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Sample records for ablation icp-ms la-icp-ms

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

    PubMed

    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.

  2. Infra-red femtosecond laser ablation: Benefit for LA-ICP-MS elemental analysis?

    NASA Astrophysics Data System (ADS)

    Poitrasson, F.; d'Abzac, F.; Freydier, R.; Seydoux-Guillaume, A.; Chmeleff, J.; Chatel, B.

    2011-12-01

    Femtosecond (fs) laser ablation systems have now been used for about a decade for elemental analysis in chemical and geosciences laboratories. Published studies investigated the influence of various analytical parameters, such as laser pulsewidth, wavelength, energy or ablation duration, on the quality of the analytical data produced by fs Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). It was rapidly found that under comparable analytical conditions, chemical fractionation effects that may occur during laser-induced particle production, transport and/or decomposition in the ICP-MS plasma torch become negligible in the fs laser ablation regime under 300 fs laser pulsewidth. Another major benefit of fs laser ablation is its restricted matrix-sensitive nature compared to ns laser ablation, thereby facilitating greatly LA-ICP-MS calibration for chemical analysis with a reference material having completely different optical and chemical properties compared to the sample to be analyzed (e.g., a standard glass to calibrate analyses of a phosphate mineral). This effect is particularly remarkable as it can be stated from both UV and IR fs laser ablation studies. Reproducible laser ablations of optical quality quartz can also be produced using such an IR laser. Precise, accurate and reproducible chemical analyses may be obtained using ns laser ablation systems. However, this is achieved under carefully controlled analytical conditions using state of the art ablation cells. Instead, it appears that fs laser ablation is making LA-ICP-MS analyses more reliable. More recently, analytical studies combined with high spatial resolution microscopic techniques allowed us to understand better the nature of fs laser-matter interaction through the direct examination of the laser-induced craters and of the particles produced. These investigations have shown the dominance of mechanical over thermal effects on the solids ablated using a fs laser. Whatever the

  3. Title: The validation of Cryogenic Laser Ablation ICP-MS (CLA-ICP-MS) methods by comparison to laser ablation (LA)-ICP-MS and solution based ICP-MS methods, for the analysis of metals in biological tissues

    NASA Astrophysics Data System (ADS)

    Hannigan, R.; Darrah, T. H.; Horton, M.

    2009-12-01

    ICP-MS and laser ablation ICP-MS (LA-ICP-MS) are well established techniques for the analysis of metals in geological and environmental samples. LA-ICP-MS is commonly used in geological applications to determine the spatial distribution of metal concentrations at small sampling intervals (as low as 10 microns). However, measurement of metals in water-rich, soft biological tissues typically requires samples to be digested into solutions, obfuscating spatial variations in metal concentrations. The cryogenic cell solidifies (by freezing) soft tissue, allowing these tissues to be analyzed by laser ablation for spatial variations in metal concentration. The cell is temperature programmable and capable of maintaining a sample at any temperature between -35C and 25C throughout prolonged analysis. We validate the cryogenic laser ablation ICP-MS (CLA-ICP-MS) method using NIST Glass SRM 612. We also compare metal concentration data analyzed by cryogenic laser ablation ICP-MS (CLA-ICP-MS), LA-ICP-MS, and solution based ICP-MS, for human and rodent brain samples. The cryogenic laser ablation cell will expand analytical capabilities for measuring spatial distribution and concentration of metals incorporated into biological tissues.

  4. LA-ICP-MS of magnetite: Methods and reference materials

    USGS Publications Warehouse

    Nadoll, P.; Koenig, A.E.

    2011-01-01

    Magnetite (Fe3O4) is a common accessory mineral in many geologic settings. Its variable geochemistry makes it a powerful petrogenetic indicator. Electron microprobe (EMPA) analyses are commonly used to examine major and minor element contents in magnetite. Laser ablation ICP-MS (LA-ICP-MS) is applicable to trace element analyses of magnetite but has not been widely employed to examine compositional variations. We tested the applicability of the NIST SRM 610, the USGS GSE-1G, and the NIST SRM 2782 reference materials (RMs) as external standards and developed a reliable method for LA-ICP-MS analysis of magnetite. LA-ICP-MS analyses were carried out on well characterized magnetite samples with a 193 nm, Excimer, ArF LA system. Although matrix-matched RMs are sometimes important for calibration and normalization of LA-ICP-MS data, we demonstrate that glass RMs can produce accurate results for LA-ICP-MS analyses of magnetite. Cross-comparison between the NIST SRM 610 and USGS GSE-1G indicates good agreement for magnetite minor and trace element data calibrated with either of these RMs. Many elements show a sufficiently good match between the LA-ICP-MS and the EMPA data; for example, Ti and V show a close to linear relationship with correlation coefficients, R2 of 0.79 and 0.85 respectively. ?? 2011 The Royal Society of Chemistry.

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

    PubMed

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

    2010-02-01

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

  6. Biomonitoring of metal contamination in a marine prosobranch snail (Nassarius reticulatus) by imaging laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    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.

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

    PubMed

    Bartle, Emma K; Watling, R John

    2007-03-01

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

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

    PubMed

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

    PubMed

    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.

  10. 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.

    PubMed

    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.

  11. Influence of femtosecond laser ablation system parameters on the characteristics of induced particles: implications for LA-ICP-MS analysis of natural monazite

    NASA Astrophysics Data System (ADS)

    D'Abzac, F.; Seydoux-Guillaume, A.; Chmeleff, J.; Datas, L.; Poitrasson, F.

    2010-12-01

    The characteristics of Infra Red femtosecond laser-induced aerosols are studied for monazite (Moacyr) ablation, in order to evaluate optimal conditions for Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) analysis. Various parameters are tested within wide ranges in order to cover near all of the usual LA-ICP-MS settings: pulse energy (E0), pulse width (τ), ablation time (t), transport length (l), nature of the carrier gas. In order to study the influence of laser wavelength on LA-ICP-MS analysis, a third harmonic generator was used to convert the fundamental λ=800nm into a λ=266nm laser emission. Acquisition protocol is the same as in d’Abzac et al. (2010)1. Data are compared with a UV-nanosecond (λ=193nm) laser ablation system using a similar ICP-MS model. Transmission Electron Microscopy (TEM) reveals that particles morphologies and chemical compositions are not affected by any parameter. Melt droplets are observed only using argon. Electronic Low Pressure Impaction (ELPI) data show that the quantity of aerosol produced is affected by all parameters. Little changes on size distribution are noted with changing settings. Detectable variations are induced during crater deepening (poor evacuation of large particles), the transport length (deposition of smallest particles) and the use of helium (shift to smaller sizes). UV-ns-LA-ICP-MS results show signal intensities similar to IR-fs-LA-ICP-MS, but a deviation of 206Pb/238U ratio with t increased by a factor of ~33. Based on recent ID-TIMS values of 206Pb/238U ratio in Moacyr2, accuracy is increased by ~22% from UV-ns to IR-fs system and repeatability is improved by 2%. Optimal LA-ICP-MS settings are given relatively to the present analytical results and the previous studies dealing with the same system1, 3. Pulse width must remain under 500fs to avoid plasma shielding and thermal diffusion, ablation time should be limited to prevent high crater depths and poor aerosols wash out, transport length must be

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

    PubMed

    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.

  13. Quantitative imaging of 2 nm monolayer-protected gold nanoparticle distributions in tissues using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    Elci, S Gokhan; Yan, Bo; Kim, Sung Tae; Saha, Krishnendu; Jiang, Ying; Klemmer, Gunnar A; Moyano, Daniel F; Tonga, Gulen Yesilbag; Rotello, Vincent M; Vachet, Richard W

    2016-04-21

    Functionalized gold nanoparticles (AuNPs) have unique properties that make them important biomedical materials. Optimal use of these materials, though, requires an understanding of their fate in vivo. Here we describe the use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to image the biodistributions of AuNPs in tissues from mice intravenously injected with AuNPs. We demonstrate for the first time that the distributions of very small (∼2 nm core) monolayer-protected AuNPs can be imaged in animal tissues at concentrations in the low parts-per-billion range. Moreover, the LA-ICP-MS images reveal that the monolayer coatings on the injected AuNPs influence their distributions, suggesting that the AuNPs remain intact in vivo and their surface chemistry influences how they interact with different organs. We also demonstrate that quantitative images of the AuNPs can be generated when the appropriate tissue homogenates are chosen for matrix matching. Overall, these results demonstrate the utility of LA-ICP-MS for tracking the fate of biomedically-relevant AuNPs in vivo, facilitating the design of improved AuNP-based therapeutics.

  14. 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.

    PubMed

    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.

  15. LIBS and LA-ICP-MS; Old techniques, new approaches

    NASA Astrophysics Data System (ADS)

    Mueller, P. A.; Foster, D. A.; Gonzalez, J.; Colucci, M.; Russo, R.

    2012-12-01

    Over the past decade laser ablation in-situ solid sampling for chemical analysis with an ICP-MS analyzer (LA-ICP-MS, single and multi-collector) has become a generally accepted technique across a wide range of disciplines (geochemistry, forensic science, life sciences, etc). More recently, Laser Induced Breakdown Spectrometry (LIBS) has developed into a complementary technique that offers full spectral analysis of the laser plasma without the need for a mass spectrometer. Both techniques provide in-situ solid sample elemental and isotopic analysis at high spatial resolution (<5 microns) with minimal sample preparation. LA-ICP-MS affords the analyst low detection limits (ppb) and the ability to optimize across a specific mass range for high precision element or isotope ratios. LIBS, while providing slightly higher detection limits (ppm), allows for simultaneous and near complete spectral coverage of the laser plasma. Both techniques are capable of producing semi-quantitative and quantitative data. Integration of a LA and LIBS system could be a powerful tool to allow full spectral element and isotope/element ratio data on the same laser plume (plasma and particulates). Although LIBS and LA typically operate under different conditions of pulse length, spot size, and energy, the ability to capture elemental abundance information from the light that is otherwise wasted during LA makes an important complement to the limited number of ions measured in multi-collector ICP-MS analyses. Such an approach would not require the compromises in sampled volume associated with either split-streams (two ICP-MS systems required; diluted aerosol streams) or with peak switching in the MS (magnetic or electrostatic) because extraction of light-based information does not impact the number of ions measured for isotope ratios. We present LIBS experiments with UV-nanosecond lasers at 17mJ energies delivered to spot sizes of <100 μm and light directed to an ICCD detection system on NIST

  16. Cerebral bioimaging of Cu, Fe, Zn, and Mn in the MPTP mouse model of Parkinson's disease using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    Matusch, Andreas; Depboylu, Candan; Palm, Christoph; Wu, Bei; Höglinger, Günter U; Schäfer, Martin K-H; Becker, J Sabine

    2010-01-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a powerful technique for the determination of metal and nonmetal distributions within biological systems with high sensitivity. An imaging LA-ICP-MS technique for Fe, Cu, Zn, and Mn was developed to produce large series of quantitative element maps in native brain sections of mice subchronically intoxicated with 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridin (MPTP) as a model of Parkinson's disease. Images were calibrated using matrix-matched laboratory standards. A software solution allowing a precise delineation of anatomical structures was implemented. Coronal brain sections were analyzed crossing the striatum and the substantia nigra, respectively. Animals sacrificed 2 h, 7 d, or 28 d after the last MPTP injection and controls were investigated. We observed significant decreases of Cu concentrations in the periventricular zone and the fascia dentata at 2 h and 7d and a recovery or overcompensation at 28 d, most pronounced in the rostral periventricular zone (+40%). In the cortex Cu decreased slightly to -10%. Fe increased in the interpeduncular nucleus (+40%) but not in the substantia nigra. This pattern is in line with a differential regulation of periventricular and parenchymal Cu, and with the histochemical localization of Fe, and congruent to regions of preferential MPTP binding described in the rodent brain. The LA-ICP-MS technique yielded valid and statistically robust results in the present study on 39 slices from 19 animals. Our findings underline the value of routine micro-local analytical techniques in the life sciences and affirm a role of Cu availability in Parkinson's disease.

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

    PubMed

    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).

