu)、锌(Zn)和磷(P)的空间分布及其关联程度定量研究.结果表明,所测元素在籽粒不同部位的浓度分布差异很大.Cu、Zn和P浓度均以糊粉

  17. 激光剥蚀电感耦合等离子体质谱法测定金属镀锡层的厚度%Quick Measurement of Thickness of Tin Coating on Metal by Laser Ablation Inductively Coupled Plasma-Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    金献忠; 谢健梅; 陈建国

    2015-01-01

    激光剥蚀电感耦合等离子体质谱法(LA -ICP -MS)应用于测定金属镀锡层的厚度时激光脉冲能量的大小及其稳定性会影响分析结果的准确度。本文采用一款自制的皮秒激光剥蚀固体进样系统(psLA),与ICP -MS 联用建立了一种测定金属镀锡层厚度的方法。在激光脉冲能量为12μJ,散焦距离为625μm 的条件下采集锡和镀锡层基材元素检测同位素的时间分辨图,根据提出的边界确定规则确定了剥蚀镀锡层的时间,同时根据厚度标准片计算单位脉冲剥蚀量。该方法的单位脉冲剥蚀量为88 nm /pulse,厚度分辨率为0.40μm,应用于测定钢镀锡厚度标准片、铜镀锡厚度标准片、有涂层马口铁和镀锡不锈钢带等样品,测定值与认定值的最大偏差为0.5μm。本方法避免了激光脉冲能量的不稳定使得单位脉冲剥蚀量发生变化的问题,提高了镀层厚度测定的准确度,适用于各种形态、各种规格金属镀层厚度的测定,也可应用于生命科学、考古、环境、司法等领域。%Thickness analysis of tin coating on metal by Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS)is affected by the laser pulse energy and its stability.A method has been proposed for quick measurement of thickness of tin coating on metal using a self-made picosecond laser ablation system coupled Inductively Coupled Plasma-Mass Spectrometry.Laser ablation was carried out using pulse energy of 12 μJ and defocus distance of 625 μm.Time resolved spectra (TRS)of 118 Sn and measured isotopes of the main elements in substrate were acquired,the time of ablation of zinc coating was gained according to the relationship of these TRS, the ablation rate was calculated by thickness standard sheet,and thickness of tin coating could be measured quickly.Ablation rate of tin coating was 88 nm /pulse and depth solution was 0.40 μm.The thickness standard sheet

  18. 基于元素对研究激光剥蚀-电感耦合等离子体质谱分析硫化物矿物的基体效应%Characterization of Matrix Effects in Microanalysis of Sulfide Minerals by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Based on An Element Pair Method

    Institute of Scientific and Technical Information of China (English)

    袁继海; 詹秀春; 胡明月; 赵令浩; 孙冬阳

    2015-01-01

    基体效应是影响LA-ICP-MS分析结果准确性的主要因素之一,但目前却没有一种量化基体效应研究的方法。提出了一种以分析元素与内标元素的强度比(Ii/Iis )为纵坐标、浓度比(ci/cis )为横坐标绘制Ii/Iis-ci/cis图,以元素对Ii/Iis-ci/cis图的线性相关系数r量化基体效应的思路。以Fe为内标,考察了13个常用玻璃标准物质与2个硫化物标准及多个硫化物矿物中6个元素对的基体效应,结果显示Cu/Fe和Zn/Fe的线性相关系数r 都小于0.99,而痕量元素对 Mn/Fe,Co/Fe,Ga/Fe,Pb/Fe 的线性相关系数r 都大于0.999;以S为内标,考察了2个硫化物标准与多个硫化物矿物中三个主量元素对Fe/S,Cu/S和Zn/S的基体效应,结果显示其线性相关系数r都小于0.999。无论是以Fe为内标结合玻璃标准为外标,还是以S为内标结合硫化物标准为外标分析硫化物矿物,主量元素大多数分析结果的误差大于10%;而以Fe 为内标时,绝大多数玻璃标准获得的痕量元素分析结果与 MASS-1较为一致,误差小于15%。研究表明,玻璃标准及硫化物矿物标准均与硫化物矿物存在一定的基体效应差异,而采用元素对Ii/Iis-ci/cis图的线性相关系数r量化基体效应具有一定的合理性与实用性。研究也表明了以Fe为内标,采用非基体匹配的玻璃标准可用于定量分析硫化物矿物中的痕量元素,尤其是具有较高痕量元素含量的NIST610。%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 calcula-tion formula to quantify matrix effect between standards and samples up to date.In this paper,the linear correlation coefficient r of the Ii/Iis-ci/cis graphs of element pairs were

  19. 激光剥蚀-等离子体质谱技术及其在地球化学宇宙化学和环境研究中的应用%Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry and Its Application in Geochemistry, Cosmochemistry and Environmental Research

    Institute of Scientific and Technical Information of China (English)

    JOCHUM Klaus Peter; KUZMIN Dmitry; MERTZ-KRAUS Regina; MüLLER Werner E G; REGNERY Julia; SOBOLEV Alexander; 王晓红; 詹秀春; STOLL Brigitte; FRIEDRICH Jon M; AMINI Marghaleray; BECKER Stefan; DüCKING Marc; EBEL Denton S; ENZWEILER Jacinta; HU Ming-yue

    2009-01-01

    激光剥蚀-等离子体质谱(LA-ICPMS)已成为地球化学、宇宙化学和环境研究领域元素和同位素原位分析最重要的技术之一.文章介绍了多种类型的质谱仪及其使用的激光器.用途最广的LA-ICPMS仪器之一是单接收器扇形磁场质谱仪,配有Nd:YAG激光剥蚀系统(激光波长分为193 nm和213 nm两种),MPI Mainz实验室使用的就是这套系统,文章对此作一详细介绍.文中阐述了数据优化技术及其多种校正过程;介绍LA-ICPMS在痕量元素和同位素分析领域的一些应用,包括参考物质的研制,Hawaiian玄武岩、Martian陨石、生物骨针和珊瑚虫中痕量元素分析及熔融包裹体和富钙-铝碳质球粒陨石中的铅和锶同位素测量.%Laser ablation (LA)-inductively coupled plasma-mass spectrometry (ICP-MS) has become one of the most important methods for in situ trace elemental and isotopic analysis in geochemistry, cosmochemistry and environmental research. For these purposes, different kinds of mass spectrometers and lasers are used, which are presented in this paper. One of the most useful LA-ICPMS instruments is the combination of a single-collector sector field mass spectrometer with Nd:YAG laser ablation systems (193 nm and 213 nm wavelengths, respectively). This design used in the MPI Mainz laboratory is described in detail in this paper. Data optimization techniques including diverse correction procedures are also discussed. To demonstrate the power of LA-ICPMS, several applications of trace elemental and isotopic analysis are presented, such as investigations of reference materials, trace element analysis in Hawaiian basalts, Martian meteorites, biological spicules and corals, as well as Pb and Sr isotope measurements of melt inclusions and Ca-Al rich inclusions of carbonaceous chondrites.

  20. Analysis of tungsten carbide coatings by UV laser ablation inductively coupled plasma atomic emission spectrometry

    Science.gov (United States)

    Kanicky, V.; Otruba, V.; Mermet, J.-M.

    2000-06-01

    Tungsten carbide coatings (thickness 0.1-0.2 mm) containing 8.0, 12.2, 17.2 and 22.9% Co were studied with laser ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES). Composition of these plasma sprayed deposits on steel disks was determined using X-ray fluorescence spectrometry and electron microprobe energy/wavelength dispersive X-ray spectrometry. The coatings were ablated by means of a Q-switched Nd:YAG laser at 266 nm (10 Hz, 10 mJ per shot) coupled to an ICP echelle-based spectrometer equipped with a segmented charge-coupled device detector. Non-linear dependences of cobalt lines intensities on the Co percentage were observed both at a single spot ablation and at a sample translation. This behaviour could be attributed to a complex phase composition of the system W-C-Co. However, employing tungsten as internal standard the linear calibration was obtained for studied analytical lines Co II 228.616 nm, Co II 230.786 nm, Co II 236.379 nm and Co II 238.892 nm.

  1. Determination of additives in PVC material by UV laser ablation inductively coupled plasma atomic emission spectrometry

    Science.gov (United States)

    Hemmerlin, M.; Mermet, J. M.; Bertucci, M.; Zydowicz, P.

    1997-04-01

    UV laser ablation inductively coupled plasma atomic emission spectrometry (LA-ICP-AES) has been applied to the direct determination of additives in solid poly(vinyl chloride) materials. A Nd:YAG laser, operating at its fourth harmonic (266 nm), was used with a beam masking device, in the most reproducible conditions, to introduce solid particles into the plasma torch of a simultaneous ICP-AES system. Emphasis was placed on both precision and accuracy in the analysis of PVC materials by LA-ICP-AES. A series of six in-house PVC reference materials was prepared by incorporating several additives in increasing concentrations. Three alternative methods were evaluated to certify the amount of incorporated elements: ICP-AES with sample dissolution, NAA and XRF. Satisfactory results and good agreement were obtained for seven elements (Al, Ca, Cd, Mg, Sb, Sn and Ti) among the ten incorporated. Sample homogeneity appeared to be satisfactory, and calibration graphs obtained by LA-ICP-AES for several elements are presented. Finally, the performance of the technique in terms of repeatability (1.6-5%), reproducibility (2-5%), and limits of detection was investigated.

  2. Determination of refractive and volatile elements in sediment using laser ablation inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Duodu, Godfred Odame [School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology (QUT), 2 George St, 4001, QLD (Australia); Goonetilleke, Ashantha [School of Civil Engineering and Built Environment, Science and Engineering Faculty, Queensland University of Technology (QUT), 2 George St, 4001, QLD (Australia); Allen, Charlotte [Institute for Future Environments, Queensland University of Technology (QUT), 2 George St, 4001, QLD (Australia); Ayoko, Godwin A., E-mail: g.ayoko@qut.edu.au [School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology (QUT), 2 George St, 4001, QLD (Australia)

    2015-10-22

    Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (−52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments. - Highlights: • Wet milling was used to produce pressed tablet sediment for LA-ICP-MS analysis. • Milling was effective for refractive elements with narrow range of particle size. • This is the first use of LA-ICP-MS for Hg analysis in sediment samples. • Acceptable accuracy and precision were obtained for most of the elements studied. • Detection limits down to parts per trillion were observed for some elements.

  3. Trace elemental imaging of coralline hydroxyapatite by laser-ablation inductively coupled plasma-mass spectroscopy.

    Science.gov (United States)

    Chou, J; Austin, C; Doble, P; Ben-Nissan, B; Milthorpe, B

    2014-07-01

    The determination of trace element concentrations, as well as their distribution in different biomaterials aimed for clinical applications, is a challenging task in both the areas of biological and materials research. In this research, LA-ICP-MS was employed for image mapping of the trace element distribution in a hydrothermally converted coralline hydroxyapatite material aimed for tissue-scaffolding applications. Quantification using synthetic matrix-matched standards was successfully applied for the determination and distribution of elements of interest, Sr and Mg, that influences the mechanical and biological properties of hydroxyapatite-based bone graft materials. The results showed that the instrument can successfully analyse trace elements and a relatively good image can be produced that identifies their distribution. The LA-ICP-MS method can provide an easy and effective tool, in the field of biomaterials with respect to distribution of trace elements, to better understand tissue-implant interactions, and will open up a new window for in vitro and in vivo analysis and imaging of different tissues and structures.

  4. Determination of refractive and volatile elements in sediment using laser ablation inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Duodu, Godfred Odame; Goonetilleke, Ashantha; Allen, Charlotte; Ayoko, Godwin A

    2015-10-22

    Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (-52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments.

  5. 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

  6. Laser ablation inductively coupled plasma optical emission spectrometry for analysis of pellets of plant materials

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Marcos S. [Departamento de Química, Universidade Federal de São Carlos, Rod. Washington Luís, km 235, 13565-905 São Carlos, SP (Brazil); Centro de Energia Nuclear na Agricultura, Universidade de São Paulo, Av. Centenário 303, 13416-000 Piracicaba, SP (Brazil); Schenk, Emily R. [Department of Chemistry and Biochemistry, Florida International University, Miami, FL (United States); International Forensic Research Institute, Florida International University, Miami, FL (United States); Santos, Dário [Departamento de Ciências Exatas e da Terra, Universidade Federal de São Paulo, Rua Professor Arthur Riedel 275, Diadema, SP (Brazil); Krug, Francisco José [Centro de Energia Nuclear na Agricultura, Universidade de São Paulo, Av. Centenário 303, 13416-000 Piracicaba, SP (Brazil); Almirall, José R., E-mail: almirall@fiu.edu [Department of Chemistry and Biochemistry, Florida International University, Miami, FL (United States); International Forensic Research Institute, Florida International University, Miami, FL (United States)

    2014-04-01

    An evaluation of laser ablation inductively coupled plasma optical emission spectroscopy (LAICP OES) for the direct analysis of pelleted plant material is reported. Ground leaves of orange citrus, soy and sugarcane were comminuted using a high-speed ball mill, pressed into pellets and sampled directly with laser ablation and analyzed by ICP OES. The limits of detection (LODs) for the method ranged from as low as 0.1 mg kg{sup −1} for Zn to as high as 94 mg kg{sup −1} for K but were generally below 6 mg kg{sup −1} for most of the elements of interest. A certified reference material consisting of a similar matrix (NIST SRM 1547 peach leaves) was used to check the accuracy of the calibration and the reported method resulted in an average bias of ∼ 5% for all the elements of interest. The precision for the reported method ranged from as low as 4% relative standard deviation (RSD) for Mn to as high as 17% RSD for Zn but averaged ∼ 6.5% RSD for all the elements (n = 10). The proposed method was tested for the determination of Ca, Mg, P, K, Fe, Mn, Zn and B, and the results were in good agreement with those obtained for the corresponding acid digests by ICP-OES, no differences being observed by applying a paired t-test at the 95% confidence level. The reported direct solid sampling method provides a fast alternative to acid digestion that results in similar and appropriate analytical figures of merit with regard to sensitivity, accuracy and precision for plant material analysis. - Highlights: • An evaluation of LA-ICP-OES for the direct analysis of pelleted plant material is reported. • Orange citrus, soy and sugarcane plants were pressed into pellets and sampled directly. • The element menu consisted of Ca, Mg, P, K, Fe, Mn, Zn and B. • LODs for the method ranged from 0.1 mg kg{sup −1} for Zn to 94 mg kg{sup −1} for K. • The precision ranged from 4% RSD for Mn to 17% RSD for Zn (∼ 6.5% RSD average)

  7. Quantitative analysis of trace elements in environmental powders with laser ablation inductively coupled mass spectrometry using non-sample-corresponding reference materials for signal evaluation

    Science.gov (United States)

    Bauer, Gerald; Limbeck, Andreas

    2015-11-01

    Laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) is an attractive alternative to traditional procedures for the analysis of environmental samples (i.e., conventional liquid measurement after sample digestion). However, for accurate quantification, certified reference materials (CRM) are necessary which match the composition of the sample and include all elements of interest at the required concentration levels. The limited availability of appropriate CRMs hampers therefore substantial application. In this work, an LA-ICP-MS procedure allowing for accurate determination of trace element contents in powdered environmental samples is presented. For LA-ICP-MS analysis, the samples are mixed with an internal standard (silver oxide) and a binder (sodium tetra borate) and subsequently pressed to pellets. Quantification is accomplished using a calibration function determined using CRMs with varying matrix composition and analyte content, pre-treated and measured in the same way as the samples. With this approach, matrix-induced ablation differences resulting from varying physical/chemical properties of the individual CRMs could be compensated. Furthermore, ICP-related matrix-effects could be minimized using collision/reaction cell technology. Applicability of the procedure has been demonstrated by assessment of Cd, Cu, Ni, and Zn in four different environmental CRMs (NIST SRM1648a (urban particulate matter), NIST SRM2709 (San Joaquin Soil), BCR144 (sewage sludge), and BCR723 (road dust)). Signal evaluation was performed by alternative use of three CRMs for calculation of the calibration function whereas the remaining fourth CRM acted as unknown sample, resulting in a good agreement between measured and certified values for all elements and reference materials.