  18. Multiplexed quantification of plant thylakoid proteins on Western blots using lanthanide-labeled antibodies and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    de Bang, Thomas Christian; Pedas, Pai; Schjoerring, Jan Kofod; Jensen, Poul Erik; Husted, Søren

    2013-05-21

    We have developed a novel calibration method that allows concurrent quantification of multiple proteins by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) after Western blotting. Calibrants were made of nitrocellulose membranes doped with lanthanide standards. Excellent linearity was obtained in the interval from 0 to 24 ng lanthanide cm(-2). Cerium-labeled lysozyme was introduced as an internal reference protein, enabling correction for up to 50% difference in transfer efficiency during the blotting of membranes. The sensitivity of the LA-ICP-MS method was comparable to state-of-the-art chemiluminescence detection and was further improved by a factor of 20, using a polymer tag. Our method allowed reproducible and multiplexed quantification of five thylakoid proteins extracted from chloroplasts of the plant species Arabidopsis thaliana (relative standard deviation (RSD) of ≤ 5% in three independent analytical series). The method was capable of measuring the L subunit in photosystem I of an Arabidopsis mutant containing <5% of this particular protein, relative to the wild type. We conclude that the developed calibration method is highly suited for multiplexed and comparative protein studies, allowing for intermembrane comparisons with high sensitivity and reproducibility.

  19. Elemental mapping in fossil tooth root section of Ursus arctos by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    Vašinová Galiová, M; Nývltová Fišáková, M; Kynický, J; Prokeš, L; Neff, H; Mason, A Z; Gadas, P; Košler, J; Kanický, V

    2013-02-15

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to map the matrix (Ca, P) and trace (Ba, Sr, Zn) elements in the root section of a fossilized brown bear (Ursus arctos) tooth. Multielemental analysis was performed on a (2.5 × 1.5)cm(2) area. For elemental distribution, a UP 213 laser ablation system was coupled either with a quadrupole or a time of flight ICP-MS. The cementum and dentine on the slice of the sample surface were clearly distinguishable, especially changes in elemental distribution in the summer and winter bands in the fossil root dentine. Migration and diet of U. arctos were determined on the basis of fluctuations in Sr/Zn ratio and their contents. Quantification was accomplished with standard reference material of bone meal (NIST 1486) and by the use of electron microprobe analysis (EMPA). Changes in Sr/Zn and Sr/Ba ratios relating to the season, and composition of food during the lifetime of the animal are discussed on basis of analysis of light stable isotopes. It was observed that there was an increase in the Sr/Zn ratio during the winter season caused by a reduction of food intake during hibernation. Above mentioned inferences drawn from elemental data obtained by LA-ICP-MS were confirmed independently by determination of carbon, nitrogen and strontium isotopes. Moreover, diagenesis and its interfering influence on the biogenic composition of cementum and dentine were resolved. According to the distribution and/or content of the element of interest, post-mortem alterations were revealed. Namely, U, Na, Fe, Mg and F predicate about the suitability of the selected area for determination of migration and diet.

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

    PubMed

    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.

  1. Imaging mass spectrometry of elements in forensic cases by LA-ICP-MS.

    PubMed

    Lauer, Estelle; Villa, Max; Jotterand, Morgane; Vilarino, Raquel; Bollmann, Marc; Michaud, Katarzyna; Grabherr, Silke; Augsburger, Marc; Thomas, Aurélien

    2017-03-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was performed to map elements in thin formalin-fixed paraffin-embedded tissue sections of two forensic cases with firearm and electrocution injuries, respectively. In both cases, histological examination of the wounded tissue regions revealed the presence of exogenous aggregates that may be interpreted as metallic depositions. The use of imaging LA-ICP-MS allowed us to unambiguously determine the elemental composition of the observed aggregates assisting the pathologist in case assessments. To the best of our knowledge, we demonstrate for the first time the use of imaging LA-ICP-MS as a complementary tool for forensic pathologists and toxicologists in order to map the presence of metals and other elements in thin tissue sections of post-mortem cases.

  2. The influence of laser pulse duration and energy on ICP-MS signal intensity, elemental fractionation, and particle size distribution in NIR fs-LA-ICP-MS.

    PubMed

    Diwakar, Prasoon K; Harilal, Sivanandan S; LaHaye, Nicole L; Hassanein, Ahmed; Kulkarni, Pramod

    Laser parameters, typically wavelength, pulse width, irradiance, repetition rate, and pulse energy, are critical parameters which influence the laser ablation process and thereby influence the LA-ICP-MS signal. In recent times, femtosecond laser ablation has gained popularity owing to the reduction in fractionation related issues and improved analytical performance which can provide matrix-independent sampling. The advantage offered by fs-LA is due to shorter pulse duration of the laser as compared to the phonon relaxation time and heat diffusion time. Hence the thermal effects are minimized in fs-LA. Recently, fs-LA-ICP-MS demonstrated improved analytical performance as compared to ns-LA-ICP-MS, but detailed mechanisms and processes are still not clearly understood. Improvement of fs-LA-ICP-MS over ns-LA-ICP-MS elucidates the importance of laser pulse duration and related effects on the ablation process. In this study, we have investigated the influence of laser pulse width (40 fs to 0.3 ns) and energy on LA-ICP-MS signal intensity and repeatability using a brass sample. Experiments were performed in single spot ablation mode as well as rastering ablation mode to monitor the Cu/Zn ratio. The recorded ICP-MS signal was correlated with total particle counts generated during laser ablation as well as particle size distribution. Our results show the importance of pulse width effects in the fs regime that becomes more pronounced when moving from femtosecond to picosecond and nanosecond regimes.

  3. Monitoring of platinum in a single hair by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) after cisplatin treatment for cancer

    NASA Astrophysics Data System (ADS)

    Pozebon, Dirce; Dressler, Valderi L.; Matusch, Andreas; Becker, J. Sabine

    2008-04-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to quantify and monitor the concentration of Pt along a single strand of hair from a patient who had been treated with cisplatin as cytostatic drug. The sensitivity of the analytical method developed could be increased by total ablation of the hair cross-section compared to partial ablationE A low-noise intensity ratio was obtained along the strand, while the blank was negligible. The variation of the Pt signal with reference to each cisplatin dose was clearly observed. Home-made standards consisting of Pt-enriched hair strands served as calibrators and sulphur (measuring 34S+) was used as the internal reference element. The correlation coefficient of the calibration curve for platinum was 0.9973 and the detection limit was 0.029 [mu]g g-1. The rate of hair growth between doses was constant. The mean relative standard deviation (R.S.D.) for five replicates of single hair strands ranged from 15 to 22%. The maximum concentrations of Pt found along the hair strands were 26.9 ± 5.3, 14.7 ± 3.3, 20.9 ± 3.9 and 26.1 ± 3.8 [mu]g g-1, which correspond to four treatment of cisplatin administered to the patient at 3-week intervals.

  4. 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.

    PubMed

    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.

  5. Analysis of Rare Earth Elements in Rock and Mineral Samples by ICP-MS and LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Sindern, Sven

    2017-02-01

    The group of the rare earth elements (REEs) serves as valuable indicator of numerous geological processes such as magma formation or fluid-rock interaction. The decay systems of the radioactive REE isotopes 138La, 147Sm and 176Lu are used for geochronometric dating of a range of events, starting from first steps of planetary formation to younger steps of geodynamic development. Thus, the abundance of all REEs occurring in a large range of concentrations as well as precise isotope ratios must be analysed in different geomaterials. The inductively coupled plasma (ICP) ion source and various types of mass spectrometers (MS) represent the basis to fulfil the analytical requirements of geoscientific studies. Today, ICP-quadrupole MS and ICP-sector field MS (SFMS) with a single detector or multiple ion collection (MC-ICP-MS) are standard instruments for REE analyses in the geosciences. Due to the need for in situ analysis, laser ablation (LA)-ICP-MS has become an important trace element microprobe technique, which is widely applied for determination of REE concentrations and isotope compositions in geoscientific laboratories. The quality of concentration analysis or isotope ratio determination of REEs by ICP-MS and LA-ICP-MS is affected by many parameters. Most significant are interferences caused by polyatomic oxide and hydroxide ion species formed in the plasma as well as fractionation effects leading to non-stoichiometric behaviour during element determination or to biased isotope ratio measurements. Laser-induced fractionation and isobaric interferences have to be considered as additional effects for LA-ICP-MS. As analyte elements and matrix are unseparated, mineral standards matching the matrix of samples are a prerequisite for accurate and precise REE concentration and isotope ratio determination. Application of fs lasers instead of the more common ns lasers in LA-ICP-MS systems turns out to be a significant step to reduce laser-induced fractionation and to

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

    PubMed

    İzgi, Belgin; Kayar, Murat

    2015-07-01

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

  7. Next generation of labeling reagents for quantitative and multiplexing immunoassays by the use of LA-ICP-MS.

    PubMed

    Kanje, S; Herrmann, A J; Hober, S; Mueller, L

    2016-11-14

    Immuno imaging by the use of Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) is a growing research field in life sciences such as biology and biomedicine. Various element labeling strategies for antibodies have been developed for the application of multiplex immunoassays analyzed by the use of LA-ICP-MS. High multiplexing capabilities, a wide linear dynamic range and the possibility of absolute quantification are the main advantages of ICP-MS. But in the context of immuno imaging by the use of LA-ICP-MS, quantification of analytes is limited due to non-controllable antibody labeling chemistry. In the presented proof-of-principle a novel antibody labeling technique has been investigated which results in a controlled labeling degree. A small affinity protein based on the C2 domain of protein G was modified with conventional metal coded tags (MeCAT) after introducing a cysteine into the C-terminus of the protein. The modified C2 domain photo-crosslinks to the Fc or Fab region of the IgG and allows specific and covalent labeling of antibodies for multiplex immunoassay analysis by the use of LA-ICP-MS. In combination with a house-made calibration membrane the amount of labeled antibody-antigen complexes in a multiplex western blot immunoassay was determined by LA-ICP-MS.

  8. Recent applications on isotope ratio measurements by ICP-MS and LA-ICP-MS on biological samples and single particles

    NASA Astrophysics Data System (ADS)

    Becker, J. Sabine; Sela, Hagit; Dobrowolska, Justina; Zoriy, Miroslav; Becker, J. Susanne

    2008-02-01

    Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have proved themselves to be powerful and sensitive inorganic mass spectrometric techniques for analysing stable and radioactive isotopes in different application fields because of their high sensitivity, low detection limits, good accuracy and precision. New applications of ICP-MS focus on tracer experiments and the development of isotope dilution techniques together with nanoflow injections for the analysis of small volumes of biological samples. Today, LA-ICP-MS is the method of choice for direct determination of metals, e.g., on protein bands in gels after the gel electrophoresis of protein mixtures. Tracer experiments using highly enriched 65Cu were utilized in order to study the formation of metal-binding bovine serum proteins. A challenging task for LA-ICP-MS is its application as an imaging mass spectrometric technique for the production of isotope images (e.gE, from thin sections of brain tissues stained with neodymium). In this paper, we demonstrate the application of imaging mass spectrometry on single particles (zircon and uranium oxide). Single Precambrian zircon crystals from the Baltic Shield were investigated with respect to isotope ratios using LA-ICP-MS for age dating. The U-Pb age was determined from the isochrone with (1.48 ± 0.14) × 109 a. Using isotope ratio measurements on 10 nuclear uranium oxide single particles the 235U/238U isotope ratio was determined to be 0.032 ± 0.004. This paper describes recent developments and applications of isotope ratio measurements by ICP-MS and LA-ICP-MS on biological samples and single particles.

  9. Allanite age-dating: Non-matrix-matched standardization in quadrupole LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Burn, M.; Lanari, P.; Pettke, T.; Engi, M.

    2014-12-01

    Allanite Th-U-Pb age-dating has recently been found to be powerful in unraveling the timing of geological processes such as the metamorphic dynamics in subduction zones and crystallization velocity of magmas. However, inconsistencies among analytical techniques have raised doubts about the accuracy of allanite age data. Spot analysis techniques such as LA-ICP-MS are claimed to be crucially dependent on matrix-matched standards, the quality of which is variable. We present a new approach in LA-ICP-MS data reduction that allows non-matrix-matched standardization via well constrained zircon reference materials as primary standards. Our data were obtained using a GeoLas Pro 193 nm ArF excimer laser ablation system coupled to an ELAN DRC-e quadrupole ICP-MS. We use 32 μm and 24 μm spot sizes; laser operating conditions of 9 Hz repetition rate and 2.5 J/cm2 fluence have proven advantageous. Matrix dependent downhole fractionation evolution is empirically determined by analyzing 208Pb/232Th and 206Pb/238U and applied prior to standardization. The new data reduction technique was tested on three magmatic allanite reference materials (SISSb, CAPb, TARA); within error these show the same downhole fractionation evolution for all allanite types and in different analytical sessions, provided measurement conditions remain the same. Although the downhole evolution of allanite and zircon differs significantly, a link between zircon and allanite matrix is established by assuming CAPb and TARA to be fixed at the corresponding reference ages. Our weighted mean 208Pb/232Th ages are 30.06 ± 0.22 (2σ) for SISSb, 275.4 ± 1.3 (2σ) for CAPb, and 409.9 ± 1.8 (2σ) for TARA. Precision of single spot age data varies between 1.5 and 8 % (2σ), dependent on spot size and common lead concentrations. Quadrupole LA-ICP-MS allanite age-dating has thus similar uncertainties as do other spot analysis techniques. The new data reduction technique is much less dependent on quality and homogeneity

  10. 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).

    PubMed

    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.

  11. A powerful tool for assessing distribution and fate of potentially toxic metals (PTMs) in soils: integration of laser ablation spectrometry (LA-ICP-MS) on thin sections with soil micromorphology and geochemistry.

    PubMed

    Scarciglia, Fabio; Barca, Donatella

    2017-03-02

    The dynamic behavior and inherent spatial heterogeneity, at different hierarchic levels, of the soil system often make the spatial distribution of potentially toxic metals (PTMs) quite complex and difficult to assess correctly. This work demonstrates that the application of laser ablation spectrometry (LA-ICP-MS) to soil thin sections constitutes an ancillary powerful tool to well-established analytical methods for tracing the behavior and fate of potential soil contaminants at the microsite level. It allowed to discriminate the contribution of PTMs in distinct soil sub-components, such as parent rock fragments, neoformed, clay-enriched or humified matrix, and specific pedogenetic features of illuvial origin (unstained or iron-stained clay coatings) even at very low contents. PTMs were analyzed in three soil profiles located in the Muravera area (Sardinia, Italy), where several, now abandoned mines were exploited. Recurrent trends of increase of many PTMs from rock to pedogenic matrix and to illuvial clay coatings, traced by LA-ICP-MS compositional data, revealed a pedogenetic control on metal fractionation and distribution, based on adsorption properties of clay minerals, iron oxyhydroxides or organic matter, and downprofile illuviation processes. The main PTMs patterns coupled with SEM-EDS analyses suggest that heavy metal-bearing mineral grains were sourced from the mine plants, in addition to the natural sedimentary input. The interplay between soil-forming processes and geomorphic dynamics significantly contributed to the PTMs spatial distribution detected in the different pedogenetic horizons and soil features.

  12. Apatite fission track dating by LA-ICP-MS and External Detector Method: How do they stack up?

    NASA Astrophysics Data System (ADS)

    Seiler, C.; Gleadow, A. J.; Kohn, B. P.

    2013-12-01

    Analysis of trace element compositions by laser ablation ICP-MS has become a widely used tool to determine in-situ ages in geochronology. Although used primarily for U-Pb dating, LA-ICP-MS has been successfully adapted to other dating techniques such as apatite fission track (Hasebe et al., 2004) or (U-Th)/He (Boyce et al., 2006), making it an ideal tool for multi-system thermochronological studies. LA-ICP-MS fission track dating has several important advantages over the traditional external detector method (EDM), particularly in terms of sample turn-around time and the fact that neutron irradiations (and the handling of radioactive materials) are no longer necessary, while providing a similar level of in-situ information. Perhaps the most important benefits of LA-ICP-MS fission track dating is that it could potentially be used as an absolute dating technique with no Zeta-calibration necessary. However, beyond the initial study of Hasebe et al. (2004), little work has been done to compare results obtained by LA-ICP-MS with those from EDM analysis, and it remains unclear whether the two methods yield equivalent results. We present an extensive dataset of fission track results that were analysed using both LA-ICP-MS and EDM dating. The samples were selected to represent a variety of compositions, with single grain ages ranging from a few million to over a billion years. Both techniques were applied on identical grains, thereby eliminating uncertainties associated with natural variability. The comparison shows that, with a few exceptions, single grain fission track ages from LA-ICP-MS and EDM are concordant within analytical uncertainties and scatter symmetrically around the 1:1 correlation line. Although the relative difference in single grain ages varies significantly in either direction (up to 70%), there are no systematic variations between the two methods suggesting that this variation is simply due to random sampling effects. However, we did find systematic

  13. Online Standard Additions Technique for La-ICP-MS Using a Desolvating Nebulizer System

    NASA Astrophysics Data System (ADS)

    Roy, J.; Asogan, D.; Moody, S.; Clarke, D.

    2014-12-01

    Historically, quantification with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been limited to the ability to matrix match both standards and samples. This can prove problematic when a particular matrix matched standard is not readily available. Liquid standard addition has been shown1-4 as an alternative technique for quantification that does not require matrix matching; however, further fundamental study is needed especially considering the different mass flow rates delivered to the plasma from traditional pneumatic nebulizers and laser ablation itself. In this work, the authors combine a specialized low-flow desolvating nebulizer system with LA-ICP-MS. This nebulizer system efficiently removes water vapour, thereby significantly reducing oxide based mass spectral interferences. For the instrument setup, the output from the laser is combined with the dried aerosol from the nebulizer system prior to entering the ICP-MS source. By using two sources of dry aerosol, mixing efficiency is improved whilst minimising plasma power lost to solvent (water vapour) processing. The method was applied to both USGS Green River Shale and an Arkansas Womble Shale. The results showed a number of elements that were correctly quantified using the technique as compared to reference values. References Gunther, D., Cousin, H., Magyar, B., Leopold, I., J. Anal. Atom. Spectrom., 1997, 12, 165 - 170. Leach, J.J., Allen, L. A., Aeschliman, D.B., Houk, R.S., Anal. Chem., 1999, 71, 440 - 445. O'Conner, C.J.P., Sharp, B.L, Evans, P.J., Anal. Atom. Spectrom., 2006, 21, 556. Yang, C.K., Chi, P.H., Lin, Y.C., Sun, Y.C., Yang, M.H., Talanta, 2010, 80, 1222 - 1227.

  14. External calibration strategy for trace element quantification in botanical samples by LA-ICP-MS using filter paper.

    PubMed

    Nunes, Matheus A G; Voss, Mônica; Corazza, Gabriela; Flores, Erico M M; Dressler, Valderi L

    2016-01-28

    The use of reference solutions dispersed on filter paper discs is proposed for the first time as an external calibration strategy for matrix matching and determination of As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, V and Zn in plants by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). The procedure is based on the use of filter paper discs as support for aqueous reference solutions, which are further evaporated, resulting in solid standards with concentrations up to 250 μg g(-1) of each element. The use of filter paper for calibration is proposed as matrix matched standards due to the similarities of this material with botanical samples, regarding to carbon concentration and its distribution through both matrices. These characteristics allowed the use of (13)C as internal standard (IS) during the analysis by LA-ICP-MS. In this way, parameters as analyte signal normalization with (13)C, carrier gas flow rate, laser energy, spot size, and calibration range were monitored. The calibration procedure using solution deposition on filter paper discs resulted in precision improvement when (13)C was used as IS. The method precision was calculated by the analysis of a certified reference material (CRM) of botanical matrix, considering the RSD obtained for 5 line scans and was lower than 20%. Accuracy of LA-ICP-MS determinations were evaluated by analysis of four CRM pellets of botanical composition, as well as by comparison with results obtained by ICP-MS using solution nebulization after microwave assisted digestion. Plant samples of unknown elemental composition were analyzed by the proposed LA method and good agreement were obtained with results of solution analysis. Limits of detection (LOD) established for LA-ICP-MS were obtained by the ablation of 10 lines on the filter paper disc containing 40 μL of 5% HNO3 (v v(-1)) as calibration blank. Values ranged from 0.05 to 0.81  μg g(-1). Overall, the use of filter paper as support for dried aqueous

  15. LA-iMageS: a software for elemental distribution bioimaging using LA-ICP-MS data.

    PubMed

    López-Fernández, Hugo; de S Pessôa, Gustavo; Arruda, Marco A Z; Capelo-Martínez, José L; Fdez-Riverola, Florentino; Glez-Peña, Daniel; Reboiro-Jato, Miguel

    2016-01-01

    The spatial distribution of chemical elements in different types of samples is an important field in several research areas such as biology, paleontology or biomedicine, among others. Elemental distribution imaging by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is an effective technique for qualitative and quantitative imaging due to its high spatial resolution and sensitivity. By applying this technique, vast amounts of raw data are generated to obtain high-quality images, essentially making the use of specific LA-ICP-MS imaging software that can process such data absolutely mandatory. Since existing solutions are usually commercial or hard-to-use for average users, this work introduces LA-iMageS, an open-source, free-to-use multiplatform application for fast and automatic generation of high-quality elemental distribution bioimages from LA-ICP-MS data in the PerkinElmer Elan XL format, whose results can be directly exported to external applications for further analysis. A key strength of LA-iMageS is its substantial added value for users, with particular regard to the customization of the elemental distribution bioimages, which allows, among other features, the ability to change color maps, increase image resolution or toggle between 2D and 3D visualizations.

  16. Progress in LA-ICP-MS Microanalysis Using a 200 nm-femtosecond Laser

    NASA Astrophysics Data System (ADS)

    Jochum, K. P.; Stoll, B.; Weis, U.; Jacob, D. E.; Mertz-Kraus, R.; Andreae, M. O.

    2013-12-01

    We have investigated the performance of LA-ICP-MS for the microanalysis of a variety of samples of different matrices using the 200 nm Ti-sapphire based fs-laser ablation system NWR Femto200 combined with the sector-field ICP-MS Thermo Element2. For comparison, we conducted similar experiments with three ns lasers: 193 nm Nd:YAG, 213 nm Nd:YAG, 193 nm ArF excimer. Measurements were performed with different spot sizes (10 - 65 μm), pulse repetition rates (5 - 250 Hz) and energy densities (0.5 - 0.7 Jcm-2) in spot and line scan analysis modes. We applied those settings to well-characterized and homogeneous synthetic silicate, geological, carbonate and phosphate microanalytical reference materials from NIST, USGS, MPI-DING and others. Our investigations show that in the case of UV-fs laser ablation line scan analysis is much more appropriate than spot analysis. In contrast to the ns lasers, fs laser spot analysis is characterized by a strong decrease of ion intensities, presumably caused by the generation of color centers by fs laser pulses [1]. On the other hand, line scan analyses yield uniform and relative high ion intensities so that detection limits for the various elements are similar to ns laser ablation. In LA-ICP-MS, the major limitations regarding measurement accuracy are matrix effects. The experiments demonstrate that in each case the fs data are more reproducible and less matrix-dependent with respect to fractionation factors [2] and mass-load induced matrix effects [3] than the results obtained using the ns lasers. The fractionation factors of refractory, volatile, lithophile and chalcophile elements are unity for the line scan mode and agree within an uncertainty of 1 %, whereas significantly lower, but matrix-independent, values for the volatile elements Pb (0.93 × 0.03) and Zn (0.88 × 0.04) were observed using the spot analysis mode. This implies that calibration can be performed reliably for quite different matrices using certified silicate

  17. Major to ultra trace element bulk rock analysis of nanoparticulate pressed powder pellets by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Peters, Daniel; Pettke, Thomas

    2016-04-01

    An efficient, clean procedure for bulk rock major to trace element analysis by 193 nm Excimer LA-ICP-MS analysis of nanoparticulate pressed powder pellets (PPPs) employing a binder is presented. Sample powders are milled in water suspension in a planetary ball mill, reducing average grain size by about one order of magnitude compared to common dry milling protocols. Microcrystalline cellulose (MCC) is employed as a binder, improving the mechanical strength of the PPP and the ablation behaviour, because MCC absorbs 193 nm laser light well. Use of MCC binder allows for producing cohesive pellets of materials that cannot be pelletized in their pure forms, such as quartz powder. Rigorous blank quantification was performed on synthetic quartz treated like rock samples, demonstrating that procedural blanks are irrelevant except for a few elements at the 10 ng g-1 concentration level. The LA-ICP-MS PPP analytical procedure was optimised and evaluated using six different SRM powders (JP-1, UB-N, BCR-2, GSP-2, OKUM, and MUH-1). Calibration based on external standardization using SRM 610, SRM 612, BCR-2G, and GSD-1G glasses allows for evaluation of possible matrix effects during LA-ICP-MS analysis. The data accuracy of the PPP LA-ICP-MS analytical procedure compares well to that achieved for liquid ICP-MS and LA-ICP-MS glass analysis, except for element concentrations below ˜30 ng g-1, where liquid ICP-MS offers more precise data and in part lower limits of detection. Uncertainties on the external reproducibility of LA-ICP-MS PPP element concentrations are of the order of 0.5 to 2 % (1σ standard deviation) for concentrations exceeding ˜1 μg g-1. For lower element concentrations these uncertainties increase to 5-10% or higher when analyte-depending limits of detection (LOD) are approached, and LODs do not significantly differ from glass analysis. Sample homogeneity is demonstrated by the high analytical precision, except for very few elements where grain size effects can

  18. Histopathological localization of cadmium in rat placenta by LA-ICP-MS analysis.

    PubMed

    Yamagishi, Yoshikazu; Furukawa, Satoshi; Tanaka, Ayano; Kobayashi, Yoshiyuki; Sugiyama, Akihiko

    2016-10-01

    In order to clarify the histological localization of cadmium (Cd) in the placenta, we analyzed paraffin sections of placentas from rats with a single Cd exposure on gestation day 18 by the LA-ICP-MS imaging method compared with the histopathological changes. The placentas were sampled at 1 hour, 2 hours, 3 hours, 6 hours, and 24 hours after treatment. Histopathologically, the trophoblasts in the labyrinth zone of the Cd group showed swelling at 1 hour. At 2 and 3 hours, the trophoblasts showed swelling and vacuolar degeneration. At 6 and 24 hours, the syncytiotrophoblasts selectively underwent necrosis/apoptosis, resulting in a decrease in number. Remarkable metallothionein expression was observed in the trophoblastic septa, particularly cytotrophoblasts at 24 hours. The LA-ICP-MS analysis detected the localization of Cd in the fetal part of the placenta from 1 hour onwards. In particular, the intensity of Cd was prominent in the labyrinth zone and tended to increase with the progression of trophoblastic septa damages. The LA-ICP-MS analysis using the paraffin sections detected the localization of Cd in the fetal part of the placenta, and this methodology will be one of the valuable tools to detect heavy metals in toxicological pathology.