  8. 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

  9. Forensic analysis of printing inks using tandem Laser Induced Breakdown Spectroscopy and Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Subedi, Kiran, E-mail: ksube001@fiu.edu; Trejos, Tatiana, E-mail: trejost@fiu.edu; Almirall, José, E-mail: almirall@fiu.edu

    2015-01-01

    Elemental analysis, using either LA-ICP-MS or LIBS, can be used for the chemical characterization of materials of forensic interest to discriminate between source materials originating from different sources and also for the association of materials known to originate from the same source. In this study, a tandem LIBS/LA-ICP-MS system that combines the benefits of both LIBS and LA-ICP-MS was evaluated for the characterization of samples of printing inks (toners, inkjets, intaglio and offset.). The performance of both laser sampling methods is presented. A subset of 9 black laser toners, 10 colored (CMYK) inkjet samples, 12 colored (CMYK) offset samples and 12 intaglio inks originating from different manufacturing sources were analyzed to evaluate the discrimination capability of the tandem method. These samples were selected because they presented a very similar elemental profile by LA-ICP-MS. Although typical discrimination between different ink sources is found to be > 99% for a variety of inks when only LA-ICP-MS was used for the analysis, additional discrimination was achieved by combining the elemental results from the LIBS analysis to the LA-ICP-MS analysis in the tandem technique, enhancing the overall discrimination capability of the individual laser ablation methods. The LIBS measurements of the Ca, Fe, K and Si signals, in particular, improved the discrimination for this specific set of different ink samples previously shown to exhibit very similar LA-ICP-MS elemental profiles. The combination of these two techniques in a single setup resulted in better discrimination of the printing inks with two distinct fingerprint spectra, providing information from atomic/ionic emissions and isotopic composition (m/z) for each ink sample. - Highlights: • The optimization of the parameters for LA-ICP-MS and LIBS in a tandem experiment are presented. • The analytical figures of merit for the tandem experiment for data collected simultaneously, are presented. • A qualitative and semi-quantitative method for the analysis of toner, inkjet, offset and Intaglio inks is presented. • The LIBS and LA-ICP-MS data are shown to be complementary and can augment discrimination over a single technique. • Major, minor and trace elements present in ink samples can serve as good discriminators for a variety of printing inks. • LIBS was successful to overcome spectral interferences of ICP-MS for some discriminating elements like K, Ca, Si and Fe. • Fusion of LIBS and LA-ICP-MS has proven to provide complementary information and enhanced discrimination for printing inks.

  10. LASER ABLATION-INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROSCOPY STUDY AT THE 222-S LABORATORY USING HOT-CELL GLOVE BOX PROTOTYPE SYSTEM

    Energy Technology Data Exchange (ETDEWEB)

    SEIDEL CM; JAIN J; OWENS JW

    2009-02-23

    This report describes the installation, testing, and acceptance of the Waste Treatment and Immobilization Plant (WTP) procured laser ablation-inductively coupled plasma-atomic emission spectroscopy (LA-ICP-AES) system for remotely analyzing high-level waste (HLW) samples in a hot cell environment. The work was completed by the Analytical Process Development (APD) group in accordance with Task Order 2005-003; ATS MP 1027, Management Plan for Waste Treatment Plant Project Work Performed by Analytical Technical Services. The APD group at the 222-S Laboratory demonstrated acceptable turnaround time (TAT) and provide sufficient data to assess sensitivity, accuracy, and precision of the LA-ICP-AES method.

  11. 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.

  12. 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'.

  13. A Review on Inductively Coupled Plasma Mass Spectroscopy

    Directory of Open Access Journals (Sweden)

    Ramyalakshmi G

    2012-12-01

    Full Text Available Inductively coupled plasma mass spectroscopy is routinely used in many diverse research fields such as earth, environmental, life and forensic sciences and in food, material, chemical, semiconductor and nuclear industries. The high ion density and the high temperature in a plasma provide an ideal atomizer and element ionizer for all types of samples and materials introduced by a specialised devices .outstanding properties such as high sensitivity, relative salt tolerance, compound-independent element response and highest quantitation accuracy lead to the unchallenged performance of ICPMS in efficiently detecting, identifying and reliably quantifying trace element. The increasing availability of relevant reference compounds and high separation selectively extend the molecular identification capability of ICPMS hyphenated to species – specific separation techniques

  14. 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.

  15. 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.

  16. 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

  17. 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…

  18. 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...

  19. Lanthanide Elements as Labels in Multiplexed Analysis of Proteins and MicroRNAs by Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    DEFF Research Database (Denmark)

    de Bang, Thomas Christian

    of the two assays were very similar. Protein or RNA samples were separated by polyacrylamide gel electrophoresis and transferred to membranes by electroblotting where specific recognition of target analytes was achieved by antibodies and DNA probes, respectively. The use of lanthanides as labels on different...

  20. Development of a 2D laser ablation inductively coupled plasma mass spectrometry mapping procedure for mercury in maize (Zea mays L.) root cross-sections

    Energy Technology Data Exchange (ETDEWEB)

    Debeljak, Marta [Analytical Chemistry Laboratory, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana (Slovenia); Department of Biology, Biotechnical Faculty, University of Ljubljana, Večna Pot 111, SI-1000 Ljubljana (Slovenia); Elteren, Johannes T. van, E-mail: elteren@ki.si [Analytical Chemistry Laboratory, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana (Slovenia); Vogel-Mikuš, Katarina [Department of Biology, Biotechnical Faculty, University of Ljubljana, Večna Pot 111, SI-1000 Ljubljana (Slovenia)

    2013-07-17

    Graphical abstract: -- Highlights: •LA-ICP-MS mapping to study the distribution of Hg in plant root cross-sections. •Sorption of LA-generated Hg vapour leads to serious memory effects. •Spot analysis with a delay time of 10 s in between spots alleviates memory effects. •Ablation straight through the sample simplifies calibration. •Hg{sup 2+} does not cross the endodermal root barrier of maize plants. -- Abstract: A LA-ICP-MS method based on a 213 nm Nd:YAG laser and a quadrupole ICP-MS has been developed for mapping of mercury in root cross-sections of maize (Zea mays L.) to investigate the mechanism of mercury uptake from soil and its potential translocation to the edible parts. Conventional rastering was found to be unusable due to sorption of mercury onto the internal parts of the LA device, giving rising to memory effects resulting in serious loss of resolution and inaccurate quantification. Spot analysis on a virtual grid on the surface of the root sections using washout times of 10 s in between spots greatly alleviated problems related to these memory effects. By ablating straight through the root sections on a poly(methyl methacrylate) support the calibration process was simplified as internal standardization and matrix-matching could be circumvented. Mercury-spiked freeze-drying embedding medium, sectioned similarly to the root sections, was used for the preparation of the standards. Standards and root sections were subjected to spot analysis using the following operational parameters: beam diameter, 15 μm; laser fluence, 2.5 J cm{sup −2}; repetition rate, 20 Hz; dwell time, 1 s; acquisition time, 0.1 s. The mercury peaks for standards and roots sections could be consistently integrated for quantification and construction of the 2D mercury maps for the root sections. This approach was successfully used to investigate the mercury distribution in root sections of maize grown in soil spiked to a level of 50 mg kg{sup −1} DW HgCl{sub 2}. It was found that at given Hg concentrations in the substrate Hg ions practically do not cross root plasma membranes of the endodermal barrier, but are entirely retained in the root apoplastic space. This suggests that maize plants grown in Hg-contaminated areas translocate Hg to the upper edible parts of the plant only to a small extent.

  1. 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 process. Moreover, the application of species-unspecific isotope dilution GE-LA-ICP-MS has the potential to offer reliable, direct and simultaneous quantification of proteins after conventional 1D and 2D gel electrophoretic separations.

  2. Matrix effects in inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xiaoshan [Iowa State Univ., Ames, IA (United States)

    1995-07-07

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

  3. 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.

  4. Use of laser ablation-inductively coupled plasma-time of flight-mass spectrometry to identify the elemental composition of vanilla and determine the geographic origin by discriminant function analysis.

    Science.gov (United States)

    Hondrogiannis, Ellen M; Ehrlinger, Erin; Poplaski, Alyssa; Lisle, Meredith

    2013-11-27

    A total of 11 elements found in 25 vanilla samples from Uganda, Madagascar, Indonesia, and Papua New Guinea were measured by laser ablation-inductively coupled plasma-time-of-flight-mass spectrometry (LA-ICP-TOF-MS) for the purpose of collecting data that could be used to discriminate among the origins. Pellets were prepared of the samples, and elemental concentrations were obtained on the basis of external calibration curves created using five National Institute of Standards and Technology (NIST) standards and one Chinese standard with (13)C internal standardization. These curves were validated using NIST 1573a (tomato leaves) as a check standard. Discriminant analysis was used to successfully classify the vanilla samples by their origin. Our method illustrates the feasibility of using LA-ICP-TOF-MS with an external calibration curve for high-throughput screening of spice screening analysis.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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%.

  13. 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...

  14. 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.

  15. 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.

  16. 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...

  17. 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.

  18. 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.

  19. 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.

  20. 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...

  1. 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...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-03-29

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

  3. 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.

  4. 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.

  5. 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.

  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. 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.

  9. [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.

  10. 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.

  11. 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%.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ebert, Christopher Hysjulien [Ames Lab., Ames, IA (United States)

    2012-01-01

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

  13. 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.

  14. 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.

  15. Inductively coupled plasma mass spectrometer with laser ablation metal ions release detection in the human mouth

    Science.gov (United States)

    Kueerova, Hana; Dostalova, Tatjana; Prochazkova, J.

    2002-06-01

    Presence of more dental alloys in oral cavity often causes pathological symptoms. Due to various and multi-faced symptomatology, they tend to be a source of significant problems not only for the patient but also for the dentist. Metal ions released from alloys can cause subjective and objective symptoms in mouth. The aim of this study was detection of metal elements presence in saliva. There were 4 groups of examined persons: with intact teeth (15 individuals) with metallic restorations, pathological currents 5-30 (mu) A, multi-faced subjective symptomatology and uncharacteristic objective diagnosis (32 patients), with metallic restorations and no subjective symptoms (14 persons) and with metallic restorations, without pathological currents and with problems related to galvanism (13 patients). Presence of 14 metal elements was checked by inductively coupled plasma mass spectrometer with laser ablation. Nd:YAG laser detector was used. There were significant differences in content of silver, gold and mercury between persons with intact teeth and other three groups. There were no differences found between subjects with and without galvanic currents, and presence of subjective and objective symptoms.

  16. 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.

  17. 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.

  18. 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.

  19. Depth profile analysis of various titanium based coatings on steel and tungsten carbide using laser ablation inductively coupled plasma--"time of flight" mass spectrometry.

    Science.gov (United States)

    Bleiner, D; Plotnikov, A; Vogt, C; Wetzig, K; Günther, D

    2000-01-01

    A homogenized 193 nm ArF* laser ablation system coupled to an inductively coupled plasma-"Time of Flight"-mass spectrometer (LA-ICP-TOFMS) was tested for depth profiling analysis on different single-layer Ti based coatings on steel and W carbides. Laser parameters, such as repetition rate, pulse energy and spatial resolution were tested to allow optimum depth related calibration curves. The ablation process using a laser repetition rate of 3 Hz, 120 microm crater diameter, and 100 mJ output energy, leads to linear calibration curves independent of the drill time or peak area used for calibrating the thickness of the layer. The best depth resolution obtained (without beam splitter) was 0.20 microm per laser shot. The time resolution of the ICP-TOFMS of 102 ms integration time per isotope was sufficient for the determination of the drill time of the laser through the coatings into the matrix with better than 2.6% RSD (about 7 microm coating thickness, n = 7). Variation of the volume of the ablation cell was not influencing the depth resolution, which suggests that the depth resolution is governed by the ablation process. However, the application on the Ti(N,C) based single layer shows the potential of LA-ICP-TOFMS as a complementary technique for fast depth determinations on various coatings in the low to medium microm region.

  20. Calibration graphs for Ti, Ta and Nb in sintered tungsten carbide by infrared laser ablation inductively coupled plasma atomic emission spectrometry.

    Science.gov (United States)

    Kanický, V; Otruba, V; Mermet, J M

    2001-12-01

    Infrared laser ablation (IR-LA) has been studied as a sample introduction technique for the analysis of sintered cobalt-cemented tungsten carbide materials by inductively coupled plasma atomic emission spectrometry (ICP-AES). Fractionation of cobalt was observed. Linearity of calibration plots was verified at least up to 15% Ti, 8% Ta, and 3% Nb. Above 1% (m/m) Ti, Ta, and Nb, the repeatability of results was better than 3% R.S.D. The relative uncertainty at the centroid of the calibration line was in the range from +/- 3% to +/- 4% for Ti, Ta, and Nb with internal standardization by tungsten and up to +/- 5% without internal standardization. The limits of detection were 0.004% Ti, 0.001% Ta, and 0.004% Nb. Elimination of the cemented hardmetal dissolution procedure is the main advantage of this method.

  1. 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.

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

    Science.gov (United States)

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

    2016-06-01

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

  3. 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.

  4. 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 ...

  5. 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...

  6. 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

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. 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.

  16. 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...

  17. 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 % .

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. The effects of analyte mass and collision gases on ion beam formation in an inductively coupled plasma mass spectrometer

    Science.gov (United States)

    Larsen, Jessica J.; Edmund, Alisa J.; Farnsworth, Paul B.

    2016-11-01

    Planar laser induced fluorescence (PLIF) was used to evaluate the effect of matrix components on the formation and focusing of a Ba ion beam in a commercial inductively coupled plasma mass spectrometer. Cross sections of the ion beams were taken in the second vacuum stage, in front of the entrance to the mass analyzer. Under normal operating conditions, the addition of Pb shifted the position of the Ba ion beam to the right. PLIF was also used to evaluate the effect of a collision reaction interface (CRI) on Ca and Ba ion beams. A wider velocity distribution of ions and a decrease in overall intensity were observed for the CRI images. The fluorescence and mass spectrometer signals decreased with increased CRI flow rates. These effects were most obvious for Ca ions with He gas.

  5. 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.

  6. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Alves, L.C.

    1993-09-01

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

  8. 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…

  9. 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

  10. 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...

  11. 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.

  12. 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.

  13. 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.

  14. 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(+).

  15. Interfacing capillary electrophoresis with inductively coupled plasma mass spectrometry by direct injection nebulization for selenium speciation

    DEFF Research Database (Denmark)

    Bendahl, Lars; Gammelgaard, Bente; Jons, O.;

    2001-01-01

    limits of 20 and 1 ng L-1 were obtained for Se-82 and Rh-103, respectively, at sample uptake rates of 10-30 muL min(-1), based on three times the standard deviation of blank solution (3 sigma (b), n = 10). The nebulizer was used as part of the interface for coupling of CE with ICP-MS and applied...... limits were in the sub mug Se L-1 range, corresponding to absolute detection limits in the range 25-125 fg selenium. Repeatability (n = 6) expressed as relative standard deviations with respect to migration times, peak heights and peak areas were better than 1.6, 6.7 and 6.0%, respectively...

  16. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Ferguson, Jill Wisnewski [Iowa State Univ., Ames, IA (United States)

    2006-01-01

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

  18. 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)

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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)

  6. 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.

  7. 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.

  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. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.)

  16. 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.

  17. 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.

  18. 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 ...

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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-).

  11. 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.

  12. 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.

  13. 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.

  14. 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)

  15. 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.

  16. 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.

  17. Comparing Theory and Experiment for Analyte Transport in the First Vacuum Stage of the Inductively Coupled Plasma Mass Spectrometer

    Science.gov (United States)

    Zachreson, Matthew R.

    The inductively coupled plasma mass spectrometer (ICP-MS) has been used in laboratories for many years. The majority of the improvements to the instrument have been done empirically through trial and error. A few fluid models have been made, which have given a general description of the flow through the mass spectrometer interface. However, due to long mean free path effects and other factors, it is very difficult to simulate the flow details well enough to predict how changing the interface design will change the formation of the ion beam. Towards this end, Spencer et al. developed FENIX, a direct simulation Monte Carlo algorithm capable of modeling this transitional flow through the mass spectrometer interface, the transitional flow from disorganized plasma to focused ion beam. Their previous work describes how FENIX simulates the neutral ion flow. While understanding the argon flow is essential to understanding the ICP-MS, the true goal is to improve its analyte detection capabilities. In this work, we develop a model for adding analyte to FENIX and compare it to previously collected experimental data. We also calculate how much ambipolar fields, plasma sheaths, and electron-ion recombination affect the ion beam formation. We find that behind the sampling interface there is no evidence of turbulent mixing. The behavior of the analyte seems to be described simply by convection and diffusion. Also, ambipolar field effects are small and do not significantly affect ion beam formation between the sampler and skimmer cones. We also find that the plasma sheath that forms around the sampling cone does not significantly affect the analyte flow downstream from the skimmer. However, it does thermally insulate the electrons from the sampling cone, which reduces ion-electron recombination. We also develop a model for electron-ion recombination. By comparing it to experimental data, we find that significant amounts of electron-ion recombination occurs just downstream from the

  18. 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.

  19. 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)).

  20. 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...

  1. 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

  2. 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

  3. 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.

  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. 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.

  6. 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...

  7. [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

  8. 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...

  9. Combining asymmetrical flow field-flow fractionation with light-scattering and inductively coupled plasma mass spectrometric detection for characterization of nanoclay used in biopolymer nanocomposites

    DEFF Research Database (Denmark)

    Schmidt, Bjørn; Petersen, Jens Højslev; Koch, C. Bender

    2009-01-01

    of polylactide (PLA) with 5% Cloisite®30B (a derivatized montmorillonite clay) as a filler. Based on AF4-MALS analyses, we found that particles ranging from 50 to 800 nm in radius indeed migrated into the 95% ethanol used as a food simulant. The full hyphenated AF4-MALS-ICP-MS system showed, however, that none...... of clay nanoparticulates, an analytical system combining asymmetrical flow field-flow fractionation (AF4) with multi-angle light-scattering detection (MALS) and inductively coupled plasma mass spectrometry (ICP-MS) is presented. In a migration study, we tested a biopolymer nanocomposite consisting...

  10. Modeling the gas flow upstream and in the sampling nozzle of the inductively coupled plasma mass spectrometer via the Direct Simulation Monte Carlo algorithm

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, Ross L. [Brigham Young University (United States)], E-mail: ross_spencer@byu.edu; Krogel, Jaron; Palmer, Jamie; Payne, Adam; Sampson, Andrew; Somers, William; Woods, Charles N. [Brigham Young University (United States)

    2009-03-15

    The Direct Simulation Monte Carlo algorithm has been applied to the flow of neutral argon gas through the first vacuum stage of the Inductively Coupled Plasma Mass Spectrometer. Good agreement is found between the simulation results and the equations of fluid dynamics, including the approximate hemispherical sink model of Douglas and French. The simulation reveals details of boundary layer formation in the nozzle, including a reduction in the total flow through the nozzle of about 15% from the ideal value calculated by Douglas and French.

  11. Study on the uptake and distribution of gadolinium based contrast agents in biological samples using laser ablation with inductively coupled plasma mass spectroscopy; Untersuchungen zur Aufnahme und Verteilung von gadoliniumbasierten Kontrastmitteln in biologischen Proben mittels Laserablation mit induktiv gekoppelter Plasma-Massenspektrometrie

    Energy Technology Data Exchange (ETDEWEB)

    Lingott, Jana

    2016-01-05

    Gadolinium based contrast agents are used for magnetic resonance imaging. After their excretion by medicated patients they reach surface water passing waste water treatment plants where they are not removed sufficiently. The behavior of the contrast agents in the environment and the interaction with organisms was investigated in this work due to the toxicity of the free Gd{sup 3+} ion and the associated risks, such as accumulation in the human food chain. In this work, the two elemental analytical imaging methods laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and synchrotron radiation X-ray fluorescence analysis (SRXRF) have been used to investigate the uptake, distribution, and excretion of Gd-based contrast agents by various biological systems. Both methods were analytically characterized and compared for this application. The detection limits of gadolinium were determined under optimized conditions by LA-ICP-MS and SRXRF. With calibration by remains of dried elemental standard droplets detection limits of 0.78 pg absolute amount of gadolinium (LA-ICP-MS), respectively 89 pg (SRXRF) were reached. Based on filamentous algae as water plants the uptake and the excretion of Gd-based contrast agents were revealed. The dependence on concentration of the contrast agent in the exposition solution and the independence of temporal uptake within one to seven days were studied for duckweed. By LA-ICP-MS gadolinium was quantified in a leaf of cress plant. The verification of the results was performed by SRXRF and ICP-MS after digestion. Furthermore, the uptake and distribution of Gd-based contrast agents in higher organisms (water flea) were observed. The exact location of gadolinium was resolved by three-dimensional μ-computed tomography by the comparison of an exposed with a Gd-free water flea. In all studies, gadolinium was detected in the investigated exposed model organisms. It can be concluded that the contrast agents were taken from the

  12. 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.

  13. 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.

  14. 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.

  15. 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 +})

  16. 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.

  17. 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.

  18. 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.

  19. 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...... at an intermediate and at a high linear velocity. The precision was better than 2.2% R.S.D. and regression analysis showed that a linear response was achieved at both flow rates (R2 > 0.9993, n = 36). The analysis time was less than 4.5 min at a flow rate of 50 microL min(-1) and limits of detection...

  20. 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

  1. 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.

  2. Arsenic speciation in seafood samples with emphasis on minor constituents. An investigation by high performance liquid chromatography with inductively coupled plasma mass spectrometric detection

    DEFF Research Database (Denmark)

    Larsen, Erik Huusfeldt; Pritzl, G.; Hansen, S. H.

    1993-01-01

    Extracts of 11 samples of shrimp, crab, fish, fish liver, shellfish and lobster digestive gland (hepatopancreas), including five certified reference materials, were investigated for their contents of arsenic compounds (arsenic speciation). The cation-exchange high performance liquid chromatography...... procedure was optimized to separate six cationic arsenicals present in the samples with internal chromatographic standardization by the trimethylselenonium ion, which was detected a m/z 82 (Se-82), in addition to arsenic at m/z 75, by inductively coupled plasma mass spectrometry. The content of each species...... gland, and another unknown (U2) was present at 0.2-6.4% in all samples. The contents of arsenite and arsenate were 0-1.4%, dimethylarsinate 8.2-29% while monomethylarsonate was detected only in oyster at 0.3% of the total extracted arsenic. Finding tetramethylarsonium ion and arsenocholine in a variety...

  3. Speciation of eight arsenic compounds in human urine by high performance liquid chromatography with inductively coupled plasma mass spectrometric detection using antimonate for internal chromatographic standardization

    DEFF Research Database (Denmark)

    Larsen, Erik Huusfeldt; Pritzl, G.; Hansen, S. H.

    1993-01-01

    Four anionic and four cationic arsenic compounds in urine were separated by anion- and cation-exchange high-performance liquid chromatography and detected by inductively coupled plasma mass spectrometry (ICP-MS) at m/z 75. The species were the anions arsenite, arsenate, monomethylarsonate...... and dimethylarsinate and the cations arsenobetaine, trimethylarsine oxide, arsenocholine and the tetramethylarsonium ion. Hexahydroxyantimonate(III) was co-chromatographed with the arsenic anions but detected at m/z 121 and used as an internal standard for their qualitative analysis. Arsenite was prone to oxidation...... to arsenate in urine but was stable after at least 4-fold dilution of the urine with water. Arsenite was unstable in both urine samples and standard mixtures when diluted with the basic (pH 10.3) mobile phase used for anion chromatography. This could not be prevented by adding ascorbic acid as antioxidant...

  4. 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...

  5. 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.

  6. 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.

  7. 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...

  8. 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).

  9. 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...

  10. Standard test method for the determination of impurities in plutonium metal: acid digestion and inductively coupled plasma-mass spectroscopy (ICP-MS) analysis

    CERN Document Server

    American Society for Testing and Materials. Philadelphia

    2006-01-01

    1.1 This Test Method covers the determination of 58 trace elements in plutonium (Pu) metal. The Pu sample is dissolved in acid, and the concentration of the trace impurities are determined by Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS). 1.2 This Test Method is specific for the determination of trace impurities in Pu metal. It may be applied to other types of Pu materials, such as Pu oxides, if the samples are dissolved and oxidized to the Pu(IV) state. However, it is the responsibility of the user to evaluate the performance of other matrices. 1.3 This standard does not purport to address all of the safety concerns associated with its use. It is the responsibility of the user of this method to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use of this standard.

  11. 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).

  12. 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.

  13. 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

  14. 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.

  15. SPECIATION OF SELENIUM AND ARSENIC COMPOUNDS BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW AND ON-LINE REDUCTION OF SELENIUM(VI) TO SELENIUM(IV) WITH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

    Science.gov (United States)

    Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV') by mixing the CE effluent with concentrated HCl. A microporo...

  16. 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%.

  17. 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.

  18. 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.)

  19. 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.

  20. 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

  1. Total zinc quantification by inductively coupled plasma-mass spectrometry and its speciation by size exclusion chromatography-inductively coupled plasma-mass spectrometry in human milk and commercial formulas: Importance in infant nutrition.

    Science.gov (United States)

    Fernández-Menéndez, Sonia; Fernández-Sánchez, María L; Fernández-Colomer, Belén; de la Flor St Remy, Rafael R; Cotallo, Gil Daniel Coto; Freire, Aline Soares; Braz, Bernardo Ferreira; Santelli, Ricardo Erthal; Sanz-Medel, Alfredo

    2016-01-01

    This paper summarises results of zinc content and its speciation in human milk from mothers of preterm and full-term infants at different stages of lactation and from synthetic formula milks. Human milk samples (colostrum, 7th, 14th, and 28th day after delivery) from Spanish and Brazilian mothers of preterm and full-term infants (and also formula milks) were collected. After adequate treatment of the sample, total Zn was determined, while speciation analysis of the Zn was accomplished by size exclusion chromatography coupled online with the ICP-MS. It is observed that total zinc content in human milk decreases continuously during the first month of lactation, both for preterm and full term gestations. All infant formulas analysed for total Zn were within the currently legislated levels. For Zn speciation analysis, there were no differences between preterm and full term human milk samples. Moreover Zn species elute mainly associated with immunoglobulins and citrate in human milk whey. Interestingly the speciation in formula milk whey turned out to be completely different as the observed Zn(2+) was bound almost exclusively to low molecular weight ligands (citrate) and only comparatively very low amounts of the metal appeared to be associated with higher mass biomolecules (e.g. proteins).

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

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

    Science.gov (United States)

    Veyseh, Somayeh; Niazi, Ali

    2016-01-15

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

  14. 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...

  15. 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.

  16. 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....

  17. 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.

  18. 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.

  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 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%.

  1. 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.

  2. 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.

  3. 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.

  4. Evaluation of lead isotope compositions of NIST NBS 981 measured by thermal ionization mass spectrometer and multiple-collector inductively coupled plasma mass spectrometer

    Directory of Open Access Journals (Sweden)

    Honglin Yuan

    2016-09-01

    Full Text Available Because Pb isotopes can be used for tracing, they are widely used in many disciplines. The detection and analysis of Pb isotopes of bulk samples are usually conducted using thermal ionization mass spectrometer (TIMS and multiple-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, both of which need external reference materials with known isotopic compositions to correct for the mass discrimination effect produced during analysis. NIST NBS 981 is the most widely used reference material for Pb isotope analysis; however, the isotopic compositions reported by various analytical laboratories, especially those using TIMS, vary from each other. In this study, we statistically evaluated 229 reported TIMS analysis values collected by GeoReM in the last 30 years, 176 reported MC-ICP-MS analysis values, and 938 MC-ICP-MS analysis results from our laboratory in the last five years. After careful investigation, only 40 TIMS results were found to have double or triple spikes. The ratios of the overall weighted averages, 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb, obtained from 40 spiked TIMS reports and 1114 MC-ICP-MS results of NIST NBS 981 isotopes were 16.9406 ± 0.0003 (2s, 15.4957 ± 0.0002 (2s, and 36.7184 ± 0.0007 (2s, respectively.

  5. 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.

  6. 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%.

  7. 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).

  8. 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.

  9. 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‰.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Resonant laser ablation of metals detected by atomic emission in a microwave plasma and by inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Cleveland, Danielle; Stchur, Peter; Hou, Xiandeng; Yang, Karl X; Zhou, Jack; Michel, Robert G

    2005-12-01

    It has been shown that an increase in sensitivity and selectivity of detection of an analyte can be achieved by tuning the ablation laser wavelength to match that of a resonant gas-phase transition of that analyte. This has been termed resonant laser ablation (RLA). For a pulsed tunable nanosecond laser, the data presented here illustrate the resonant enhancement effect in pure copper and aluminum samples, chromium oxide thin films, and for trace molybdenum in stainless steel samples, and indicate two main characteristics of the RLA phenomenon. The first is that there is an increase in the number of atoms ablated from the surface. The second is that the bandwidth of the wavelength dependence of the ablation is on the order of 1 nm. The effect was found to be virtually identical whether the atoms were detected by use of a microwave-induced plasma with atomic emission detection, by an inductively coupled plasma with mass spectrometric detection, or by observation of the number of laser pulses required to penetrate through thin films. The data indicate that a distinct ablation laser wavelength dependence exists, probably initiated via resonant radiation trapping, and accompanied by collisional broadening. Desorption contributions through radiation trapping are substantiated by changes in crater morphology as a function of wavelength and by the relatively broad linewidth of the ablation laser wavelength scans, compared to gas-phase excitation spectra. Also, other experiments with thin films demonstrate the existence of a distinct laser-material interaction and suggest that a combination of desorption induced by electronic transition (DIET) with resonant radiation trapping could assist in the enhancement of desorption yields. These results were obtained by a detailed inspection of the effect of the wavelength of the ablation laser over a narrow range of energy densities that lie between the threshold of laser-induced desorption of species and the usual analytical

  16. 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

  17. 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).