  19. The influence of ns- and fs-LA plume local conditions on the performance of a combined LIBS/LA-ICP-MS sensor

    SciTech Connect

    LaHaye, Nicole L.; Phillips, Mark C.; Duffin, Andrew M.; Eiden, Gregory C.; Harilal, Sivanandan S.

    2016-01-01

    Both laser-induced breakdown spectroscopy (LIBS) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are well-established analytical techniques with their own unique advantages and disadvantages. The combination of the two analytical methods is a very promising way to overcome the challenges faced by each method individually. We made a comprehensive comparison of local plasma conditions between nanosecond (ns) and femtosecond (fs) laser ablation (LA) sources in a combined LIBS and LA-ICP-MS system. The optical emission spectra and ICP-MS signal were recorded simultaneously for both ns- and fs-LA and figures of merit of the system were analyzed. Characterization of the plasma was conducted by evaluating temperature and density of the plume under various irradiation conditions using optical emission spectroscopy, and correlations to ns- and fs-LIBS and LA-ICP-MS signal were made. The present study is very useful for providing conditions for a multimodal system as well as giving insight into how laser ablation plume parameters are related to LA-ICP-MS and LIBS results for both ns- and fs-LA.

  20. Detection of transgenerational barium dual-isotope marks in salmon otoliths by means of LA-ICP-MS.

    PubMed

    Huelga-Suarez, Gonzalo; Fernández, Beatriz; Moldovan, Mariella; García Alonso, J Ignacio

    2013-03-01

    The present study evaluates the use of an individual-specific transgenerational barium dual-isotope procedure and its application to salmon specimens from the Sella River (Asturias, Spain). For such a purpose, the use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in combination with multiple linear regression for the determination of the isotopic mark in the otoliths of the specimens is presented. In this sense, a solution in which two barium-enriched isotopes ((137)Ba and (135)Ba) were mixed at a molar ratio of ca. 1:3 (N Ba137/N Ba135) was administered to eight returning females caught during the spawning period. After injection, these females, as well as their offspring, were reared in a governmental hatchery located in the council of Cangas de Onís (Asturias, Spain). For comparison purposes, as well as for a time-monitoring control, egg and larva data obtained by solution analysis ICP-MS are also given. Otoliths (9-month-old juveniles) of marked offspring were analysed by LA-ICP-MS demonstrating a 100 % marking efficacy of this methodology. The capabilities of the molar fraction approach for 2D imaging of fish otoliths are also addressed.

  1. Using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to explore geochemical taphonomy of vertebrate fossils in the upper cretaceous two medicine and Judith River formations of Montana

    USGS Publications Warehouse

    Rogers, R.R.; Fricke, H.C.; Addona, V.; Canavan, R.R.; Dwyer, C.N.; Harwood, C.L.; Koenig, A.E.; Murray, R.; Thole, J.T.; Williams, J.

    2010-01-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine rare earth element (REE) content of 76 fossil bones collected from the Upper Cretaceous (Campanian) Two Medicine (TMF) and Judith River (JRF) Formations of Montana. REE content is distinctive at the formation scale, with TMF samples exhibiting generally higher overall REE content and greater variability in REE enrichment than JRF samples. Moreover, JRF bones exhibit relative enrichment in heavy REE, whereas TMF bones span heavy and light enrichment fields in roughly equal proportions. TMF bones are also characterized by more negative Ce anomalies and greater U enrichment than JRF bones, which is consistent with more oxidizing diagenetic conditions in the TMF. Bonebeds in both formations show general consistency in REE content, with no indication of spatial or temporal mixing within sites. Previous studies, however, suggest that the bonebeds in question are attritional assemblages that accumulated over considerable time spans. The absence of geochemical evidence for mixing is consistent with diagenesis transpiring in settings that remained chemically and hydrologically stable during recrystallization. Lithology-related patterns in REE content were also compared, and TMF bones recovered from fluvial sandstones show relative enrichment in heavy REE when compared with bones recovered from fine-grained floodplain deposits. In contrast, JRF bones, regardless of lithologic context (sandstone versus mudstone), exhibit similar patterns of REE uptake. This result is consistent with previous reconstructions that suggest that channel-hosted microfossil bonebeds of the JRF developed via the reworking of preexisting concentrations embedded in the interfluve. Geochemical data further indicate that reworked elements were potentially delivered to channels in a recrystallized condition, which is consistent with rapid adsorption of REE postmortem. Copyright ?? 2010, SEPM (Society for

  2. Chemical Characterization of Bed Material Coatingsby LA-ICP-MS and SEM-EDS

    NASA Astrophysics Data System (ADS)

    Piispanen, M. H.; Mustonen, A. J.; Tiainen, M. S.; Laitinen, R. S.

    Bed material coatings and the consequent agglomeration of bed material are main ash-related problems in FB-boilers. The bed agglomeration is a particular problem when combusting biofuels and waste materials. Whereas SEM-EDS together with automated image processing has proven to be a convenient method to study compositional distribution in coating layers and agglomerates, it is a relatively expensive technique and is not necessarily widely available. In this contribution, we explore the suitability of LA-ICP-MS to provide analogous information of the bed.

  3. LA-ICP-MS of rare earth elements concentrated in cation-exchange resin particles for origin attribution of uranium ore concentrate.

    PubMed

    Asai, Shiho; Limbeck, Andreas

    2015-04-01

    Rare earth elements (REE) concentrated on cation-exchange resin particles were measured with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to obtain chondrite-normalized REE plots. The sensitivity of REE increased in ascending order of the atomic number, according to the sensitivity trend in pneumatic nebulization ICP-MS (PN-ICP-MS). The signal intensities of REE were nearly proportional to the concentrations of REE in the immersion solution used for particle-preparation. Minimum measurable concentration calculated from the net signals of REE was approximately 1 ng/g corresponding to 0.1 ng in the particle-preparation solution. In LA analysis, formation of oxide and hydroxide of the light REE and Ba which causes spectral interferences in the heavy REE measurement was effectively attenuated due to the solvent-free measurement capability, compared to conventional PN-ICP-MS. To evaluate the applicability of the proposed method, the REE-adsorbed particles prepared by immersing them in a U-bearing solution (commercially available U standard solution) were measured with LA-ICP-MS. Aside from the LA analysis, each concentration of REE in the same U standard solution was determined with conventional PN-ICP-MS after separating REE by cation-exchange chromatography. The concentrations of REE were ranging from 0.04 (Pr) to 1.08 (Dy) μg/g-U. The chondrite-normalized plot obtained through LA-ICP-MS analysis of the U standard sample exhibited close agreement with that obtained through the PN-ICP-MS of the REE-separated solution within the uncertainties.

  4. Trace element mapping by LA-ICP-MS: assessing geochemical mobility in garnet

    NASA Astrophysics Data System (ADS)

    Raimondo, Tom; Payne, Justin; Wade, Benjamin; Lanari, Pierre; Clark, Chris; Hand, Martin

    2017-04-01

    A persistent problem in the study of garnet geochemistry is that the consideration of major elements alone excludes a wealth of information preserved by trace elements, particularly the rare-earth elements (REEs). This is despite the fact that trace elements are generally less vulnerable to diffusive resetting, and are sensitive to a broader spectrum of geochemical interactions involving the entire mineral assemblage, including the growth and/or dissolution of accessory minerals. We outline a technique for the routine acquisition of high-resolution 2D trace element maps by LA-ICP-MS, and introduce an extension of the software package XMapTools for rapid processing of LA-ICP-MS data to visualise and interpret compositional zoning patterns. These methods form the basis for investigating the mechanisms controlling geochemical mobility in garnet, which are argued to be largely dependent on the interplay between element fractionation, mineral reactions and partitioning, and the length scales of intergranular transport. Samples from the Peaked Hill shear zone, Reynolds Range, central Australia, exhibit contrasting trace element distributions that can be linked to a detailed sequence of growth and dissolution events. Trace element mapping is thus employed to place garnet evolution in a specific paragenetic context and derive absolute age information by integration with existing U-Pb monazite and Sm-Nd garnet geochronology. Ultimately, the remarkable preservation of original growth zoning and its subtle modification by subsequent re-equilibration is used to `see through' multiple superimposed events, thereby revealing a previously obscure petrological and temporal record of metamorphism, metasomatism, and deformation.

  5. Determination of Trace and Volatile Element Abundance Systematics of Lunar Pyroclastic Glasses 74220 and 15426 Using LA-ICP-MS

    NASA Technical Reports Server (NTRS)

    McIntosh, E. Carrie; Porrachia, Magali; McCubbin, Francis M.; Day, James M. D.

    2017-01-01

    Since their recognition as pyroclastic glasses generated by volcanic fire fountaining on the Moon, 74220 and 15426 have garnered significant scientific interest. Early studies recognized that the glasses were particularly enriched in volatile elements on their surfaces. More recently, detailed analyses of the interiors of the glasses, as well as of melt inclusions within olivine grains associated with the 74220 glass beads, have determined high H2O, F, Cl and S contents. Such elevated volatile contents seem at odds with evidence from moderately volatile elements (MVE), such as Zn and K, for a volatile- depleted Moon. In this study, we present initial results from an analytical campaign to study trace element abundances within the pyroclastic glass beads. We report trace element data determined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for 15426 and 74220.

  6. Uranium-lead dating of perovskite from the Afrikanda plutonic complex (Kola Peninsula, Russia) using LA-ICP-MS.

    NASA Astrophysics Data System (ADS)

    Reguir, E.; Camacho, A.; Yang, P.; Chakhmouradian, A. R.; Halden, N. M.