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

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

    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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  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. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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).

  16. 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‰.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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

  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. 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

  10. 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

  11. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-06-01

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

  13. 激光烧蚀-电感耦合等离子体质谱法测定塑料中的Pb、Cd、Cr和Hg%Determination of Pb, Cd, Cr and Hg in plastic materials by laser ablation inductively coupled plasma mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    金献忠; 陈建国; 杨文潮; 潘炜娟

    2010-01-01

    采用激光烧蚀固体进样技术的电感耦合等离子体质谱法(LA-ICP-MS)测定了塑料中的Pb、Cd、Cr和Hg. 选择了线扫描激光烧蚀方式,并从灵敏度和稳定性角度优化了工作参数. 根据计算分馏因子考察了分馏效应,结果表明,所测元素分馏效应小. 塑料中Hg的记忆效应严重,认为主要来自样品表面吸附,减小样品的表面积可减小Hg的记忆效应. 以聚丙烯标准物质及其空白片作校准曲线,应用于ABS、PPS、PA66+30% GF、PVC、PTFE等实际塑料样品的测定,测定结果与ICP-OES (XRF)法测定值基本吻合. Pb、Cd、Cr和Hg的检测下限分别为0.002、0.001、0.08和1.5 mg/kg.

  14. 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

  15. 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

  16. Coupling sequential injection on-line preconcentration using a PTFE beads packed column to direct injection nebulization inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Wang, Jianhua; Hansen, Elo Harald

    2002-01-01

    An automated sequential injection on-line preconcentration procedure for trace metals by using a PTFE bead-packed microcolumn coupled to ICP-MS is described, and used for simultaneous analyses of cadmium and lead. In dilute nitric acid (0.5%, v/v), neutral complexes between the analytes and chela......An automated sequential injection on-line preconcentration procedure for trace metals by using a PTFE bead-packed microcolumn coupled to ICP-MS is described, and used for simultaneous analyses of cadmium and lead. In dilute nitric acid (0.5%, v/v), neutral complexes between the analytes...... and chelating reagent, diethyldithiophosphate (DDPA), are formed and adsorbed onto the surface of the PTFE beads. The adsorbed complexes are afterwards eluted with 20% nitric acid and the leading part of the eluate (40 mul) is stored in a sample loop (SL), the contents of which are subsequently transported, via...

  17. 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.

  18. FI/SI on-line solvent extraction/back extraction preconcentration coupled to direct injection nebulization inductively coupled plasma mass spectrometry for determination of copper and lead

    DEFF Research Database (Denmark)

    Wang, Jianhua; Hansen, Elo Harald

    2002-01-01

    at a sample flow rate of 6.0 ml/min The precisions (RSD) at the 0.2 mug/1 level were 4.4% (Cu) and 4.8% (Pb), respectively. The applicability of the procedure is demonstrated for the determination of copper and lead in three certified reference materials and a urine sample.......An automated sequential injection on-line preconcentration procedure for determination of trace levels of copper and lead via solvent extraction/back extraction coupled to ICP-MS is described. In citrate buffer of pH 3, neutral complexes between the analytes and the chelating reagent, ammonium...

  19. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-07-15

    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

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Report on three aliphatic dimethylarsinoyl compounds as common minor constituents in marine samples. An investigation using high-performance liquid chromatography inductively coupled plasma mass spectrometry and electrospray ionisation tandem mass spectrometry

    DEFF Research Database (Denmark)

    Sloth, Jens Jørgen; Larsen, Erik Huusfeldt; Julshamn, K.

    2005-01-01

    Three water-soluble aliphatic arsenicals, dimethylarsinoyl acetate (DMAA), dimethylarsinoyl ethanol (DMAE), and dimethylarsinoyl propionate (DMAP), were identified in marine biological samples. Sample extracts in methanol/water (1 + 1) were analysed by cation-exchange high-performance liquid...... chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS). Eluate fractions from the HPLC/ICPMS analyses containing the compounds in question were collected and subjected to analysis by electrospray ionisation tandem mass spectrometry (ESI-MS/MS), which provided supportive evidence...... for the structures of the three compounds. The concentrations of the three arsenicals were determined in 37 marine organisms comprising algae, crustaceans, bivalves, fish and mammals by HPLC/ICPMS. The three arsenicals DMAA, DMAE and DMAP, which occurred at mug kg(-1) concentrations, were detected in 25, 23 and 17...

  8. 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.

  9. 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).

  10. In-house validation of a method for determination of silver nanoparticles in chicken meat based on asymmetric flow field-flow fractionation and inductively coupled plasma mass spectrometric detection

    DEFF Research Database (Denmark)

    Löschner, Katrin; Navratilova, Jana; Grombe, Ringo;

    2015-01-01

    spectrometric detection (AF4-ICP-MS) was applied for quantitative analysis of silver nanoparticles (AgNPs) in a chicken meat matrix following enzymatic sample preparation. For the first time an analytical validation of nanoparticle detection in a food matrix by AF4-ICP-MS has been carried out and the results......Nanomaterials are increasingly used in food production and packaging, and validated methods for detection of nanoparticles (NPs) in foodstuffs need to be developed both for regulatory purposes and product development. Asymmetric flow field-flow fractionation with inductively coupled plasma mass...... showed repeatable and intermediately reproducible determination of AgNP mass fraction and size. The findings demonstrated the potential of AF4-ICP-MS for quantitative analysis of NPs in complex food matrices for use in food monitoring and control. The accurate determination of AgNP size distribution...

  11. A comparison of ion and atom behavior in the first stage of an inductively coupled plasma mass spectrometer vacuum interface: Evidence of the effect of an ambipolar electric field

    Energy Technology Data Exchange (ETDEWEB)

    Farnsworth, Paul B. [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States)], E-mail: paul_farnsworth@byu.edu; Spencer, Ross L.; Radicic, W. Neil; Taylor, Nicholas; Macedone, Jeffrey; Ma Haibin [Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 (United States)

    2009-09-15

    Velocities of argon atoms and calcium ions were measured in the first vacuum stage of an inductively coupled plasma mass spectrometer using high-resolution laser-excited fluorescence spectroscopy. The calcium ions reached terminal velocities in the supersonic expansion that were consistently 5-6% higher than those of argon atoms, despite minimal differences in the masses of the two species. A computational model of the expansion was developed that shows the development of an ambipolar electric field along the expansion axis. With reasonable assumptions about electron temperatures in the expansion, the model accounts for the differences between the terminal velocities of the neutral argon atoms and the singly-charged calcium ions.

  12. 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

  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. 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.

  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

    operating characteristics of the entire hyphenated system. An isocratic HPLC system, which employs an aqueous mobile phase with organic buffer constituents, is well suited for introduction into the ICP-MS because of the stability of the detector response and high degree of analyte sensitivity attained......Achievement of optimum selectivity, sensitivity and robustness in speciation analysis using high performance liquid chromatography (HPLC) with inductively coupled mass spectrometry (ICP-MS) detection requires that each instrumental component is selected and optimized with a view to the ideal....... 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. Study of ion chromatographic behavior of inorganic and organic antimony species by using inductively coupled plasma mass spectrometric (ICP-MS) detection

    Energy Technology Data Exchange (ETDEWEB)

    Ulrich, N. [University of Hannover, Department of Inorganic Chemistry (Germany)

    1998-04-01

    An on-line method for the analysis of Sb(III), Sb(V) and trimethylstiboxide (TMSbO) is presented. The separation is performed using ion chromatography (IC) on a strong anion-exchange column with phthalic acid plus 2% acteone at pH 5 as mobile phase. The chromatographic system is coupled to an ICP-MS as detector. The influence of different complexing agents on the chromatographic behavior of the antimony species is studied. Rather stable complexes of Sb(III) seem to be formed with citrate and tartrate under the experimental conditions. TMSbO forms a dianionic species with citrate in contrast to the otherwise monoanionic complex. (orig.) With 3 figs., 2 tabs., 8 refs.

  18. 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)

  19. 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.

  20. 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.

  1. 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.)

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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%.

  14. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Saetveit, Nathan Joe [Iowa State Univ., Ames, IA (United States)

    2008-01-01

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

  16. 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%.

  17. 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.

  18. 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.

  19. In-vivo evaluation of the permeability of the blood-brain barrier to arsenicals, molybdate, and methylmercury by use of online microdialysis-packed minicolumn-inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Su, Cheng-Kuan; Yang, Cheng-Hung; Lin, Cheng-Hsing; Sun, Yuh-Chang

    2014-01-01

    To study the permeability of the blood-brain barrier (BBB) to arsenates, arsenite, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), molybdate, and methylmercury, and the transfer behavior of these species, we constructed an automatic online analytical system comprising a microdialysis sampling device, a minicolumn packed with nonfunctionalized poly(vinyl chloride) beads, and an inductively coupled plasma mass spectrometer for continuous in-vivo measurement of their dynamic variation in the extracellular space of the brains of living rats. By using ion-polymer interactions as a novel working mechanism for sample pretreatment of volume-limited microdialysate, we simplified the operating procedure of conventional solid-phase extraction and reduced the contribution to the blank of the chemicals used. After optimizing this hyphenated system, we measured its performance by analysis of NIST standard reference materials 1640a (trace elements in natural water) and 2672a (trace elements in human urine) and by in-vivo monitoring of the dynamic variation of the compounds tested in the extracellular fluid (ECF) of rat brain. We found that intraperitoneal administration led to observable BBB permeability of arsenates, arsenite, DMA, MMA, and molybdate. Nevertheless, the limited sensitivity of the system and the size of microdialysis samples meant that detection of MeHg in ECF remained problematic, even when we administered a dose of 20 mg MeHg kg(-1) body weight. On the basis of these practical demonstrations, we suggest that our analytical system could be used not only for dynamic monitoring of the transfer kinetics of the four arsenicals and molybdate in the rat brain but also to describe associated neurotoxicity in terms of exposure to toxic metals and their species.

  20. 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.

  1. 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.

  2. Uncertainty evaluation for the detection limit of inductively coupled plasma mass spectrometer%四极杆电感耦合等离子体质谱仪检出限的不确定度评定

    Institute of Scientific and Technical Information of China (English)

    畅小军; 周巍松; 冯晓旭

    2011-01-01

    依据JJF1159 - 2006《四极杆电感耦合等离子体质谱仪校准规范》,使用标准溶液GBW(E) 130242(Be,In,Bi混合溶液)校准了四极杆电感耦合等离子体质谱仪的检出限,并对其可能引入的不确定度分量(空白溶液测量列的标准偏差、测量重复性、标准溶液的定值以及仪器的分辨力等)进行了分析,建立了数学模型,最后以合成标准不确定度乘以95%置信概率下的扩展因子2获得检出限的扩展不确定度.%Based on JJF1159-2006 "Calibration Specification for Quadrupole Inductively Coupled Plasma Mass Spectrometers", the detection limits of quadrupole ICP-MS are calibrated using the state standard solution GBW(E) 130242(mixed solution of Be,In,Bi elements). The main uncertainty components in determination process (standard deviation of blank solution,measurement repeatability,certified value of standard solution and instrumental resolution) were reasonably evaluated. A mathematical model was thus established. The expanded uncertainty of detection limit was obtained through multiplying the combined standard uncertainty by 2(expanded factor under confidence probability of 95%).

  3. 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.

  4. High-throughput sequential injection method for simultaneous determination of plutonium and neptunium in environmental solids using macroporous anion-exchange chromatography, followed by inductively coupled plasma mass spectrometric detection.

    Science.gov (United States)

    Qiao, Jixin; Hou, Xiaolin; Roos, Per; Miró, Manuel

    2011-01-01

    This paper reports an automated analytical method for rapid and simultaneous determination of plutonium and neptunium in soil, sediment, and seaweed, with detection via inductively coupled plasma mass spectrometry (ICP-MS). A chromatographic column packed with a macroporous anion exchanger (AG MP-1 M) was incorporated in a sequential injection (SI) system for the efficient retrieval of plutonium, along with neptunium, from matrix elements and potential interfering nuclides. The sorption and elution behavior of plutonium and neptunium onto AG MP-1 M resin was compared with a commonly utilized AG 1-gel-type anion exchanger. Experimental results reveal that the pore structure of the anion exchanger plays a pivotal role in ensuring similar separation behavior of plutonium and neptunium along the separation protocol. It is proven that plutonium-242 ((242)Pu) performs well as a tracer for monitoring the chemical yield of neptunium when using AG MP-1 M resin, whereby the difficulties in obtaining a reliable and practicable isotopic neptunium tracer are overcome. An important asset of the SI setup is the feasibility of processing up to 100 g of solid substrates using a small-sized (ca. 2 mL) column with chemical yields of neptunium and plutonium being ≥79%. Analytical results of three certified/standard reference materials and two solid samples from intercomparison exercises are in good agreement with the reference values at the 0.05 significance level. The overall on-column separation can be completed within 3.5 h for 10 g of soil samples. Most importantly, the anion-exchange mini-column suffices to be reused up to 10-fold with satisfactory chemical yields (>70%), as demanded in environmental monitoring and emergency scenarios, making the proposed automated assembly well-suited for unattended and high-throughput analysis.

  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. 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.

  7. Quantitative Analysis of Sulfide Minerals by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using Glass Reference Materials with Matrix Normalization Plus Sulfur Internal Standardization Calibration%玻璃标样结合硫内标归一定量技术在激光剥蚀-等离子体质谱分析硫化物矿物中的应用

    Institute of Scientific and Technical Information of China (English)

    袁继海; 詹秀春; 范晨子; 赵令浩; 孙冬阳; 贾泽荣; 胡明月; 蒯丽君

    2012-01-01

    A novel strategy for microanalysis of sulfides by laser ablation (LA)-ICP-MS was established. In this method, the relative sensitivity factor of Ca relative to S in anhydrite mineral reference material was taken as a transition bridge, by which the relative sensitivity factors of interesting elements in glass reference materials relative to Ca could be converted into relative sensitivity factors relative to S by the transition bridge, then the quantitative analysis of multi-elements in sulfide minerals by multi-glass reference materials with matrix normalization plus sulfur internal standardizationcalibration was carried out. 20 elements in the American polymetal sulfide mineral reference material MASS-1 were analyzed using this new method. The relative errors of major elements in MASS-1 were less than 10% ? And the results of trace elements with reference values were nearly within the uncertainty of the preliminary values. Multi-elements in 12 sulfide single minerals were analyzed by applying this new method. The relative errors of the greatest number of major elements were less than 10% , with which the results of most major elements were accurate than those obtained by MASS-1 as calibration standard with matrix normalization plus internal standardization or internal standard calibration. And the results to trace elements agreed well with the calibrated results by MASS-1 with matrix normalization plus internal standardization or internal standard calibration. This method overcomes the problem of non-matrix matched standards, enables to accurately determine the major composition of sulfur in sulfide minerals and suggests a new approach for analysis of sulfide minerals.%以硬石膏矿物标样中Ca相对于S的灵敏度因子为基准,将玻璃标样中主量和痕量元素相对于Ca的灵敏度因子转换成元素相对于S的灵敏度因子,建立了多玻璃标样结合硫内标归一定量技术分析硫化物单矿物多元素的新方法.利用本方法分析了美国合成多金属硫化物矿物标样MASS-1中20种元素,主量元素分析结果的相对误差小于10%,痕量元素分析结果几乎都落在给定值士不确定度范围内.利用本方法对12个硫化物单矿物分析结果表明,绝大多数主量元素含量测定值的相对误差小于10%,且多数主量元素甚至优于以MASS-1为外标、内标归一定量法及内标校准法分析结果,而痕量元素与MASS-1校准结果较为一致.本方法克服了基体不匹配的问题,能比较准确地定量分析硫化物矿物中的主成分S,可用于定量校准硫化物矿物.