    2009-04-01

    Perovskite (CaTiO3) is a common early crystallizing accessory phase in a variety of alkaline rocks, and has been shown to contain enough U and Th for U-Pb dating. U and Pb analysis of perovskite has been primarily carried out using the SHRIMP or ID-TIMS techniques, and the resulting U-Pb dates commonly yield the emplacement age of the host rock. To our knowledge, only one U-Pb study of perovskite has been done using the LA-ICP-MS (Cox and Wilton, 2006). Some of the advantages of this method over the SHRIMP and ID-TIMS techniques include greater speed and lower cost of analysis. In this work, the U-Pb ages of perovskite from the Afrikanda plutonic complex (Russia) were obtained in situ using the LA-ICP-MS. The measured 238U/206Pb and 207Pb/206Pb ratios were corrected for time-dependent mass-bias using the well-calibrated zircon standard GJ-1 (608.5 ± 0.4 Ma; Jackson et al., 2004). On a Tera-Wasserburg diagram (Tera and Wasserburg, 1972) the analyses of perovskite from two magmatic phases (clinopyroxenite and carbonatite) plot in separate clusters. Although the variations in the 238U/206Pb and 207Pb/206Pb ratios within each group are small, there is enough dispersion between the two clusters to obtain a reasonably precise age of 375 ± 13 Ma (2; MSWD = 0.23), which strongly suggests that the carbonatitic rocks are broadly coeval with the clinopyroxenite. The only other isotopic study on the Afrikanda Complex was done on a clinopyroxenite using the Rb-Sr method and yielded a whole rock-mineral (perovskite, biotite, augite and apatite) isochron age of 364.0 ± 3.1 Ma (2; MSWD = 0.72). This age is within error of our U-Pb date, which demonstrates that LA-ICP-MS-based U-Pb dating of perovskite can serve as a reliable geochronological tool. References Cox, R.A. and Wilton, D.H.C. (2006) U-Pb dating of perovskite by LA-ICP-MS: An example from the Oka carbonatite, Quebec, Canada. Chem. Geol., 235, 21-32. Jackson, S.E., Pearson, N.J., Griffin, W.L. and Belousova, E.A. (2004

  7. LA-ICP-MS as Tool for Provenance Analyses in Arctic Marine Sediments

    NASA Astrophysics Data System (ADS)

    Wildau, Antje; Garbe-Schönberg, Dieter

    2015-04-01

    The hydraulic transport of sediments is a major geological process in terrestrial and marine systems and is responsible for the loss, redistribution and accumulation of minerals. Provenance analyses are a powerful tool for assessing the origin and dispersion of material in ancient and modern fluvial and marine sediments. Provenance-specific heavy minerals (e.g., zircon, rutile, tourmaline) can therefore be used to provide valuable information on the formation of ore deposits (placer deposits), and the reconstruction of paleogeography, hydrology, climate conditions and developments. The application of provenances analyses for the latter reason is of specific interest, since there is need for research on the progressing climate change, and heavy minerals represent good proxies for the evaluation of recent and past changes in the climate. The study of these fine particles provides information about potential regional or long distance transport paths, glacial / ice drift and current flows, freezing and melting events as well as depositional centers for the released sediments. Classic methods applied for provenance analyses are mapping of the presence / absence of diagnostic minerals, their grain size distribution, modal mineralogy and the analysis of variations in ratio of two or more heavy minerals. Electron microprobe has been established to discover changes in mineral chemistry of individual mineral phases, which can indicate fluctuations or differences in the provenance. All these methods bear the potential of high errors that lower the validity of the provenance analyses. These are for example the misclassification of mineral species due to undistinguishable optical properties or the limitations in the detection / variations of trace elements using the election microprobe. For this case study, marine sediments from the Arctic Ocean have been selected to test if LA-ICP-MS can be established as a key technique for precise and reliable provenance analyses. The Laptev

  8. LA-ICP-MS Allows Quantitative Microscopy of Europium-Doped Iron Oxide Nanoparticles and is a Possible Alternative to Ambiguous Prussian Blue Iron Staining.

    PubMed

    Scharlach, Constantin; Müller, Larissa; Wagner, Susanne; Kobayashi, Yuske; Kratz, Harald; Ebert, Monika; Jakubowski, Norbert; Schellenberger, Eyk

    2016-05-01

    The development of iron oxide nanoparticles for biomedical applications requires accurate histological evaluation. Prussian blue iron staining is widely used but may be unspecific when tissues contain substantial endogenous iron. Here we tested whether microscopy by laser ablation coupled to inductively coupled plasma mass spectrometry (LA-ICP-MS) is sensitive enough to analyze accumulation of very small iron oxide particles (VSOP) doped with europium in tissue sections. For synthesis of VSOP, a fraction of Fe3+ (5 wt%) was replaced by Eu3+, resulting in particles with 0.66 mol% europium relative to iron (Eu-VSOP) but with otherwise similar properties as VSOP. Eu-VSOP or VSOP was intravenously injected into ApoE-/- mice on Western cholesterol diet and accumulated in atherosclerotic plaques of these animals. Prussian blue staining was positive for ApoE-/- mice with particle injection but also for controls. LA-ICP-MS microscopy resulted in sensitive and specific detection of the europium of Eu-VSOP in liver and atherosclerotic plaques. Furthermore, calibration with Eu-VSOP allowed calculation of iron and particle concentrations in tissue sections. The combination of europium-doped iron oxide particles and LA-ICP-MS microscopy provides a new tool for specific and quantitative analysis of particle distribution at the tissue level and allows correlation with other elements such as endogenous iron.

  9. Genesis of Augite-Bearing Ureilites: Evidence From LA-ICP-MS Analyses of Pyroxenes and Olivine

    NASA Technical Reports Server (NTRS)

    Herrin, J. S.; Lee, C-T. A.; Mittlefehldt, D. W.

    2008-01-01

    Ureilites are ultramafic achondrites composed primarily of coarse-grained low-Ca pyroxene and olivine with interstitial carbonaceous material, but a number of them contain augite [1]. Ureilites are considered to be restites after partial melting of a chondritic precursor, although at least some augite-bearing ureilites may be partially cumulate [1, 2]. In this scenario, the augite is a cumulus phase derived from a melt that infiltrated a restite composed of typical ureilite material (olivine+low-Ca pyroxene) [2]. To test this hypothesis, we examined the major and trace element compositions of silicate minerals in select augite-bearing ureilites with differing mg#. Polished thick sections of the augite-bearing ureilites ALH 84136 , EET 87511, EET 96293, LEW 88201, and META78008 and augite-free typical ureilite EET 90019 were examined by EPMA for major and minor elements and laser ablation ICP-MS (LA-ICP-MS) for trace elements, REE in particular. Although EET 87511 is reported to contain augite, the polished section that we obtained did not.

  10. Improvement of the determination of element concentrations in quartz-hosted fluid inclusions by LA-ICP-MS and Pitzer thermodynamic modeling of ice melting temperature

    NASA Astrophysics Data System (ADS)

    Leisen, Mathieu; Dubessy, Jean; Boiron, Marie-Christine; Lach, Philippe

    2012-08-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has become an essential analytical tool for the study of paleofluid chemistry through the analysis of individual fluid inclusions. The calculation of major and trace element concentrations in fluid inclusions is usually based on empirical equations whose significance and accuracy are questionable. In addition, methods for estimation of analytical uncertainties element concentration in individual fluid inclusions are lacking. This study describes a method based upon Pitzer's thermodynamic model for the calculation of major element (Na, K, Mg and Ca) concentrations in low-to moderate-salinity fluid inclusions. A signal processing protocol, used in combination with the new method is also developed to calculate the concentration, for each inclusion, and uncertainty for each major and trace element. In order to validate the proposed method, synthetic and natural fluid inclusions (from Alpine quartz veins) were ablated with a 193 nm ArF excimer laser and analyzed with a quadrupole ICP-MS, equipped with an octopole collision-reaction cell. The difference between the calculated and actual element concentration (i.e. accuracy) does not exceed 20% and the calculated relative standard deviation (i.e. precision) for all element concentrations is ˜10% in standards (glasses, solutions in capillary tubes and synthetic fluid inclusions). The element concentrations obtained with this new method for the Alpine fluid inclusions are in good agreement with those previously measured using Laser Induced Breakdown Spectroscopy (LIBS) or crush-leach methods. Finally, the calculated concentrations and associated uncertainties determined for each element in individual fluid inclusions show that the sensitivity of LA-ICP-MS analysis is high enough to reflect small variations of major and trace element concentrations in the Alpine paleofluid, initially considered to have a constant chemistry. The new approach presented in

  11. Sorption of Eu(III) on granite: EPMA, LA-ICP-MS, batch and modeling studies.

    PubMed

    Fukushi, Keisuke; Hasegawa, Yusuke; Maeda, Koushi; Aoi, Yusuke; Tamura, Akihiro; Arai, Shoji; Yamamoto, Yuhei; Aosai, Daisuke; Mizuno, Takashi

    2013-11-19

    Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages.

  12. Precise and Accurate Trace Element Analysis of Calcium Carbonate by LA-ICP-MS and its Application to Stalagmites

    NASA Astrophysics Data System (ADS)

    Jochum, K. P.; Scholz, D.; Stoll, B.; Weis, U.; Yang, Q.; Andreae, M. O.

    2011-12-01

    Interest in high-spatial-resolution in-situ micro-analysis of calcium carbonates (e.g., speleothems, corals, ostracods) has increased substantially in recent years, because these samples provide important information on past climate variability. The most commonly used method is LA-ICP-MS, which combines the advantages of low detection limits (ng/g range) with high spatial resolution (10 - 100 μm). Most studies apply low mass resolution ICP-MS, and the synthetic NIST 610 and 612 silicate glasses for instrumental calibration. However, there are several drawbacks of this procedure: (1) the NIST glasses have not been certified for micro-analytical purposes, (2) molecules and doubly charged ions may interfere with the mass lines of interest, and (3) the silicate matrix is quite different from the carbonate matrix. We have, therefore, systematically investigated these points by using the low (300) and medium (4000) mass resolution modes of the Thermo Element2 ICP-MS, application of different laser ablation systems (193 nm and 213 nm wavelengths, respectively) and reference materials of different matrix (NIST silicate glass, calcium carbonate, natural geological). Recently, Jochum et al. (2011) investigated the use of the NIST glasses in micro-analysis and provided both new reference values and the corresponding uncertainties at 95 % confidence level following ISO guidelines. These values differ significantly (by as much as 10 %) from the most commonly used values of Pearce et al. (1997). Our study demonstrates that many mass lines are affected by interferences in low mass resolution mode, such as the 24Mg line, which is interfered by 48Ca++ in carbonate samples, the 67Zn line, which is interfered with 27Al40Ar+ in silicate glasses, and 31P, which may be affected by 15N16O+and 14N17O+. In addition, a "gas blank" correction is insufficient in case of a significant increase of Ca and C molecules during ablation of calcium carbonate samples. These mass lines should

  13. A new LA-ICP-MS method for Ti-in-Quartz: Implications and application to HP rutile-quartz veins from the Czech Erzgebirge

    NASA Astrophysics Data System (ADS)

    Cruz-Uribe, A. M.; Mertz-Kraus, R.; Zack, T.; Feineman, M. D.; Woods, G.

    2014-12-01

    Experimental determination of the pressure and temperature controls on Ti solubility in quartz provide a calibration of the Ti-in-quartz (TitaniQ) geothermometer applicable to geologic conditions up to ~20 kbar (Thomas et al. (2010) Contrib Mineral Petrol 160, 743-759). One of the greatest limitations to analyzing Ti in metamorphic quartz by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is the lack of a suitable matrix-matched reference material. Typically LA-ICP-MS analyses of Ti in minerals use 49Ti as a normalizing mass because of an isobaric interference from 48Ca, which is present in most well characterized reference glasses, on 48Ti. The benefit of using a matrix-matched reference material to analyze Ti in quartz is the opportunity to use 48Ti (73.8 % abundance) as a normalizing mass, which results in an order of magnitude increase in signal strength compared to the less abundant isotope 49Ti (5.5 % abundance), thereby increasing the analytical precision. Here we characterize Ti-bearing SiO2 glasses from Heraeus Quarzglas and natural quartz grains from the Bishop Tuff by cathodoluminescence (CL) imaging, electron probe microanalysis (EPMA), and LA-ICP-MS, in order to determine their viability as reference materials for Ti in quartz. Titanium contents in low-CL rims in the Bishop Tuff quartz grains were determined to be homogenous by EPMA (41 ± 2 µg/g Ti, 2σ), and are a potential natural reference material. We present a new method for determining 48Ti concentrations in quartz by LA-ICP-MS at the 1 µg/g level, relevant to quartz in HP-LT terranes. We suggest that natural quartz such as the homogeneous low-CL rims of the Bishop Tuff quartz are more suitable than NIST reference glasses as an in-house reference material for low Ti concentrations because matrix effects are limited and Ca isobaric interferences are avoided, thus allowing for the use of 48Ti as a normalizing mass. Titanium concentration from 33 analyses of low

  14. Quantitative 3-D Elemental Mapping by LA-ICP-MS of a Basaltic Clast from the Hanford 300 Area, Washington, USA

    SciTech Connect

    Sheng, Peng; Hu, Qinhong; Ewing, Robert P.; Liu, Chongxuan; Zachara, John M.

    2012-03-01

    Laser ablation with inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to measure elemental concentrations at the 100 {micro}m scale in a 3-dimensional manner in a basalt sample collected from the Hanford 300 Area in south-central Washington State. A modified calibration method was developed to quantify the LA-ICP-MS signal response using a constant-sum mass fraction of eight major elements; the method produced reasonable concentration measurements for both major and trace elements when compared to a standard basalt sample with known concentrations. 3-dimensional maps (stacked 2-D contour layers, each measuring 2100 {micro}m x 2100 {micro}m) show relatively uniform concentration with depth for intrinsic elements such as Si, Na, and Sr. However, U and Cu accumulation were observed near the rock surface, consistent with the site's release history of these pollutants. U and Cu show substantial heterogeneity in their concentration distributions in horizontal slices, while the intrinsic elements are essentially uniformly distributed. From measured U concentrations of this work and reported mass fractions, cobbles and gravels were estimated to contain from 0.6% to 7.5% of the contaminant U, implicating the coarse fraction as a long-term release source.