  8. Multielement characterization of metal-humic substances complexation by size exclusion chromatography, asymmetrical flow field-flow fractionation, ultrafiltration and inductively coupled plasma-mass spectrometry detection: a comparative approach.

    Science.gov (United States)

    Bolea, E; Gorriz, M P; Bouby, M; Laborda, F; Castillo, J R; Geckeis, H

    2006-10-06

    The use of three different separation techniques, ultrafiltration (UF), high performance size exclusion chromatography (HPSEC) and asymmetrical flow field-flow fractionation (AsFlFFF), for the characterization of a compost leachate is described. The possible interaction of about 30 elements with different size fractions of humic substances (HS) has been investigated coupling these separation techniques with UV-vis absorption spectrophotometry and inductively coupled plasma-mass spectrometry (ICP-MS) as detection techniques. The organic matter is constituted by a polydisperse mixture of humic substances ranging from low molecular weights (around 1kDa) to significantly larger entities. Elements can be classified into three main groups with regard to their interaction with HS. The first group is constituted by primarily the monovalent alkaline metal ions and anionic species like B, W, Mo, As existing as oxyanions all being not significantly associated to HS. The second group consists of elements that are at least partly associated to a smaller HS size fraction (such as Ni, Cu, Cr and Co). A third group of mainly tri- and tetravalent metal ions like Al, Fe, the lanthanides, Sn and Th are rather associated to larger-sized HS fractions. The three separation techniques provide a fairly consistent size classification for most of the metal ions, even though slight disagreements were observed. The number-average molecular weight (Mn), the weight-average molecular weight (Mw) and the polydispersity (rho) parameters have been calculated both from AsFlFFF and HPSEC experiments and compared for HS and some metal-HS species. Differences in values can be partly explained by an overloading effect observed in the AsFlFFF experiments induced by electrostatic repulsion effects in the low ionic strength, high pH carrier solution. Size information obtained from ultrafiltration is not as resolved as for the other methods. Molecular weight cut-offs (MWCO) of the individual filter

  9. Development of procedure for measurement of Pb isotope ratios in seawater by application of seaFAST sample pre-treatment system and Sector Field Inductively Coupled Plasma Mass Spectrometry

    Science.gov (United States)

    Vassileva, Emilia; Wysocka, Irena

    2016-12-01

    Anthropogenic Pb in the oceans, derived from high-temperature industrial processes, fuel combustion and incineration can have an isotopic signature distinct from naturally occurring Pb, supplied by rock weathering. To identify the different pollution sources accurately and to quantify their relative contributions, Pb isotope ratios are widely used. Due to the high salt content (approximately 3.5% of total dissolved solids) and very low levels of Pb (typically from 1 to 100 ng L- 1) in seawater the determination of Pb isotope ratios requires preliminary matrix separation and analyte preconcentration. An analytical protocol for the measurements of Pb isotope ratios in seawater combining seaFAST sample pre-treatment system and Sector Field Inductively Coupled Plasma Mass Spectrometry (SF ICP-MS) was developed. The application of seaFAST system was advantageous, because of its completely closed working cycle and small volumes of chemicals introduced in pre-treatment step, resulting in very low detection limits and procedural blanks. The preconcentration/matrix separation step was also of crucial importance for minimizing the isobaric and matrix interferences, coming from the seawater. In order to differentiate between anthropogenic and natural Pb sources, particular attention was paid to the determination of 204Pb isotope because of its implication in some geological interpretations. The validation of the analytical procedure was effectuated according to the recommendations of the ISO/IEC 17025 standard. The method was validated by processing the common Pb isotope reference material NIST SRM 981. All major sources of uncertainty were identified and propagated together following the ISO/GUM guidelines. The estimation of the total uncertainty associated to each measurement result was fundamental tool for sorting the main sources of possible biases. The developed analytical procedure was applied to the coastal and open seawater samples, collected in different regions of

  10. 微波消解ICP-MS法检测生物检材中汞元素%Determination of Hg in Biological Samples by Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    马栋; 张丹; 卓先义; 刘伟; 沈保华; 沈敏

    2011-01-01

    Objective To establish an inductively coupled plasma mass spectrometry (ICP-MS) method for determination of Hg in biological samples. Methods The samples were digested with microwave digestion instru ment. ICP-MS was applied to detect Hg in blood, urine and hair specimens by using ll5In as an internal marker. The ability of gold to eliminate the memory effect of mercury was investigated with the gold amalga mate produced by gold and mercury. Results The limits of detection were in the 0.01 |xg/L, and the accu racy of the method ranged from 97.0% to 107.1%. The concentration of gold was 10μg/L and the memory effect of mercury was resolved. Conclusion The method is accurate, rapid, sensitive and suitable for the cases of mercury poisoning and the clinical diagnosis and monitoring for patients with mercury poisoning.%目的 建立生物检材中汞的电感耦合等离子体质谱分析方法.方法 采用微波消解法处理样品,以铟(115In)作内标,用电感耦合等离子体质谱仪对血液、尿液和头发中的汞含量进行分析.选择金与汞形成金汞齐,对金消除汞记忆效应的能力进行考察.结果 方法检出限为0.01μg/L,准确度为97.0%~107.1%.检测中添加金质量浓度在10μg/L时,可消除检测中汞的记忆效应.结论 建立的方法准确、快速、灵敏度高,适用于汞中毒案件的检测以及临床中汞中毒病人的诊断和监测.

  11. 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

  12. 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

  13. 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.%建立了电感耦合等离子体质谱法(ICP-MS)对光伏用多晶硅中B,Cu,Fe,Al,K,Ca,Cr,Mn,Fe,Co,Ni,Cu,Zn,As,Mo,W,Cd,Pb共计18个可能共存的杂质元素同时定量测定的方法.以硝酸、氢氟酸分解多晶硅试样,称重法确定加入试剂的量.采用动态反应池(DRC)技术,在池内引入氨气(NH_3)作为反应气体来消除质谱干扰.在选定的条件下,被测元素的检出限为0.8~6.9 pg/g(3σ),样品的加标回收率在83.0%~106%之间,相对标准偏差(RSD)为0.27%~2.7%(n=11).所建立的分析方法实现了对光伏用多晶硅样品中痕量元素的全分析,实际样品的测定结果与参考值相符.

  14. Simultaneous Determination of Nb and Ta in Geochemical Samples by Inductively Coupled Plasma Mass Spectrometry%ICP- MS同时测定地球化学样品中的铌钽

    Institute of Scientific and Technical Information of China (English)

    赵朝辉; 雷勇; 易建春

    2011-01-01

    建立了测定地球化学样品中铌、钽元素的ICP - MS方法.试样加入硝酸、氢氟酸、高氯酸,于电热板上加热消解样品,再以新配置王水提取,使铌、钽完全进入溶液,以内标法校正干扰,电感耦合等离子体质谱仪( ICP -MS)测定样品消解液中铌、钽元素.其中铌采用铑元素作为内标,以93质量数分析;钽采用铼元素作为内标,以181质量数分析.方法的检出限为Nb0.02 μg/g,Ta0.01μg/g精密度优于5%.整个方法检出限低、简单、快速和准确.经过国家一级地球化学标准物质的分析验证,结果与标准值吻合,方法已应用于国土资源调查的试样分析.%An analytical method for the determination of niobium ( Nb) and tantalum (Ta) in geochemical samples by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The samples were digested on electrical hot plate by mixed acid consisted of nitric acid, hydrofluoric acid and perchloric acid. After digestion newly -prepared aqua regia was added to ensure the complete dissolution of Nb and Ta. Internal standards were adopted for the interference correction of ICP-MS analysis,among which Rh93 and Re181 were selected as internal standarc elements of Nb and Ta respectively. The limits of detection for Nb and Ta were 0.02 ug · g-1 and 0.01 ug · -1respectively with the relative standard deviation (RSD) better than 5%. The method was validated by the analysis of primary geochemical reference materials,with all of its results consistent with standard values, which was then applied to analyze land and resource survey samples,and was proved to be simple,sensitive and accurate.

  15. Mercury speciation in seawater by liquid chromatography-inductively coupled plasma-mass spectrometry following solid phase extraction pre-concentration by using an ionic imprinted polymer based on methyl-mercury-phenobarbital interaction.

    Science.gov (United States)

    Rodríguez-Reino, María Pilar; Rodríguez-Fernández, Roi; Peña-Vázquez, Elena; Domínguez-González, Raquel; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

    2015-04-24

    Trace levels of inorganic mercury, methyl-mercury and ethyl-mercury have been assessed in seawater by high performance liquid chromatography (HPLC) hyphenated with inductively coupled plasma-mass spectrometry (ICP-MS) after solid phase extraction (SPE) pre-concentration with a novel synthesized ionic imprinted polymer. The adsorbent material was prepared by trapping a non-vinylated chelating ligand (phenobarbital) via imprinting of a ternary mixed ligand complex of the non-vinylated chelating agent, the template (methyl-mercury), and the vinyl ligand (metacrylic acid, MAA). Ethylene dimetacrylate (EDMA) and 2,2'-azobisisobutyronitrile (AIBN) were used as cross-linker and initiator reagents, respectively; and the precipitation polymerization technique was used in a porogen of acetonitrile/water (4:1). The best retention properties for methyl-mercury, inorganic mercury and ethyl-mercury species from seawater were obtained when loading 200 mL of sample adjusted to pH 8.0 and at a flow rate of 2.0 mL min(-1) on a column-packed with 200mg of the material. Quantitative mercury species recoveries were obtained using 4 mL of an eluting solution consisting of 0.8% (v/v) 2-mercaptoethanol and 20% (v/v) methanol (pH adjusted to 4.5) pumped at a flow rate of 2.0 mL min(-1). Mercury species separation was achieved on a Kinetex C18 column working under isocratic conditions (0.4% (v/v) 2-mercaptoethanol, 10% (v/v) methanol, pH 2.5, flow rate 0.7 mL min(-1)). ICP-MS detection was performed by monitoring the mercury mass to charge ratio of 202. The limits of quantification of the method were 11, 6.7, and 12 ng L(-1), for inorganic mercury, methyl-mercury and ethyl-mercury, respectively (pre-concentration factor of 50); whereas, analytical recoveries ranged from 96 to 106%. The developed method was successfully applied to several seawater samples from unpolluted areas.

  16. Novel bimodal porous N-(2-aminoethyl)-3-aminopropyltrimethoxysilane-silica monolithic capillary microextraction and its application to the fractionation of aluminum in rainwater and fruit juice by electrothermal vaporization inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Zheng, Fei; Hu, Bin

    2008-01-01

    A novel bimodal porous N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AAPTS)-silica monolithic capillary was prepared by sol-gel technology, and used as capillary microextraction (CME) column for aluminum fractionation by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV)-ICP-MS with the use of polytetrafluoroethylene (PTFE) slurry as fluorinating agent. The extraction behaviors of different Al species were studied and it was found that in the pH range of 4-7, labile monomeric Al (free Al 3+, Al-OH and Al-F) could be retained quantitatively on the monolithic capillary, while non-labile monomeric Al (Al-Cit and Al-EDTA) passed through the capillary directly. The labile monomeric Al retained on monolithic capillary was eluted with 10 μL 1 mol L - 1 HCl and the elution was introduced into the ETV for fluorination assisted ETV-ICP-MS determination. The total monomeric Al fraction was also determined by AAPTS-silica monolithic CME-fluorination-assisted electrothermal vaporization (FETV)-ICP-MS after the sample solution was adjusted to pH 8.8. Non-labile monomeric Al was obtained by subtracting labile monomeric Al from the total monomeric Al. Under the optimized conditions, the relative standard deviation (R.S.D) was 6.2% ( C = 1 μg L - 1 , n = 7; sample volume, 5 mL), and the limit of detection was 1.6 ng L - 1 for Al with an enrichment factor of 436 fold and a sampling frequency of 9 h - 1 . The prepared AAPTS-silica monolithic capillary showed an excellent pH tolerance and solvent stability and could be used for more than 250 times without decreasing adsorption efficiency. The developed method was applied to the fraction of Al in rainwater and fruit juice, and the results demonstrated that the established system had advantages over the existing 8-hydroxyquinoline (8-HQ) chelating system for Al fractionation such as wider pH range, higher tolerance of interference and better regeneration.

  17. 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.

  18. 电感耦合等离子体质谱法检测龙舌兰酒中22种元素%Detection of 22 Elements in Tequila by Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    张建; 田玲; 杨俊; 卢垣宇

    2016-01-01

    建立电感耦合等离子体质谱(ICP-MS)法同时快速测定进口龙舌兰酒中22种元素锂、钠、镁、铝、钾、钙、钒、铬、锰、铁、钴、镍、铜、锌、砷、硒、银、镉、钡、铅、铋、锶的分析方法。龙舌兰酒经水浴挥发乙醇处理,采用ICP-MS测定,外标法定量。结果表明,该方法测定22种元素的线性范围宽,线性关系良好(r>0.999),检出限低,各元素的加标回收率在90%~110%之间,相对标准偏差均小于5%。方法具有简单、快速、灵敏度高、准确度高、回收率高等特点,完全可以满足龙舌兰酒中22种元素的分析要求。%A method for rapid and simultaneous detection of 22 elements in imported Tequila including lithium, sodium, magnesium, alumi-num, potassium, calcium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, arsenic, selenium, silver, cadmium, barium, lead, bismuth, strontium etc. has been developed by inductively coupled plasma mass spectrometry (ICP-MS). In the detection, Tequila was treated by water evaporation of ethanol and then measured by ICP-MS with external standard method quantification. The results showed that, the meth-od has a wide linear range,good linear relationships (r>0.999),and low detection limits,and the recovery rate of each element is within 90%~110%,and the relative standard deviation is less than 5%. In conclusion, the method had the advantages including simple and rapid operation, high sensitivity, high accuracy, and high recovery rate etc. and it could fully meet the requirements of the analysis of 22 elements in Tequila.

  19. 电感耦合等离子体质谱法测定钼矿石和钼精矿中铼%Determination of rhenium in molybdenum ores and molybdenum concentrate by inductively coupled plasma mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    程秀花; 黎卫亮

    2013-01-01

    采用氧化镁焙烧样品,热水浸提后不需分离富集,电感耦合等离子体质谱法直接测定钼矿石及钼精矿中铼.对不同焙烧熔剂、焙烧条件、浸提条件以及仪器测定条件进行了研究,结果表明:以氧化镁为焙烧试剂,在650℃保温90 min,趁热用热水浸提为最佳溶样条件,测定时选用103 Rh为内标元素,可有效校正仪器漂移,减小基体效应的干扰.方法检出限为0.005 μg/g,回收率在94%~102%之间.本方法经国家标准物质分析验证,结果与认定值吻合,相对标准偏差(RSD,n=5)≤3.6%,适合钼矿石及钼精矿中含量为0.05~300 μg/g铼的测定.%Molybdenum ore and molybdenum concentrate were calcined by magnesium oxide. After hot water extraction,the sample was directly determined by inductively coupled plasma mass spectrometry to obtain the content of rhenium. A study was conducted on the calcination solvent & conditions,extraction conditions and instrumental determination conditions. Results indicated that: magnesium oxide was taken as calcination solvent; the sample was kept at 650 °C for 90 min; the optimal dissolution conditions was to use hot water for leaching; 103Rh was selected as internal element to effectively correct instrumental drift and reduce the interference of matrix effect. The detection limit was 0. 005 μg/g and recoveries were between 94 % and 102 %. The method was tested by certified reference materials with the result consistent with certified value and RSD (n = 5) ≤ 3. 6 %. The method is suitable for the determination of rhenium with the content of 0. 05 ~ 300 μg/g in molybdenum ore and molybdenum concentrate.

  20. In situ determination of V(V) by diffusive gradients in thin films and inductively coupled plasma mass spectrometry techniques using amberlite IRA-410 resin as a binding layer.

    Science.gov (United States)

    Luko, Karen Silva; Menegário, Amauri Antonio; Suárez, Carlos Alfredo; Tafurt-Cardona, Makenly; Pedrobom, Jorge Henrique; Rolisola, Ana Marta Cavinato Marchini; Sulato, Everton Tiago; Kiang, Chang Hung

    2017-01-15

    Amberlite IRA-410 anionic exchange resin was evaluated as the binding layer for sampling V(V) by using Diffusive Gradients in Thin Films (DGT). V(V) was determined by inductively coupled plasma mass spectrometry (ICP-MS). Mass vs. time DGT deployments (ionic strength = 0.03 mol L(-1) NaNO3, pH = 5.6 and T = 23.5 ± 0.5 °C) was characterized by excellent linear relationship (R(2) = 0.9993) and a significant retention of V(V) by the binding layer. An exchange capacity of at least 40 μg V g(-1) resin was achieved for the proposed binding layer. The diffusion coefficient obtained (7.13 ± 0.6 10(-6) cm(2) s(-1)) agrees with the literature. The accumulation rate of V(V) was not significantly affected by ionic strength of solutions up to 0.03 mol L(-1) and for the entire studied pH range (from 3 to 9). Furthermore, when comparing the concentrations obtained using IRA-410-DGT and those obtained by direct measurement of the solution concentrations, the proposed approach provided a reduction of the (35)Cl(16)O interference on V(V) determination by ICP-MS. Determination of V in normal mode (without collision cell) in solutions containing analyte:Cl(-) concentration ratio up to 1:500,000 was not affected by interference of (35)Cl(16)O(+) polyatomic ion even when normal mode ICP-MS was used. Potential interfering ions on sampling V(V) by DGT (PO4(3-) and SO4(2-)) showed no significant effects on the accumulation rate of V(V). Laboratory tests performed using synthetic samples, natural freshwater and acid drainage water showed an excellent performance (recoveries from 93% to 110%). For in situ deployment, measurements of V(V) by the proposed approach was not significantly different (95.5%) from the value of dissolved V concentration.

  1. Speciation of Volatile Selenium Species in Plants Using Gas Chromatography/Inductively Coupled Plasma Mass Spectrometry%气相色谱/电感耦合等离子体质谱测定植物中挥发性硒化合物

    Institute of Scientific and Technical Information of China (English)

    Juris MEIJA; Maria MONTES-BAY(O)N; Joseph A CARUSO; Danika L LEDUC; Norman TERRY

    2004-01-01

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

  2. The coupling of capillary electrophoresis-inductively coupled plasma mass spectrometer as a speciation instrument for actinides at trace level; Le couplage electrophorese capillaire-spectrometre de masse a source plasma en tant qu'instrument de speciation des actinides a l'etat de traces

    Energy Technology Data Exchange (ETDEWEB)

    Delorme, A

    2004-07-01

    An interface between the separation technique (capillary electrophoresis) and the analytical technique (Inductively Coupled Plasma - Mass Spectrometer) was developed. In that sense, bibliographic and parametric studies allowed to define necessary conditions for the good working of both techniques. The results obtained led to the realisation of an interface capillary electrophoresis / ICP-MS (CE / ICP-MS). This one was experimentally validated on classical separations (alkalis / earth-alkalis and lanthanides) and the detection limit of the analytical system was determined equal to 4 x 10{sup -11} mol.L{sup -1} for plutonium. This result exhibits a gain in detection limit of a factor higher than 10{sup 4} compared to the capillary electrophoresis in standard detection (UV). The studies were made in order to check the capacity of the CE / ICP-MS coupling as a speciation instrument for actinides at trace level and to define the associated analytical procedures. The coupling turned out to be a suited instrument for the determination of absolute electrophoretic mobilities at infinite dilution (physico-chemical property which allows to predict the migration time of an ion under an electrical field in a given electrolyte), for the determination of thermodynamic constants and for the separation of different actinide oxidation states in solution. (author)

  3. Determination of aminopolycarboxylic acids at ultra-trace levels by means of online coupling ion exchange chromatography and inductively coupled plasma-mass spectrometry with indirect detection via their Pd²⁺-complexes.

    Science.gov (United States)

    Nette, David; Seubert, Andreas

    2015-07-16

    A new indirect IC-ICP-MS method for the determination of aminopolycarboxylic acids in water samples is described. It is based on the addition of an excess of Pd(II) to water samples. The analytes are forced into very strong and negatively charged palladium complexes, separated by ion exchange chromatography and detected by their palladium content, utilizing an on-line coupled ICP-MS. This method is suitable to determine the concentration of 8 aminopolycarboxylic acids (nitrilotriacetic acid (NTA), (2-carboxyethyl) iminodiacetic acid (β-ADA), methylglycinediacetic acid (MGDA), 2-hydroxyethyl) ethylenediamine triacetic acid (HEDTA), diethylene triamine pentaacetic acid (DTPA), ethylendiamine tetraacetic acid (EDTA), 1,3-diaminopropane tetraacetic acid (1,3-PDTA) and 1,2-diaminopropane tetraacetic acid (1,2-PDTA) at the ng kg(-1) level. The method is faster and easier than the established gas chromatography (GC)-method ISO 16588:2002 and up to two orders of magnitude more sensitive than the ion pair chromatography based method of DIN 38413-8. Analytic performance is superior to ISO 16588:2002 and the comparability is good.

  4. Determination of Common Metal Elements in Eleven-ingredients Shenqi Capsules by Inductively Coupled Plasma Mass Spectrometry%ICP-MS检测十一味参芪胶囊中常见金属元素

    Institute of Scientific and Technical Information of China (English)

    胡军高; 梁旭霞; 梁晓艳; 王晶; 陈光强

    2012-01-01

    common metal elements, ferrum(Fe), chromium(Cr), manganese(Mn), nickel(Ni), cuprum(Cu), zinc(Zn), arsenicum(As), argentums(Ag), chromium(Cd), stannum(Sn), stibine(Sb), barium(Ba), and plurabum(Pb), in Eleven-ingredient Shengqi Capsules, and to detect those elements in the capsules. Methods Three batches of Eleven-ingredient Shengqi Capsules were randomly sampled and weighed individually into 0.4 g. The three weighed samples were digested by wet method with concentrated nitric acid(HNO3) into colorless or yellowish solution, the metered volume being 10 mL. Based on online internal standards, the analysis method for common metal elements in the samples was set up. The accuracy and precision of the analysis method was verified with certified reference materials lyophilised beech leave powder and tea leaves. Common metal elements in the three batches of samples were analysed by inductively coupled plasma mass spectrometry(ICP-lV)S). The instrument parameters were below: radio frequency (RF) power at 1350 W, Barbinglon atomizer, carrier gas flow rate at 1.4 mL· min-1 sampling depth at 8.5 mm, Spectrum collection mode, and sample lifting speed at 0.4 L·min-1. Results The linear correlative coefficients for the common thirteen elements in the capsules were higher than 0.9990. The accuracy, precision and stability of the method were detected, and they all conformed to the analysis standard. RSD of within-day error was in the range of 0.50 %~4.56 %, and that of inter-day error was in the range of 1.17 %~5.03 %. Recoveries were 95.8 %~100.5 %(RSD being 1.82 %~2.68 %), 86.0 %~104.9 %(RSD being 1.70 %~6.33 %), 97.1 %~103.9 % (RSD being 2.51 %~5.19 %) and 92.1 %~110.0 %(RSD being 2.75 %~14.48 %) when the contents of metals were higher than 100 mg·kg-1, in the range of 1~100 mg·kg-1, 0.1~1 mg·kg-1 and lower than 0.1 mg·kg-1, respectively. Contents of Pb, Cd, Sn, Sb and Ag in the three batches of samples were lower than 1 mg·kg-1, Cr, Ni and Cu in the range of 1.3~4.6 mg·kg-1

  5. Plasma Mass Filters For Nuclear Waste Reprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Fetterman, Abraham J. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Fisch, Nathaniel J. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States)

    2011-05-01

    Practical disposal of nuclear waste requires high-throughput separation techniques. The most dangerous part of nuclear waste is the fission product, which contains the most active and mobile radioisotopes and produces most of the heat. We suggest that the fission products could be separated as a group from nuclear waste using plasma mass filters. Plasmabased processes are well suited to separating nuclear waste, because mass rather than chemical properties are used for separation. A single plasma stage can replace several stages of chemical separation, producing separate streams of bulk elements, fission products, and actinoids. The plasma mass filters may have lower cost and produce less auxiliary waste than chemical processing plants. Three rotating plasma configurations are considered that act as mass filters: the plasma centrifuge, the Ohkawa filter, and the asymmetric centrifugal trap.

  6. Plasma Mass Filters For Nuclear Waste Reprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Abraham J. Fetterman and Nathaniel J. Fisch

    2011-05-26

    Practical disposal of nuclear waste requires high-throughput separation techniques. The most dangerous part of nuclear waste is the fission product, which contains the most active and mobile radioisotopes and produces most of the heat. We suggest that the fission products could be separated as a group from nuclear waste using plasma mass filters. Plasmabased processes are well suited to separating nuclear waste, because mass rather than chemical properties are used for separation. A single plasma stage can replace several stages of chemical separation, producing separate streams of bulk elements, fission products, and actinoids. The plasma mass filters may have lower cost and produce less auxiliary waste than chemical processing plants. Three rotating plasma configurations are considered that act as mass filters: the plasma centrifuge, the Ohkawa filter, and the asymmetric centrifugal trap.

  7. Rapid determination of ¹³⁵Cs and precise ¹³⁵Cs/¹³⁷Cs atomic ratio in environmental samples by single-column chromatography coupled to triple-quadrupole inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Yang, Guosheng; Tazoe, Hirofumi; Yamada, Masatoshi

    2016-02-18

    For source identification, measurement of (135)Cs/(137)Cs atomic ratio not only provides information apart from the detection of (134)Cs and (137)Cs, but it can also overcome the application limit that measurement of the (134)Cs/(137)Cs ratio has due to the short half-life of (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 (135)Cs/(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 (133)Cs, at m/z 134, 135, and 137. The developed analytical method was successfully applied to measure (135)Cs/(137)Cs atomic ratios and (135)Cs activities in environmental samples (soil and sediment) for radiocesium source identification.

  8. 浊点萃取-电感耦合等离子体质谱法测定植物样品中的痕量铂与钯%Determination of trace platinum and palladium in plant samples by cloud point extraction coupled with inductively coupled plasma-mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    刘崴; 张欣; 李冰; 胡俊栋; 杨红霞; 黄中起

    2013-01-01

    建立了浊点萃取电感耦合等离子体质谱法测定植物样品中痕量铂与钯的方法,方法检出限分别为0.17 ng/g和0.10 ng/g,样品加标回收率在85%~110%之间.利用建立的方法对采自北京环路旁的植物样品进行了测定,铂与钯含量范围分别为0.35 ~5.35 ng/g和1.95~10.85 ng/g,钯的含量普遍高于铂的含量.%A method for the determination of trace amounts of platinum and palladium in plant samples using cloud point extraction ( CPE) coupled with inductively coupled plasma mass spectrometry ( ICP-MS) is described. The method detection limits for Pt and Pd were 0. 17 ng/g and 0. 10 ng/g, respectively. The standard recoveries were 85% ~110%. The method was successfully applied to the analysis of amounts of Pt and Pd in plant samples collected from the sides of the main ring roads in Beijing. The results indicated that the content ranges of Pt and Pd were 0. 35 ~5. 35 ng/g and 1. 95 ~10. 85 ng/g, respectively, and the content of Pd was more than Pt content generally.

  9. Identificação de resíduos de disparos de armas de fogo por meio da técnica de espectrometria de massas de alta resolução com fonte de plasma indutivo Identification of gunshot residues by high resolution inductively coupled plasma mass spectrometry

    Directory of Open Access Journals (Sweden)

    Edson Luis Tocaia dos Reis

    2004-06-01

    Full Text Available The violence derived from crimes involving firearms represents one of the main concerns of society. For this reason modern techniques have emerged in forensic science to identify suspects at crime scenes. This work describes a methodology to identify residues present in the hands of suspect by using a high resolution inductively coupled plasma mass spectrometry and collection procedure based on ethylenediaminetetraacetic acid (EDTA solution as a complexing agent in moistened swabs. In order to distinguish real gunshot residues from others types of residues present in the hand of suspect, ternary ratio per cent diagrams were developed for antimony (Sb, barium (Ba and lead (Pb detected on the hands of volunteers, before and immediately after shooting tests, revealing a remarkable difference in both situations.

  10. Evaluation of uncertainty for determination of trace thorium in U3O8 by isotope dilution inductively coupled plasma mass spectrometry%ID-ICP-MS测定八氧化三铀中痕量钍的不确定度评定

    Institute of Scientific and Technical Information of China (English)

    初泉丽; 曹淑琴; 张亮

    2011-01-01

    Taking determination of trace thorium in U3O8 by isotope dilution inductively coupled plasma mass spectrometry(ID-ICP-MS) as example, the uncertainty in measurement was evaluated. All parameters needed for the calculation process were collected and calculated, and a mathematical model was set up. The sources of the uncertainty in measurement were determined, and components of the uncertainty in measurement were synthetized with EXCEL software.%对同位素稀释电感耦合等离子体质谱法(ID-ICP-MS)测定八氧化三铀中痕量钍的不确定度进行评定,确定了不确定度来源,并使用EXCEL进行不确定度各分量的定量、合成.