  15. Elemental bioimaging in kidney by LA-ICP-MS as a tool to study nephrotoxicity and renal protective strategies in cisplatin therapies.

    PubMed

    Moreno-Gordaliza, Estefanía; Giesen, Charlotte; Lázaro, Alberto; Esteban-Fernández, Diego; Humanes, Blanca; Cañas, Benito; Panne, Ulrich; Tejedor, Alberto; Jakubowski, Norbert; Gómez-Gómez, M Milagros

    2011-10-15

    A laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)-based methodology is presented for Pt, Cu, and Zn bioimaging on whole kidney 3 μm sagittal sections from rats treated with pharmacological doses of cisplatin, which were sacrificed once renal damage had taken place. Pt turned out to accumulate in the kidney cortex and corticomedullary junction, corresponding to areas where the proximal tubule S3 segments (the most sensitive cells to cisplatin nephrotoxicity) are located. This demonstrates the connection between platinum accumulation and renal damage proved by histological examination of HE-stained sections and evaluation of serum and urine biochemical parameters. Cu and Zn distribution maps revealed a significant displacement in cells by Pt, as compared to control tissues. A dramatic decrease in the Pt accumulation in the cortex was observed when cilastatin was coadministered with cisplatin, which can be related to its nephroprotective effect. Excellent imaging reproducibility, sensitivity (LOD 50 fg), and resolution (down to 8 μm) were achieved, demonstrating that LA-ICP-MS can be applied as a microscopic metal detector at cellular level in certain tissues. A simple and quick approach for the estimation of Pt tissue levels was proposed, based on tissue spiking.

  16. Printing metal-spiked inks for LA-ICP-MS bioimaging internal standardization: comparison of the different nephrotoxic behavior of cisplatin, carboplatin, and oxaliplatin.

    PubMed

    Moraleja, Irene; Esteban-Fernández, Diego; Lázaro, Alberto; Humanes, Blanca; Neumann, Boris; Tejedor, Alberto; Luz Mena, M; Jakubowski, Norbert; Gómez-Gómez, M Milagros

    2016-03-01

    The study of the distribution of the cytostatic drugs cisplatin, carboplatin, and oxaliplatin along the kidney may help to understand their different nephrotoxic behavior. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) allows the acquisition of trace element images in biological tissues. However, results obtained are affected by several variations concerning the sample matrix and instrumental drifts. In this work, an internal standardization method based on printing an Ir-spiked ink onto the surface of the sample has been developed to evaluate the different distributions and accumulation levels of the aforementioned drugs along the kidney of a rat model. A conventional ink-jet printer was used to print fresh sagittal kidney tissue slices of 4 μm. A reproducible and homogenous deposition of the ink along the tissue was observed. The ink was partially absorbed on top of the tissue. Thus, this approach provides a pseudo-internal standardization, due to the fact that the ablation sample and internal standard take place subsequently and not simultaneously. A satisfactory normalization of LA-ICP-MS bioimages and therefore a reliable comparison of the kidney treated with different Pt-based drugs were achieved even for tissues analyzed on different days. Due to the complete ablation of the sample, the transport of the ablated internal standard and tissue to the inductively coupled plasma-mass spectrometry (ICP-MS) is practically taking place at the same time. Pt accumulation in the kidney was observed in accordance to the dosages administered for each drug. Although the accumulation rate of cisplatin and oxaliplatin is high in both cases, their Pt distributions differ. The strong nephrotoxicity observed for cisplatin and the absence of such side effect in the case of oxaliplatin could explain these distribution differences. The homogeneous distribution of oxaliplatin in the cortical and medullar areas could be related with its higher affinity for

  17. High-Precision Measurement of Eu/Eu* in Geological Glasses via LA-ICP-MS Analysis

    NASA Technical Reports Server (NTRS)

    Tang, Ming; McDonough, William F.; Arevalo, Ricardo, Jr.

    2014-01-01

    Elemental fractionation during laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis has been historically documented between refractory and volatile elements. In this work, however, we observed fractionation between light rare earth elements (LREEs) and heavy rare earth elements (HREEs) when using ablation strategies involving large spot sizes (greater than 100 millimeters) and line scanning mode. In addition: (1) ion yields decrease when using spot sizes above 100 millimeters; (2) (Eu/Eu*)(sub raw) (i.e. Europium anomaly) positively correlates with carrier gas (He) flow rate, which provides control over the particle size distribution of the aerosol reaching the ICP; (3) (Eu/Eu*)(sub raw) shows a positive correlation with spot size, and (4) the changes in REE signal intensity, induced by the He flow rate change, roughly correlate with REE condensation temperatures. The REE fractionation is likely driven by the slight but significant difference in their condensation temperatures. Large particles may not be completely dissociated in the ICP and result in preferential evaporation of the less refractory LREEs and thus non-stoichiometric particle-ion conversion. This mechanism may also be responsible for Sm-Eu-Gd fractionation as Eu is less refractory than Sm and Gd. The extent of fractionation depends upon the particle size distribution of the aerosol, which in turn is influenced by the laser parameters and matrix. Ablation pits and lines defined by low aspect ratios produce a higher proportion of large particles than high aspect ratio ablation, as confirmed by measurements of particle size distribution in the laser induced aerosol. Therefore, low aspect ratio ablation introduces particles that cannot be decomposed and/or atomized by the ICP and thus results in exacerbated elemental fractionation. Accurate quantification of REE concentrations and Eu/Eu* requires reduction of large particle production during laser ablation. For the reference

  18. Refining LA-ICP-MS techniques for the exploration of ultra-thin layers in Alpine and Polar ice

    NASA Astrophysics Data System (ADS)

    Spaulding, Nicole; Bohleber, Pascal; Mayewski, Paul; Wagenbach, Dietmar; Kurbatov, Andrei; Sneed, Sharon; Handley, Mike; Erhardt, Tobias

    2015-04-01

    Laser ablation inductively coupled plasma mass spectrometry, (LA)-ICP-MS, offers minimally destructive ice core impurity analysis at unsurpassed sub-mm depth resolution. As such it is uniquely suited for exploring the closely spaced layers of ice cores collected in low accumulation sites or in regions of compressed and thinned ice. Here we present an updated characterization of the LA system developed at the University of Maine Climate Change Institute's Keck Laser Ice Facility, as determined through 1) experimentation with sticks of frozen distilled water and 2) exploitation of the exceptionally thin layers within a new ice core drilled at the Alpine glacier saddle Colle Gnifetti (4450m asl, Monte Rosa, Swiss-Italian Alps) and the variety of high-density chemical data collected from it. Colle Gnifetti (CG) is characterized by low net accumulation rates and strong vertical shear, which causes its annual layers to rapidly thin below the cm-resolution of conventional ice core analysis techniques. To best utilize its unique archive, LA measurements of Ca and Na were directly compared to those from continuous flow analysis. Through this comparison, we demonstrate that LA captures low frequency trends similar to traditional melting techniques while also emphasizing the benefits of its increased resolution. The resolution was itself verified through experimental determination of peak decay times, where peaks were created by spiking frozen distilled water at known interval with high concentration riverine water standards. Using ion chromatography and liquid-based ICP-MS measurements of discrete meltwater samples from CG we were also able to explore high-resolution profiles of S as measured by LA. The ability to resolve S at sub-mm resolution (a capability not yet demonstrated for LA analysis of ice cores) may allow more accurate determination of the character and timing of volcanic eruptions. We illustrate this finding using an exemplary S-anomaly, potentially of volcanic

  19. Allanite from the El Muerto Pegmatite, Oaxaca, Mexico: A Potential New Standard for 232Th-208Pb Dating by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Price, J.; Crowley, J. L.; Solari, L.; Prol-Ledesma, R.

    2012-12-01

    Allanite dating may be important to studies addressing tectonomagmatic evolution, provenance of monocyclic sediment, and mineral weathering. Obtaining accurate allanite ages by SIMS has been challenging and time-consuming due to the mineral's extreme chemical variability which often prevents finding adequately matrix-matched standards. Isotopic measurements by LA-ICP-MS minimize the need for standards of nearly identical composition to the unknown allanite being analyzed, and it is done relatively rapidly. Dating by LA-ICP-MS requires high quality standards for isotopic fractionation corrections. However, readily accessible and well characterized allanite standards are scarce. We investigated gemstone allanite from the El Muerto pegmatite, Oaxaca, Mexico, as a potential new geochronology standard for 232Th-208Pb allanite dating by LA-ICP-MS. Compositional homogeneity was thoroughly investigated by scanning and backscatter electron microscopy, cathodoluminescence, quantitative and qualitative energy dispersive x-ray spectroscopy, electron microprobe, and LA-ICP-MS. The possibility of metamictization was investigated by extensive X-ray diffraction analyses. The El Muerto allanite was U-Pb dated by ID-TIMS, with common Pb ratios determined from cogenetic K-feldspar by ID-TIMS and LA-MC-ICP-MS. Future work includes Th-Pb dating by ID-TIMS. The samples investigated are homogeneous with respect to major and trace elements. Major element compositional results are generally in agreement with published values, and no metamictization was identified despite the allanite being nearly 1 Ga. The only limitation of the El Muerto allanite is that it contains small, generally <100 μm, scarce inclusions of quartz, calciothorite, albite, calcite, and biotite. However, these grains are easily recognized and avoided during LA-ICP-MS analyses. Based on these results, the El Muerto allanite has the potential to serve as a standard for LA-ICP-MS dating.

  20. In-situ Cl/Br measurements in scapolite and fluid inclusions by LA-ICP-MS: A powerful tool to constrain fluid sources

    NASA Astrophysics Data System (ADS)

    Hammerli, J.; Rusk, B.; Spandler, C.; Oliver, N. H. S.; Emsbo, P.

    2012-04-01

    Chlorine and bromine are highly conservative elements, and are therefore widely used to trace the origin of fluids in sedimentary and hydrothermal/magmatic systems (e.g. Hanor & McIntosh, 2007; Nahnybida et al., 2009). Halogens are important ligands for metal transport in hydrothermal solutions and thus their behavior in hydrothermal environments is crucial for comprehending ore-forming processes. Besides fluid inclusions, scapolite-group minerals hold great potential as a tracer of igneous, metamorphic, and hydrothermal processes, as no Cl/Br fractionation in scapolite has been observed and therefore halogen ratios in scapolite are thought to mirror the halogen ratios in coexisting melts and fluids (Pan & Dong, 2003). Hence, Cl/Br ratios in fluid inclusions and minerals can be utilized to trace the origin of fluids and fluid-rock interaction pathways. Due to their high ionization energies, bromine and chlorine are not routinely measured by LA-ICP-MS and suitable standards are rare. Little is known about the potential interferences and analytical limitations of in-situ chlorine and bromine analysis by LA-ICP-MS. Nevertheless, Seo et al. (2011) showed that quantification of Br and Cl in single synthetic and natural fluid inclusions is possible. In this study, we have analyzed several scapolite grains of known bromine and chlorine concentrations by LA-ICP-MS and assess the capabilities and limitations of this method. The results show that Cl/Br ratios measured by LA-ICP-MS closely reproduce known values determined by microprobe (Cl), the Noble Gas Method (Br) and INAA (Br) (Kendrick, 2011; Lieftink et al., 1993) using laser ablation spot sizes from 24-120 μm. The well-characterized scapolite grains cover bromine concentrations from 50-883 ppm and chlorine concentrations from 3 to 4 wt.%. In order to further assess the method, we analyzed Cl/Br ratios in natural fluid inclusions hosted in sphalerite that were previously characterized by crush and leach ion

  1. Developing a Correction to Remove Systematic Bias in U-Pb LA-ICP-MS Zircon Ages Related to Zircon "Matrix Effects"

    NASA Astrophysics Data System (ADS)

    Matthews, W. A.; Angelo, T. V.; Guest, B.

    2014-12-01

    For more than a decade the occurrence of systematic discrepancies between the U-Pb ages of zircons determined by LA-ICP-MS and ID-TIMS has been acknowledged. Trace element concentrations, crystallographic orientation and damage to the crystal lattice by radioactive decay have all been cited as possible causes for the discrepancy termed the "matrix effect". Recent studies have concluded that differences in Laser Induced Elemental Fractionation (LIEF) between zircon reference materials results from variations in the ablation rate between the primary reference, which is used to build a model for LIEF during data reduction, and the unknowns. These variations are likely related to physical differences in the crystal lattice caused by alpha particle ejection. We tested this hypothesis by measuring the ablation rate for ~200 individual ablation pits in a variety of reference materials using an optical profilometer. Our data demonstrate a clear relationship between delta age (the difference between the age calculated by LA-ICP-MS and the accepted ID-TIMS age, expressed as a percentage) and ablation rate. The relationship between calculated alpha dosage for each ablation and delta age is less clear. This suggests that the zircon's thermal history may play an important role in controlling ablation rate through annealing of crystal lattice defects. However, alpha dosage is readily quantifiable during routine zircon U-Pb analyses and therefore its relationship to delta age may provide a useful first order correction to remove systematic biases from U-Pb ages. Raman spectroscopy could provide a more robust measure of radiation damage in the zircon lattice and could help to refine our understanding of the processes involved.