  11. Determination of Arsenic in Soil Samples by Inductively Coupled Plasma-Mass Spectrometry with Different Digestion Methods%不同消解方法对电感耦合等离子体质谱法测定土壤中砷含量的影响

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    Used the nitric acid and hydrochloric acid reflux digestion and the aqua regia digestion method to digest environmental standard materials of soils before determining of arsenic by inductively coupled plasma-mass spectrometry (ICP-MS), and compared the results. The results showed that the aqua regia digestion method was superior to the nitric acid and hydrochloric acid reflux digestion method.%  采用硝酸-盐酸回流消解法和王水消解法同时前处理环境土壤标准物质,用电感耦合等离子体质谱法(ICP-MS)测定其中砷的含量,对两种方法的消解效果进行对比。结果表明,王水消解法要优于硝酸-盐酸回流消解法。

  12. Determination of 49 Trace Elements in Coal by High Resolution Inductively Coupled Plasma Mass Spectrometry%高分辨电感耦合等离子体质谱法测定煤质样品中49种痕量元素

    Institute of Scientific and Technical Information of China (English)

    张彦辉; 武朝晖; 郭虹; 薛丽丽

    2005-01-01

    Various trace elements, especially potential toxic trace elements such as As, Cd, Cr, Cu, Hg, Pb, Ni, Se, Tl, Zn, would be concentrated in processing of coal. Determination of these elements in coal is very important for identification of coal quality. A method is developed for determination of 49 trace elements in coal by high resolution inductively coupled plasma mass spectrometry (HR-ICPMS). Microwave acid digestion and low-temperature airproof acid digestion for sample preparation were investigated. It is shown that the low-temperature airproof acid digestion method is of lower blank, and more suitalbe for the coal sample preparation. The on-line internal standard (Rh) sample introduction is applied to compensate matrix effects in measurement by ICPMS. The method gives low detection limits (0.002-1.60 μg/g) and better relative standard deviations (0.60%-4.78%) for the determined 49 elements in coal.

  13. 电感耦合等离子体质谱法测定水体中65种元素标准方法建立的必要性分析%Necessity of Determina-tion of 65 Elements in Water by Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    王霞; 张绪美; 顾海东; 王隽

    2015-01-01

    Inductively coupled plasma mass spectrometry (ICP-MS) had obvious advantages,such as low detection limit, high sensitivity, good stability, less dis-turbance, wide linear range, quick anal-ysis of a variety of elements at the same time, was widely applied in environment, metallurgy, food and other fields. The published of The determination of 65 el-ements in water by inductively coupled plasma mass spectrometry (HJ 700 -2014) provided accurate and reliable method to test 65 types of element con-tent in water, and provided a powerful technical support for heavy metals in water pollution control.%电感耦合等离子体质谱法(ICP-MS)具有检出限低、灵敏度高、稳定性好、干扰少、线性范围宽、可快速同时分析多种元素等优点,在环境、冶金、食品等领域得到了广泛应用。《水质65种元素的测定电感耦合等离子体质谱法》(HJ 700-2014)的发布,为检测水体中65种元素含量提供了准确、可靠的方法,为水中重金属元素的污染防治提供了有力的技术支撑。

  14. Determination of inorganic arsenic in marine products by high performance liquid chromatography and inductively coupled plasma mass spectrometry%高效液相色谱-电感耦合等离子体质谱联用测定海洋产品中无机砷

    Institute of Scientific and Technical Information of China (English)

    庞艳华; 朱鸣鹤; 赵景红; 王秋艳

    2011-01-01

    采用高效液相色谱( HPLC)和电感耦合等离子体质谱(ICP-MS)联用技术测定了海洋产品中的无机砷.动物性和植物性海洋产品试样经过10% H3PO溶液(V/V)提取,阴离子交换色谱分离,ICP-MS测定其中As(Ⅲ)和As(Ⅴ)的含量.实验结果表明As(Ⅲ)和As(Ⅴ)的检出限分别为5.0和8.0 μg/kg,线性范围为5~100 μg/L,相关系数均大于0.9994,加标回收率为81.8%~107.6%,相对标准偏差小于6.7%(n=6).对选取的海洋产品测定结果显示,无机砷的含量均未超出国家卫生标准限量.%A high performance liquid chromatography and inductively coupled plasma mass spectrometric method was established for the determination of inorganic arsenic, including As ( M ) and As ( V ). The animal and vegetative samples were pretreated by phosphoric acid with the concentration of 10% ( V/V) , and inorganic arsenic was separated by anion exchange high performance chromatography and detected by inductively coupled plasma mass spectrometry (ICP-MS). The results showed that the linear ranges for As( M) and As( V) were all between 5 and 100 μg/L with correlation coefficients more than 0. 9994, and the detection limits were 5. 0 and 8. 0 μg/kg respectively. The relative standard deviations ( RSDs) were less than 6. 7% and the recoveries were between 81. 8% and 107. 6%. The results indicated that inorganic arsenic in marine products did not exceed national permission limits.

  15. Speciation of arsenic of liquid and gaseous emissions from soil in a microcosmos experiment by liquid and gas chromatography with inductively coupled plasma mass spectrometer (ICP-MS) detection

    Energy Technology Data Exchange (ETDEWEB)

    Prohaska, T.; Stingeder, G. [University of Agricultural Sciences - BOKU Wien (Austria). Inst. of Chemistry; Pfeffer, M.; Tulipan, M.; Mentler, A.; Wenzel, W.W. [Vienna University of Agricultural Sciences - BOKU Wien (Austria). Inst. of Soil Science

    1999-07-01

    Gas chromatography and high-performance liquid chromatography coupled to a double focusing sectorfield ICP-MS as sensitive element specific detector are used for the speciation of arsenic of liquid and gaseous emissions from soil samples, which were equilibrated in a microcosmos experiment. Speciation of liquid samples was performed by HPLC and hydride generation was used as introduction system to ICP-MS. An online prereduction step was introduced to enhance the sensitivity for As(V). A home-built and laboratory-ready transfer line from GC to ICP-MS is presented and quantification of As in gaseous emissions was performed by external calibration via hydride generation. The microcosmos experiment revealed only low production rates of organoarsenic compounds and reflected a limited capability of the biovolatilization experiment for the simulation of natural systems. (orig.) With 5 figs., 5 tabs., 29 refs.

  16. Induced lead binding phytochelatins in Brassica juncea and Sesuvium portulacastrum investigated by orthogonal chromatography inductively coupled plasma-mass spectrometry and matrix assisted laser desorption ionization-time of flight-mass spectrometry.

    Science.gov (United States)

    Zaier, H; Mudarra, A; Kutscher, D; Fernández de la Campa, M R; Abdelly, C; Sanz-Medel, A

    2010-06-25

    The accumulation and transport of lead in Brassica juncea and Sesuvium portulacastrum plants and the possible formation of complexes of this element with bioligands such as phytochelatins was studied in roots and shoots of plants exposed to different amounts of Pb(NO(3))(2). Speciation studies on the plant extracts were conducted using size exclusion liquid chromatography and ion pair liquid chromatography coupled to UV and ICP-MS to monitor lead and sulphur. The identification of the species separated by chromatography was performed by MALDI-TOF-MS. In both types of exposed plants it was possible to identify the presence of the phytochelatin isoform PC(3). The results obtained suggest that both types of plants can be useful in studies of phytoremediation but the ability of S. portulacastrum to accumulate and redistribute Pb from root to shoot is more effective than B. juncea.

  17. Individual glass shard trace element analyses confirm that all known Toba tephra reported from India is from the c. 75-ka Youngest Toba eruption

    Digital Repository Service at National Institute of Oceanography (India)

    Pearce, N.J.G.; Westgate, J.A.; Gatti, E.; Pattan, J.N.; Parthiban, G.; Achyuthan, H.

    compositions, analysing the same grains by both electron probe micro analysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Despite the limited number of sites where OTT and MTT occur, Westgate et al. (2013) were able... thank the four anonymous referees for their positive and rapid reviews. Abbreviations. DRE, dense rock equivalent; EPMA, electron probe microanalysis; LA-ICP-MS, laser ablation inductively coupled plasma mass spectrometry; MTT, Middle Toba Tuff; OTT...

  18. Platinum group metallodrug-protein binding studies by capillary electrophoresis - inductively coupled plasma-mass spectrometry: a further insight into the reactivity of a novel antitumor ruthenium(III) complex toward human serum proteins.

    Science.gov (United States)

    Polec-Pawlak, Kasia; Abramski, Jan K; Semenova, Olga; Hartinger, Christian G; Timerbaev, Andrei R; Keppler, Bernhard K; Jarosz, Maciej

    2006-03-01

    Biochemical speciation analysis has become a hot area of CE research due largely to growing emergence of inductively coupled plasma (ICP)-MS as a proper detection technique. A benefit of CE-ICP-MS coupling in species-selective analysis of anticancer metal-based drugs is the possibility of distinguishing the signals of the intact drug and its metabolites and hence of quantifying them independently. This advantage (over CE with UV-vis detection) was exploited here in order to gain better knowledge about the rate and degree of the transformation of indazolium [trans-tetrachlorobis(1H-indazole)ruthenate(III)] (KP1019), a promising tumor-inhibiting agent that successfully finished phase I clinical studies, upon its binding toward individual serum transport proteins. At increasing the KP1019/protein molar ratio, the reaction rate expressed by an evolving peak of the protein adduct became faster, with the equilibrium state being reached after about 40 and 60 min of incubation at 37 degrees C for transferrin and albumin, respectively. The binding reaction was shown to obey the first-order character that enabled for reliable calculation of the corresponding rate constants as (28.7 +/- 1.5) x 10(-4) and (10.6 +/- 0.7) x 10(-4)/s, respectively. When incubated with a ten-fold excess of KP1019, albumin and transferrin bound, respectively, up to 8 and 10 equiv. of ruthenium (Ru). Relative affinity of KP1019 toward different proteins under simulated physiological conditions was also characterized in terms of the overall binding constants (5600 and 10 600/M, respectively). To emphasize the difference in the protein-binding behavior, a competitive interaction of KP1019 was followed by CE-ICP-MS at the actual molar ratio of proteins in blood, i.e. a ten-fold excess of albumin over transferrin. The fact that KP1019 binds to albumin stronger than to transferrin was manifested by finding almost all ruthenium (98-99%) in the albumin fraction.

  19. Analysis of Hydrophilic Mercury-Binding Proteins in Medaka (Oryzias latipes) Using High Performance Liquid Chromatography Coupled with Inductively Coupled Plasma-Mass Spectrometry%高效液相色谱-电感耦合等离子体质谱研究Medaka体内水溶性汞结合蛋白

    Institute of Scientific and Technical Information of China (English)

    李璐; 何滨; 江桂斌

    2011-01-01

    The hydrophilic mercury-binding proteins in the brain and liver extractions of Medaka after methylmercury and inorganic mercury exposure were analyzed by high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry. Size exclusion chromatography was selected in the experiment with a mobile phase of 0. 15 mol/L NHaAc, running at a 0.5 mL/min flow rate. Concentrations of total copper, zinc and mercury in the brain and liver extracts of Medaka were determined by ICP-MS. Detection limits for these three elements were in the range of 0.01 μg/L to 0.05 μg/L, and the spike recoveries ranged from 93. 1%-97. 0%. Compared with the control group, high level of mercury is accumulated in the brain and liver of exposure groups. The distribution patterns of mercury-containing proteins in the brain and liver extracts of Medaka between methylmercury and inorganic mercury exposure group were different. The concentrations of copper and zinc in the brain and liver extractions of both exposure groups were decreased. The studies of the mercurycontaining protein fractions in Medaka are helpful for the understanding of the mechanisms of mercury toxicity.%采用高效液相色谱与电感耦合等离子体质谱联用技术,对不同形态汞暴露后的Medaka肝脏和脑组织中水溶性蛋白进行研究,以体积排阻柱为液相分离柱,流动相为0.15 mol/L NH4Ac,流速为0.5 mL/min.利用电感耦合等离子体质谱对Medaka肝脏和脑组织提取液中铜、锌和汞的含量进行了分析,检出限为0.01~0.05 μg/L,元素的加标回收率为93.1%~97.0%.通过与空白组对比发现,汞暴露后的Medaka鱼体肝脏和脑组织对水体中的汞有一定程度的富集;不同形态汞暴露后,在Medaka肝脏和脑组织中的分布明显不同,并且都会在一定程度上降低Medaka肝脏和脑组织中铜与锌的含量,有利于进一步研究汞在生物体内的毒性机理.

  20. Solid phase extraction for analysis of biogenic carbonates by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS): an investigation of rare earth element signatures in otolith microchemistry

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Zikri; Paulson, Anthony J

    2003-01-10

    Uptake of trace elements into fish otoliths is governed by several factors such as life histories and environment in addition to stock and species differences. In an attempt to elucidate the elemental signatures of rare earth elements (REEs) in otoliths, a solid phase extraction (SPE) protocol was used in combination with electrothermal vaporization (ETV) as a sample introduction procedure for the determinations by inductively coupled plasma quadrupole mass spectrometry (ICP-MS). Effects of various parameters, such as carrier gas flow rate, atomization temperature and chemical modification, were examined for optimization of the conditions by ETV-ICP-MS. Atomization was achieved at 2800 deg. C. Lower temperatures (i.e. 2600 deg. C) resulted in severe memory problems due to incomplete atomization. Palladium was used as a chemical modifier. It was found that an increase in Pd concentration up to 0.5 {mu}g in the injection volume (70 {mu}l) led up to four-fold enhancement in the integrated signals. This phenomenon is attributed to the carrier effect of Pd rather than the stabilization since no significant losses were observed for high temperature drying around 700 deg. C even in the absence of Pd. Preconcentration was performed on-line at pH 5 by using a mini-column of Toyopearl AF-Chelate 650M chelating resin, which also eliminated the calcium matrix of otolith solutions. After preconcentration of 6.4 ml of solution, the concentrate was collected in 0.65 ml of 0.5% (v/v) HNO{sub 3} in autosampler cups, and then analyzed by ETV-ICP-MS. The method was validated with the analysis of a fish otolith certified reference material (CRM) of emperor snapper, and then applied to samples. Results obtained from otoliths of fish captured in the same habitat indicated that otolith rare earth element concentrations are more dependent on environmental conditions of the habitat than on species differences.

  1. Optimization of an anion-exchange high performance liquid chromatography-inductively coupled plasma-mass spectrometric method for the speciation analysis of oxyanion-forming metals and metalloids in leachates from cement-based materials.

    Science.gov (United States)

    Mulugeta, Mesay; Wibetoe, Grethe; Engelsen, Christian J; Lund, Walter

    2010-10-01

    A method was developed for the speciation analysis of the oxyanions of As(III), As(V), Cr(VI), Mo(VI), Sb(III), Sb(V), Se(IV), Se(VI) and V(V) in leachates from cement-based materials, based on anion-exchange HPLC coupled with ICP-MS. The method was optimized in a two-step multivariate approach: the effect of sample pH and mobile phase composition on resolution, peak symmetry and analysis time was studied. Optimum conditions were then identified for the significant experimental factors by studying their interdependence. A mobile phase composition of 20 mM ammonium nitrate, 50 mM ammonium tartrate and pH 9.5 was found to be a compromise optimum for the separation of the target analytes using isocratic elution. The optimum condition provided separation of the analytes in less than 6 min, at a mobile phase flow rate of 1.0 mL/min. The signal intensities of the analytes were improved by adding 1% methanol to the mobile phase. The limit of detection of the method was in the range 0.2-2.2 μg/L for the various species. The effect of sample constituents was studied using spiked concrete leachates. The method was used to determine the target oxyanionic species in leachates generated from a concrete material in the pH range 3.5-12.4; CrO(4)(2-), MoO(4)(2-) and VO(4)(3-) were detected in most of the leachates.

  2. Analysis of biogenic carbonates by inductively coupled plasma-mass spectrometry (ICP-MS). Flow injection on-line solid-phase preconcentration for trace element determination in fish otoliths.

    Science.gov (United States)

    Arslan, Z; Paulson, A J

    2002-04-01

    The aragonite deposits within the ear bones (otoliths) of teleost fish retain a chemical signal reflecting the life history of fish (similar to rings of trees) and the nature of fish habitats. Otoliths dissolved in acid solutions contain high concentrations of calcium and a variety of proteins. Elimination of matrix salts and organic interferences during preconcentration is essential for accurate determination of trace elements in otolith solutions by inductively coupled plasma-quadrupole mass spectrometry. An iminodiacetate-based chelating resin (Toyopearl AF-Chelate 650 M) has been used for on-line preconcentration and matrix separation for the determination of 31 transition and rare elements. Successful preconcentration of the elements was achieved at pH 5 by on-line buffering, except Mn which required pH 8.8. Sample solutions were loaded on to the column for 1 min at 3.2 mL min(-1), and then eluted directly into the mass spectrometer with 4% v/v nitric acid. This procedure enabled up to 25-fold preconcentration with successful removal of the calcium matrix. The effect of heat-assisted oxidation with concentrated nitric acid was investigated to eliminate the organic matrix. It was found that heating to dryness after dissolution and further mineralization with the acid significantly improved the retention of the transition elements. The method was validated by analysis of a certified reference material produced from saggittal otoliths of emperor snapper ( Lutjanus sebae), and then applied to the determination of trace metal concentrations in juvenile bluefin tuna ( Thunnus thynnus) from the Western Pacific Ocean.

  3. Analysis of biogenic carbonates by inductively coupled plasma-mass spectrometry (ICP-MS). Flow injection on-line solid-phase preconcentration for trace element determination in fish otoliths

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Z.; Paulson, A.J. [National Oceanic and Atmospheric Administration (NOAA), Northeast Fisheries Science Center (NFSC), James J. Howard Marine Sciences Laboratory, Highlands, NJ (United States)

    2002-04-01

    The aragonite deposits within the ear bones (otoliths) of teleost fish retain a chemical signal reflecting the life history of fish (similar to rings of trees) and the nature of fish habitats. Otoliths dissolved in acid solutions contain high concentrations of calcium and a variety of proteins. Elimination of matrix salts and organic interferences during preconcentration is essential for accurate determination of trace elements in otolith solutions by inductively coupled plasma-quadrupole mass spectrometry. An iminodiacetate-based chelating resin (Toyopearl AF-Chelate 650 M) has been used for on-line preconcentration and matrix separation for the determination of 31 transition and rare elements. Successful preconcentration of the elements was achieved at pH 5 by on-line buffering, except Mn which required pH 8.8. Sample solutions were loaded on to the column for 1 min at 3.2 mL min{sup -1}, and then eluted directly into the mass spectrometer with 4% v/v nitric acid. This procedure enabled up to 25-fold preconcentration with successful removal of the calcium matrix. The effect of heat-assisted oxidation with concentrated nitric acid was investigated to eliminate the organic matrix. It was found that heating to dryness after dissolution and further mineralization with the acid significantly improved the retention of the transition elements. The method was validated by analysis of a certified reference material produced from saggittal otoliths of emperor snapper (Lutjanus sebae), and then applied to the determination of trace metal concentrations in juvenile bluefin tuna (Thunnus thynnus) from the Western Pacific Ocean. (orig.)

  4. Evaluation of ultrasound-assisted extraction as sample pre-treatment for quantitative determination of rare earth elements in marine biological tissues by inductively coupled plasma-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Costas, M.; Lavilla, I.; Gil, S.; Pena, F.; Calle, I.; Cabaleiro, N. de la [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Facultad de Quimica, Universidad de Vigo, As Lagoas-Marcosende s/n, 36310 Vigo (Spain); Bendicho, C., E-mail: bendicho@uvigo.es [Departamento de Quimica Analitica y Alimentaria, Area de Quimica Analitica, Facultad de Quimica, Universidad de Vigo, As Lagoas-Marcosende s/n, 36310 Vigo (Spain)

    2010-10-29

    In this work, the determination of rare earth elements (REEs), i.e. Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu in marine biological tissues by inductively coupled-mass spectrometry (ICP-MS) after a sample preparation method based on ultrasound-assisted extraction (UAE) is described. The suitability of the extracts for ICP-MS measurements was evaluated. For that, studies were focused on the following issues: (i) use of clean up of extracts with a C18 cartridge for non-polar solid phase extraction; (ii) use of different internal standards; (iii) signal drift caused by changes in the nebulization efficiency and salt deposition on the cones during the analysis. The signal drift produced by direct introduction of biological extracts in the instrument was evaluated using a calibration verification standard for bracketing (standard-sample bracketing, SSB) and cumulative sum (CUSUM) control charts. Parameters influencing extraction such as extractant composition, mass-to-volume ratio, particle size, sonication time and sonication amplitude were optimized. Diluted single acids (HNO{sub 3} and HCl) and mixtures (HNO{sub 3} + HCl) were evaluated for improving the extraction efficiency. Quantitative recoveries for REEs were achieved using 5 mL of 3% (v/v) HNO{sub 3} + 2% (v/v) HCl, particle size <200 {mu}m, 3 min of sonication time and 50% of sonication amplitude. Precision, expressed as relative standard deviation from three independent extractions, ranged from 0.1 to 8%. In general, LODs were improved by a factor of 5 in comparison with those obtained after microwave-assisted digestion (MAD). The accuracy of the method was evaluated using the CRM BCR-668 (mussel tissue). Different seafood samples of common consumption were analyzed by ICP-MS after UAE and MAD.

  5. Regular Maintenance and Malfunction Eliminating of NexION-300 Inductively Coupled plasma-Mass Spectrometry%NexION 300X型电感耦合等离子体质谱仪的日常维护及故障排除

    Institute of Scientific and Technical Information of China (English)

    苑国强; 赵晶晶; 何秀娟

    2015-01-01

    In the process of daily use of NexION 300 inductively coupled plasma mass spectrometry (ICP–MS) which was made by PE company,common faults occurred such as difficult to“ignite”,easy to“turn off”,low sensitivity,high oxide and bad precision. The reasons were analyzed and the troubleshooting methods were put forward. The suggestions for the daily maintenance of the ICP–MS were discussed.%在使用PE公司生产的NexION 300型电感耦合等离子体质谱仪(ICP–MS)过程中,出现了点不着火、易熄火、检测灵敏度低、精密度不好等故障,分析了故障产生的原因,提出了故障排除方法。对该仪器的日常维护提出了建议。

  6. Ultra-trace determination of Strontium-90 in environmental soil samples from Qatar by collision/reaction cell-inductively coupled plasma mass spectrometry (CRC-ICP-MS/MS)

    Energy Technology Data Exchange (ETDEWEB)

    Al-Meer, S. H.; Amr, M. A. [Central Laboratories Unit, Qatar University, Doha (Qatar); Helal, A.I. [Atomic Energy Authority, Cairo (Egypt); Al-Kinani, A.T. [Minstery of Environment, Doha (Qatar)

    2013-07-01

    Because of the very low level of {sup 90}Sr in the environmental soil samples and its determination by beta counting may take several weeks, we developed a procedure for ultra-trace determination of {sup 90}Sr using collision reaction cell-inductively coupled plasma tandem mass spectrometry (CRC-ICP-MS/MS, Agilent 8800). Soil samples were dried at 105 deg. C and then heated in a furnace at 550 deg. C to remove any organics present. 500 g of each soil samples were aliquoted into 2000 ml glass beakers. Each Soils samples were soaked in 2 ppm Sr solution carrier to allow determination of chemical yield. The solid to liquid ratio was 1:1. Finally the soil samples were dried at 105 deg. C. Five hundred milliliters concentrated nitric acid and 250 ml hydrochloric acid volumes were added on 500 g soil samples. The samples were digested on hot plate at 80 deg. C to prevent spraying with continuous manual mixing. The leachate solution was separated. The solids were rinsed with 500 ml deionized water, warmed on a hot plate and the leachate plus previous leachate were filtered and the total volume was reduced to 500 ml by evaporation. Final leachate volume was transferred to a centrifuge tubes. The centrifuge tubes were centrifuged at 3,500 rpm for 10 min. The leachate was transferred to a 1 L beaker and heated on a hot plate to evaporate the leachate to dryness. The reside was re-dissolved in 100 ml of 2% HNO{sub 3} and reduced by evaporation to 10 mL. The solution was measured directly by CRC-ICP-MS/MS by setting the first quadruple analyzer to m/z 90 and introducing oxygen gas into the reaction cell for elimination isobar interference from zirconium-90. The method was validated by measurements of standard reference materials and applied on environmental soil samples. The overall time requirement for the measurement of strontium-90 by CRC-ICP-MS/MS is 2 days, significantly shorter than any radioanalytical protocol currently available. (authors)

  7. 高效液相色谱-电感耦合等离子体质谱同时分析鸡肉中洛克沙生、阿散酸和硝苯胂酸%Simultaneous Determination of Roxarsone,Arsanilic and Nitarsone in Chicken by High Performance Liquid Chromatography/Inductively Coupled Plasma Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    杨丽君; 刘玉敏; 崔凤杰; 郭伟; 徐成钢; 李兆杰

    2011-01-01

    An analytical method was developed to simultaneously determine roxarsone,arsanilic and nitarsone in chicken by high performance liquid chromatography/inductively coupled plasma mass spectrometry(HPLC-ICP-MS).Samples were extracted with methanol/water solution.The chromatographic separation was performed on a Phenomenex Luna C18 using methanol and water(containing 0.05% trifluoroacetic acid) as the mobile phase.Identification and quantification were achieved by using ICP-MS.Good linearity was observed in the range of 1 to 50 μg/kg with correlation coefficients above 0.99.The method was validated at the spike levels of 1,2,10 μg/kg.The validation results indicated that the average recoveries of arsenicum praeparatum ranged from 85.4% to 103.1% with a relative standard deviation of 3.3%-7.2%.The quantification limits of 3 arsenicum praeparatum were 1μg/kg.The method had good reproducibility,high sensitivity and simple pre-treatment.Its performance could meet both domestic and international legislation requirements.This method is applicable for simultaneous determination of arsenicum praeparatum in chicken.%建立一种同时测定鸡肉中洛克沙生、阿散酸和硝苯胂酸等3种有机砷类制剂的高效液相色谱-电感耦合等离子体质谱(high performance liquid chromatography tandem inductively coupled plasma mass spectrometry,HPLC-ICP-MS)分析方法。样品经甲醇溶液提取,采用Phenomenex Luna C18色谱柱,体积分数0.05%的三氟乙酸溶液-甲醇作为流动相进行洗脱,经高效液相色谱分离,电感耦合等离子体质谱进行定性和定量分析。结果表明:1~50μg/kg范围内各砷制剂线性良好,相关系数r2均在0.99以上;在1、2、10μg/kg三个加标水平下进行方法验证,平均回收率为85.4%~103.1%,相对标准偏差为3.3%~7.2%;3种有机砷类制剂的定量限均为1μg/kg。方法重现性好、灵敏度高、前处理简单,各项指标均满足国内外法规要求,适用

  8. 微波消解—碰撞反应池技术电感耦合等离子体质谱法测定食品中的铅%Determination of lead in foods by inductively coupled plasma mass spectrometry based on collided reaction cell technology after microwave digestion

    Institute of Scientific and Technical Information of China (English)

    殷忠; 周彬; 汪思顺

    2013-01-01

    OBJECTIVE To establish a method for determination of lead in foods by inductively coupled plasma mass spectrometry based on collided reaction cell technology after microwave digestion.METHODS After microwave digestion,the samples were directly determined by inductively coupled plasma mass spectrometry based on collided reaction cell technology.Internal standard element of Thallium (204TI) was used to correct matrix interference and signal drifting,high-performance Xs interface was used to reduce non-mass spectrum interferences,and the collided reaction cell technology (CCT mode) was used to eliminate mass spectrum interferences.RESULTS The optimal linear range of the method was 0-40μg/L with a correlation coefficient of 0.999 8.The detection limit of the method,the lowest quantitative limit,the relative standard deviation and the recovery rate were 0.000 5 mg/kg,0.001 7 mg/kg,1.1%-3.8% and 93.3%-104.0%,respectively.CONCLUSION The method is sensitive,accurate,simple and fast.There is no significant difference between the results from the method and graphic furnace atomic absorption spectrometry and is suitable for analysis of lead in foods.%目的 建立食品中铅的微波消解—碰撞反应池技术电感耦合等离子体质谱法.方法 样品经微波消化后直接用碰撞反应池电感技术的耦合等离子体质谱仪(ICP-MS)进行测定.用铊(204TI)内标校正基体干扰和漂移,用高性能Xs接口降低非质谱干扰,用碰撞反应池技术(CCT模式)消除质谱干扰.结果 方法的标准曲线线性范围为0~40μg/L,相关系数为0.999 8.方法检出限为0.000 5mg/kg,最低检出浓度为0.001 7 mg/kg,相对标准偏差为1.1%~3.8%,回收率为93.3%~104.0%.结论 本方法灵敏、准确,操作简便、快速,对样品的测定结果与石墨炉原子吸收光度法之间无显著性差异,能用于食品中铅的准确测定.

  9. 微波消解-碰撞反应池技术电感耦合等离子体质谱法测定食品总砷的方法研究%Methodology research on determination of total arsenic in foods by inductively coupled plasma mass spectrometry based on collided reaction cell technology with microwave digestion

    Institute of Scientific and Technical Information of China (English)

    殷忠

    2013-01-01

    Objective To establish a method for determination of total arsenic in foods by inductively coupled plasma mass spectrometry based on collided reaction cell technology with microwave digestion and provide a new reliable method for accurate quantitative analysis of total arsenic in foods.Methods After microwave digestion,the samples were directly determined by inductively coupled plasma mass spectrometry based on collided reaction cell technology.Internal standard element of Yttrium(89Y) was used to correct matrix interference and signal drifting,high-performance Xs interface was used to reduce non-mass spectrum interferences,and the collided reaction cell technology (CCT mode) was used to eliminate mass spectrum interferences.Meanwhile,arsenic measurement results were compared with the arbitral method.Results The optima 1 linear range of the method standard curve was 0-40 μg/L with a correlation coefficient of 0.9998.The detection limit of the method,the lowest quantitative limit,the relative standard deviation and the recovery rate were 0.0025 mg/kg,0.082 mg/kg,1.5%-4.2% and 95.0%-105.0%,respectively.The detection results of the three standard reference materials were satisfactory.Compared with the arbitral method,there was no obvious difference (P < 0.05).Conclusions The method not only has lower detection limit,but also is simple,fast and more accurate.The results are consistent with those by arbitral method,and the new method is available for accurate quantitative analysis of total arsenic in foods.%目的 建立测定食品总砷的微波消解-碰撞反应池技术电感耦合等离子体质谱法,为食品总砷的准确定量提供新的方法.方法 样品经微波消化后直接用碰撞反应池电感技术的耦合等离子体质谱仪(ICP-MS)进行测定分析.用钇(89Y)内标校正基体干扰和漂移,用高性能Xs接口降低非质谱干扰,用碰撞反应池技术(CCT模式)消除质谱干扰.同时,将砷的测定结果

  10. 电热板消解电感耦合等离子体质谱法测定人发中33种无机元素的含量%Determination of 33 Inorganic Elements in Human Hair by Electricity Plate Digestion and Inductively Coupled Plasma-Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    骆如欣; 马栋; 张素静; 卓先义

    2013-01-01

    目的 建立头发中33种无机元素的电热板消解电感耦合等离子体质谱(inductively