  2. Au-Skarn Mineralization: Constraints from LA-ICP-MS U-Pb Zircon Dating

    NASA Astrophysics Data System (ADS)

    Gaspar, M.; Vervoort, J. D.; Meinert, L. D.

    2003-12-01

    In situ U-Pb zircon geochronology by laser ablation ICP-MS was performed on samples from the intrusive rocks of the Buckhorn Mountain, Washington in order to constrain the age of the Crown Jewel Au-skarn deposit. The analyses were conducted at Washington State University using a ThermoFinnigan Element2 single collector, high resolution magnetic sector ICP-MS, and a New Wave UP 213 Nd-YAG (213 nm) laser ablation system. The analytical parameters included a repetition rate of 10 Hz, a 40 microns spot size, and a total analysis time of 30 seconds per spot. A 94-35 cascade standard was used to bracket the samples. Two distinct 206Pb/238 U ages were obtained, 52.3 Ma +/- 1.6, 165.0 Ma +/- 5.9, 163.4 +/- 5.7, and 169.8 +/- 12.1 (all errors are 2 sigma). These ages represent distinct magmatic events occuring during the two main tectonic periods in the region. The oldest age ( ˜165 Ma) is associated with the accretion of the Quesnel terrain during the Middle Jurassic while the younger age ( ˜52 Ma) represents the magmatism during the Eocene extension that is well represented by the Challis Volcanics in the vicinity. The Jurassic ages were obtained in one sample from a deformed granodiorite dike and two samples from the main granodiorite intrusive facies that, based on the skarn mineralogy zonation, is spatially associated with the skarn. The Eocene intrusive unit was intercepted in one drill core but is clearly distinct from the granodiorites both geochemically and mineralogically. This facies is more an adamellite, with a distinctive pinkish colour due to a K-spar alteration. It is higher in silica, and depleted in compatible elements (Ca, Fe, Ti, Mg, P, Y, and V) relative to the granodiorite. Geochemically the granodiorite has a composition typical of plutons associated with Au-skarns worldwide. Because Au mineralization is erratically distributed and does not correlate with any of the skarn mineralogy, a question can be raised. Does the Au mineralization have any

  3. In situ quantification of Br and Cl in minerals and fluid inclusions by LA-ICP-MS: a powerful tool to identify fluid sources

    USGS Publications Warehouse

    Hammerli, Johannes; Rusk, Brian; Spandler, Carl; Emsbo, Poul; Oliver, Nicholas H.S.

    2013-01-01

    Bromine and chlorine are important halogens for fluid source identification in the Earth's crust, but until recently we lacked routine analytical techniques to determine the concentration of these elements in situ on a micrometer scale in minerals and fluid inclusions. In this study, we evaluate the potential of in situ Cl and Br measurements by LA-ICP-MS through analysis of a range of scapolite grains with known Cl and Br concentrations. We assess the effects of varying spot sizes, variable plasma energy and resolve the contribution of polyatomic interferences on Br measurements. Using well-characterised natural scapolite standards, we show that LA-ICP-MS analysis allows measurement of Br and Cl concentrations in scapolite, and fluid inclusions as small as 16 μm in diameter and potentially in sodalite and a variety of other minerals, such as apatite, biotite, and amphibole. As a demonstration of the accuracy and potential of Cl and Br analyses by LA-ICP-MS, we analysed natural fluid inclusions hosted in sphalerite and compared them to crush and leach ion chromatography Cl/Br analyses. Limit of detection for Br is ~8 μg g−1, whereas relatively high Cl concentrations (> 500 μg g−1) are required for quantification by LA-ICP-MS. In general, our LA-ICP-MS fluid inclusion results agree well with ion chromatography (IC) data. Additionally, combined cathodoluminescence and LA-ICP-MS analyses on natural scapolites within a well-studied regional metamorphic suite in South Australia demonstrate that Cl and Br can be quantified with a ~25 μm resolution in natural minerals. This technique can be applied to resolve a range of hydrothermal geology problems, including determining the origins of ore forming brines and ore deposition processes, mapping metamorphic and hydrothermal fluid provinces and pathways, and constraining the effects of fluid–rock reactions and fluid mixing.

  4. Quantification of Al2O3 nanoparticles in human cell lines applying inductively coupled plasma mass spectrometry (neb-ICP-MS, LA-ICP-MS) and flow cytometry-based methods.

    PubMed

    Böhme, Steffi; Stärk, Hans-Joachim; Meißner, Tobias; Springer, Armin; Reemtsma, Thorsten; Kühnel, Dana; Busch, Wibke

    2014-01-01

    In order to quantify and compare the uptake of aluminum oxide nanoparticles of three different sizes into two human cell lines (skin keratinocytes (HaCaT) and lung epithelial cells (A549)), three analytical methods were applied: digestion followed by nebulization inductively coupled plasma mass spectrometry (neb-ICP-MS), direct laser ablation ICP-MS (LA-ICP-MS), and flow cytometry. Light and electron microscopy revealed an accumulation and agglomeration of all particle types within the cell cytoplasm, whereas no particles were detected in the cell nuclei. The internalized Al2O3 particles exerted no toxicity in the two cell lines after 24 h of exposure. The smallest particles with a primary particle size (xBET) of 14 nm (Alu1) showed the lowest sedimentation velocity within the cell culture media, but were calculated to have settled completely after 20 h. Alu2 (xBET = 111 nm) and Alu3 (xBET = 750 nm) were calculated to reach the cell surface after 7 h and 3 min, respectively. The internal concentrations determined with the different methods lay in a comparable range of 2-8 µg Al2O3/cm(2) cell layer, indicating the suitability of all methods to quantify the nanoparticle uptake. Nevertheless, particle size limitations of analytical methods using optical devices were demonstrated for LA-ICP-MS and flow cytometry. Furthermore, the consideration and comparison of particle properties as parameters for particle internalization revealed the particle size and the exposure concentration as determining factors for particle uptake.

  5. LA-ICP/MS Analysis of Plastics as a Method to Support Polymer Assay in the Assessment of Materials for Low Background Detectors

    SciTech Connect

    Grate, Jay W.; Bliss, Mary; Farmer, Orville T.; Thomas, Linda MP; Liezers, Martin

    2016-03-12

    Ultra low-background radiation measurements are essential to several large-scale physics investigations, such as those involving neutrinoless double-beta decay, dark matter detection (such as SuperCDMS), and solar neutrino detection. There is a need for electrically and thermally insulating dielectric materials with extremely low-background radioactivity for detector construction. This need is best met with plastics. Most currently available structural plastics have milliBecquerel-per-kilogram total intrinsic radioactivity. Modern low-level detection systems require a large variety of plastics with low microBecquerel-per-kilogram levels. However, the assay of polymer materials for extremely low levels of radioactive elements, uranium and thorium in particular, presents new challenges. It is only recently that any certified reference materials (CRMs) for toxic metals such as lead or cadmium in plastics have become available. However, there are no CRMs for uranium or thorium in thermoplastics. This paper discusses our assessment of the use of laser ablation (LA) for sampling and inductively coupled plasma mass spectrometry (ICP-MS) for analysis of polyethylene (PE) samples, with an emphasis on uranium determination. Using a CRM for lead in PE, we examine LA and ICP-MS parameters that determine whether the total atom efficiencies for uranium and lead are similar, and explore methods to use the lead content in a plastic as part of the process of estimating or determining the uranium content by LA-ICP-MS.

  6. Trace element profiles in modern horse molar enamel as tracers of seasonality: Evidence from micro-XRF, LA-ICP-MS and stable isotope analysis

    NASA Astrophysics Data System (ADS)

    de Winter, Niels; Goderis, Steven; van Malderen, Stijn; Vanhaecke, Frank; Claeys, Philippe

    2016-04-01

    A combination of laboratory micro-X-ray Fluorescence (μXRF) and stable carbon and oxygen isotope analysis shows that trace element profiles from modern horse molars reveal a seasonal pattern that co-varies with seasonality in the oxygen isotope records of enamel carbonate from the same teeth. A combination of six cheek teeth (premolars and molars) from the same individual yields a seasonal isotope and trace element record of approximately three years recorded during the growth of the molars. This record shows that reproducible measurements of various trace element ratios (e.g., Sr/Ca, Zn/Ca, Fe/Ca, K/Ca and S/Ca) lag the seasonal pattern in oxygen isotope records by 2-3 months. Laser Ablation-ICP-Mass Spectrometry (LA-ICP-MS) analysis on a cross-section of the first molar of the same individual is compared to the bench-top tube-excitation μXRF results to test the robustness of the measurements and to compare both methods. Furthermore, trace element (e.g. Sr, Zn, Mg & Ba) profiles perpendicular to the growth direction of the same tooth, as well as profiles parallel to the growth direction are measured with LA-ICP-MS and μXRF to study the internal distribution of trace element ratios in two dimensions. Results of this extensive complementary line-scanning procedure shows the robustness of state of the art laboratory micro-XRF scanning for the measurement of trace elements in bioapatite. The comparison highlights the advantages and disadvantages of both methods for trace element analysis and illustrates their complementarity. Results of internal variation within the teeth shed light on the origins of trace elements in mammal teeth and their potential use for paleo-environmental reconstruction.

  7. LA-ICP-MS analysis of isolated phosphatic grains indicates selective rare earth element enrichment during reworking and transport processes

    NASA Astrophysics Data System (ADS)

    Auer, Gerald; Reuter, Markus; Hauzenberger, Christoph A.; Piller, Werner E.

    2016-04-01

    Rare earth elements (REE) are a commonly used proxy to reconstruct water chemistry and oxygen saturation during the formation history of authigenic and biogenic phosphates in marine environments. In the modern ocean REE exhibit a distinct pattern with enrichment of heavy REE and strong depletion in Cerium. Studies of ancient phosphates and carbonates, however, showed that this 'modern' pattern is only rarely present in the geological past. Consequently, the wide range of REE enrichment patterns found in ancient marine phosphates lead to the proposition that water chemistry had to have been radically different in the earth's past. A wealth of studies has already shown that both early and late diagenesis can strongly affect REE signatures in phosphates and severely alter primary marine signals. However, no previous research was conducted on how alteration processes occurring prior to final deposition affect marine phosphates. Herein we present a dataset of multiple LA-ICP-MS measurements of REE signatures in isolated phosphate and carbonate grains deposited in a carbonate ramp setting in the central Mediterranean Sea during the middle Miocene "Monterey event". The phosphates are represented by authigenic, biogenic and detrital grains emplaced in bioclastic grain- to packstones dominated by bryozoan and echinoderm fragments, as well as abundant benthic and planktic foraminifers. The results of 39 grain specific LA-ICP-MS measurements in three discrete rock samples reveals four markedly different REE patterns (normalized to the Post Archean Australian Shale standard) in terms of total enrichment and pattern shape. Analyses of REE diagenesis proxies show that diagenetic alteration affected the samples only to a minor degree. Considering grain shape and REE patterns together indicate that authigenic, detrital and biogenic phosphates have distinct REE patterns irrespective of the sample. Our results show that the observed REE patterns in phosphates only broadly reflect

  8. Trace elements in pyrite from the Petropavlovsk gold-porphyry deposit (Polar Urals): Results of LA-ICP-MS analysis

    NASA Astrophysics Data System (ADS)

    Vikentiev, I. V.; Abramova, V. D.; Ivanova, Yu. N.; Tyukova, E. E.; Kovalchuk, E. V.; Bortnikov, N. S.

    2016-09-01

    The first study of the pyrite composition from gold deposit in the Urals by the LA-ICP-MS method has been carried out. In the pyrite high contents of Au (up to 49 ppm), Ag (105 ppm), and other micronutrients (As (417 ppm), Ag (105 ppm), Co (2825 ppm), Ni (75 ppm), Cu (1442 ppm), and Zn (19 ppm)) were detected. Furthermore, an increase in the concentrations of trace elements from early to later generations of pyrite (from Py-1 to Py-3) Au, Ag, Te, Sn, Te, and Bi and depletion of Co, As, and Ni have been revealed. Gold is mainly concentrated in the pyrite of the second generation (Py-2) and occurs mostly as an "invisible" form with prevalence of nano-sized particles of native Au, similar in composition to electrum AuAg, as well as Au- and Au-Ag tellurides. The presence in the pyrite of admixtures of Cu, Co, Ni, Pb, As, and Te, possibly favors the entrance of Au into it (up to 5-50 ppm), while in common pyrite, poor in the mentioned impurities, the gold content is <1 ppm.

  9. Coupling of Uranium and Thorium Series Isotope Systematics for Age Determination of Late Pleistocene Zircons using LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Sakata, S.; Hirakawa, S.; Iwano, H.; Danhara, T.; Hirata, T.

    2014-12-01

    Zircon U-Th-Pb dating method is one of the most important tools for estimating the duration of magmatism by means of coupling of uranium, actinium and thorium decay series. Using U-Pb dating method, its reliability is principally guaranteed by the concordance between 238U-206Pb and 235U-207Pb ages. In case of dating Quaternary zircons, however, the initial disequilibrium effect on 230Th and 231Pa should be considered. On the other hands, 232Th-208Pb dating method can be a simple but powerful approach for investigating the age of crystallization because of negligible influence from initial disequilibrium effect. We have developed a new correction model for accurate U-Pb dating of the young zircon samples by taking into consideration of initial disequilibrium and a U-Pb vs Th-Pb concordia diagram for reliable age calibration was successfully established. Hence, the U-Th-Pb dating method can be applied to various zircons ranging from Hadean (4,600 Ma) to Quaternary (~50 ka) ages, and this suggests that further detailed information concerning the thermal history of the geological sequences can be made by the coupling of U-Th-Pb, fission track and Ar-Ar ages. In this presentation, we will show an example of U-Th-Pb dating for zircon samples from Sambe Volcano (3 to 100 ka), southwest Japan and the present dating technique using LA-ICP-MS.

  10. Impact history of the Chelyabinsk meteorite: Electron microprobe and LA-ICP-MS study of sulfides and metals

    NASA Astrophysics Data System (ADS)

    Andronikov, A. V.; Andronikova, I. E.; Hill, D. H.

    2015-12-01

    Electron microprobe and LA-ICP-MS study of sulfides and metals from two fragments of the LL5 Chelyabinsk meteorite were conducted. The fragments are impact breccias, one fragment contains both chondritic and shock vein lithologies, and the other contains shock-darkened chondritic clasts and vesicular impact melts. The chondritic lithology and shock veins display very similar opaque mineral compositions. The mineral compositions in the impact-melt breccias are distinctly different. The brecciated state of the Chelyabinsk meteorite suggests strong involvement of shock-related processes during the evolution of the parent body. Multiple heavy impact events occurred on the parent asteroid and on the Chelyabinsk meteoroid itself over the time period from ca. 4.5 Ga until ca. 1.2 Ma. The shock veins were produced in situ on the parent body. The impact-melt breccias could have formed because of the dramatic impact to the parent LL-chondrite body that could be partly disintegrated. The fragment containing shock-darkened chondritic clasts and vesicular impact melt lithologies preserves a record of melting, volatilization, partial degassing, and quenching of the molten material. The abundance and size (up to 1 mm) of the vesicles suggest that the impact melt must have been buried at some depth after formation. After impact and subsequent melting occurred, the impact-induced pressure on the shallow asteroid interior was released that caused "boiling" of volatiles and generation of S-rich bubbles. Such an impact excavated down to depths of the body generating multiple fragments with complicated histories. These fragments reaccumulated into a gravitational aggregate and formed the parental meteoroid for the Chelyabinsk meteorite.

  11. In situ U-Pb rutile dating by LA-ICP-MS: 208Pb correction and prospects for geological applications

    NASA Astrophysics Data System (ADS)

    Zack, Thomas; Stockli, Daniel F.; Luvizotto, George L.; Barth, Matthias G.; Belousova, Elena; Wolfe, Melissa R.; Hinton, Richard W.

    2011-09-01

    Rutile is a common accessory mineral that occurs in a wide spectrum of metamorphic rocks, such as in blueschists, eclogites, and granulites and as one of the most stable detrital heavy minerals in sedimentary rocks. The advent of rutile trace element thermometry has generated increased interest in a better understanding of rutile formation. This study documents important analytical advances in in situ LA-ICP-MS U/Pb geochronology of rutile: (1) Matrix matching, necessary for robust in situ dating is fulfilled by calibrating and testing several rutile standards (R10, R19, WH-1), including the presentation of new TIMS ages for the rutile standard R19 (489.5 ± 0.9 Ma; errors always stated as 2 s). (2) Initial common lead correction is routinely applied via 208Pb, which is possible due to extremely low Th/U ratios (usually <0.003) in most rutiles. Employing a 213 nm Nd:YAG laser coupled to a quadrupole ICP-MS and using R10 as a primary standard, rutile U/Pb concordia ages for the two other rutile standards (493 ± 10 Ma for R19; 2640 ± 50 Ma for WH-1) and four rutile-bearing metamorphic rocks (181 ± 4 Ma for Ivrea metapelitic granulite; 339 ± 7 Ma for Saidenbach coesite eclogite; 386 ± 8 Ma for Fjortoft UHP metapelite; 606 ± 12 Ma for Andrelandia metepelitic granulite) always agree within 2% with the reported TIMS ages and other dating studies from the same localities. The power of in situ U/Pb rutile dating is illustrated by comparing ages of detrital rutile and zircon from a recent sediment from the Christie Domain of the Gawler Craton, Australia. While the U/Pb age spectrum from zircons show several pronounced peaks that are correlated with magmatic episodes, rutile U/Pb ages are marked by only one pronounced peak (at ca 1,675 Ma) interpreted to represent cooling ages of this part of the craton. Rutile thermometry of the same detrital grains indicates former granulite-facies conditions. The methods outlined in this paper should find wide application in studies

  12. Investigating Compositional Variation of Ceramic Materials during the Late Neolithic on the Great Hungarian Plain - Preliminary LA-ICP-MS Results

    NASA Astrophysics Data System (ADS)

    Riebe, Danielle J.; Niziolek, Lisa C.

    2015-10-01

    Investigations have been undertaken to assess the extent to which compositional analysis can be used to determine trade and interaction on the Great Hungarian Plain during the Late Neolithic. Ceramic and clay samples in the Körös and Berettyó River Basins were analyzed at the Elemental Analysis Facilities (EAF) at The Field Museum of Natural History in Chicago, IL, USA. With the use of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), the aim of the project was to ascertain if micro-regional or site-specific compositional signatures could be determined in a region that is typically characterized as highly geologically homogenous. Identifying site-specific signatures enables archaeologists to model prehistoric interactions and, in turn, determine the relationship between interaction and various socio-cultural changes. This paper focuses on the preliminary compositional results of materials analyzed from three different sites across the Plain and the methodological implications for future anthropological research in the region.

  13. In situ LA-ICP-MS and EPMA trace element characterization of Fe-Ti oxides from the phoscorite-carbonatite association at Phalaborwa, South Africa

    NASA Astrophysics Data System (ADS)

    Milani, Lorenzo; Bolhar, Robert; Cawthorn, R. Grant; Frei, Dirk

    2016-11-01

    In situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and electron probe microanalysis (EPMA) are used to characterize magnetite and ilmenite of the phoscorite-carbonatite association at Phalaborwa. We trace the behavior of the compatible elements for two different generations of magnetite related to (1) a magmatic stage, with variable Ti-V content, which pre-dates the copper mineralization, and (2) a late hydrothermal, low-Ti, low-temperature event, mostly post-dating sulfide formation. Magnetite is shown to be a robust petrogenetic indicator; no influence on its chemical composition is detected from the intergrowth with the accompanying phases, including the interaction with coexisting sulfides. High spatial resolution EPMA characterize the tiny late-stage hydrothermal magnetite veins, as well as the ilmenite granular and lamellar exsolutions mostly developed in the magnetite from the phoscorite. By combining geochemical data with geothermo-oxybarometry calculations for magnetite-ilmenite pairs, we infer that the most primitive magnetite probably formed at oxygen fugacity above the nickel nickel oxide (NNO) buffer, revealing an evolutionary trend of decreasing temperature and oxygen fugacity. Geochemical similarity exists between magnetite from phoscorite and carbonatite, thus supporting a common mantle source for the phoscorite-carbonatite association.

  14. Rediscovering the palette of Alentejo (Southern Portugal) earth pigments: provenance establishment and characterization by LA-ICP-MS and spectra-colorimetric analysis

    NASA Astrophysics Data System (ADS)

    Gil, M.; Green, R.; Carvalho, M. L.; Seruya, A.; Queralt, I.; Candeias, A. E.; Mirão, J.

    2009-09-01

    Colored earth pigments sourced from Alentejo, Portugal, can be geologically categorized as either weathered carbonate rocks (terra rossas), schist units, or weathered iron ore deposits. The material was used until the mid-1900s by local residents as an ingredient in their traditional lime wash paintings and possibly in the production of artistic murals across the Alentejo region since pre-historic times. An integrated methodology incorporating laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and spectra-colorimetric analysis (CIELAB coordinates and reflectance curves), complemented by XRD, WDXRF, SEM-EDX, optical microscopy, and granulometric analysis, was used to characterize thirty-one Alentejo colored earths in an effort to correlate provenance with pigments properties. Data obtained from elemental analysis (major and trace) revealed a generic and similar elemental “fingerprint” that unable their distinction according to geographic provenance. Samples of weathered iron ore deposits derived from explored iron, copper, and sulfur mines are more easily discriminated using the chalcophilic (“sulfur-loving“) elements. Color analysis revealed a range of hues; olive-yellow to dark reddish-brown owing mainly to differences in the type and proportion of the color component present, independent of the accessory mineral.

  15. REE in skarn systems: A LA-ICP-MS study of garnets from the Crown Jewel gold deposit

    NASA Astrophysics Data System (ADS)

    Gaspar, Miguel; Knaack, Charles; Meinert, Lawrence D.; Moretti, Roberto

    2008-01-01

    Metamorphic and magmatic garnets are known to fractionate REE, with generally HREE-enriched patterns, and high Lu/Hf and Sm/Nd ratios, making them very useful as geochemical tracers and in geochronological studies. However, these garnets are typically Al-rich (pyrope, almandine, spessartine, and grossular) and little is known about garnets with a more andraditic (Fe 3+) composition, as frequently found in skarn systems. This paper presents LA-ICP-MS data for garnets from the Crown Jewel Au-skarn deposit (USA), discusses the factors controlling incorporation of REE into garnets, and strengthens the potential of garnet REE geochemistry as a tool to help understand the evolution of metasomatic fluids. Garnets from the Crown Jewel deposit range from Adr 30Grs 70 to almost pure andradite (Adr >99). Fe-rich garnets (Adr >90) are isotropic, whereas Al-rich garnets deviate from cubic symmetry and are anisotropic, often showing sectorial dodecahedral twinning. All garnets are extremely LILE-depleted, Ta, Hf, and Th and reveal a positive correlation of ΣREE 3+ with Al content. The Al-rich garnets are relatively enriched in Y, Zr, and Sc and show "typical" HREE-enriched and LREE-depleted patterns with small Eu anomalies. Fe-rich garnets (Adr >90) have much lower ΣREE and exhibit LREE-enriched and HREE-depleted patterns, with a strong positive Eu anomaly. Incorporation of REE into garnet is in part controlled by its crystal chemistry, with REE 3+ following a coupled, YAG-type substitution mechanism ([X]-1VIII[REE]+1VIII[Si]-1IV[Z]+1IV), whereas Eu 2+ substitutes for X 2+ cations. Thermodynamic data (e.g., Hmixing) in grossular-andradite mixtures suggest preferential incorporation of HREE in grossular and LREE in more andraditic compositions. Variations in textural and optical features and in garnet geochemistry are largely controlled by external factors, such as fluid composition, W/ R ratios, mineral growth kinetics, and metasomatism dynamics, suggesting an overall system

  16. Quantitative lead determination in coating paint on children's outwear by LA-ICP-MS: a practical calibration strategy for solid samples.

    PubMed

    Mercan, Selda; Ellez, Sevinç Zeynep; Türkmen, Zeynep; Yayla, Murat; Cengiz, Salih

    2015-01-01

    Lead is a hazardous compound that affects the central nervous system in people, particularly children, and may cause some reversible and irreversible diseases. Legal regulations try to prevent the exposure from products especially produced for children such as coating paints, jewelry, toys, bed linen, textile, etc. The aim of this study was to determine the lead levels of coating paints on children׳s outwear selling in district bazaar by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and to specify the percent of non-complying samples. Here we described the solid matrix calibration method and confirmed the results with the microwave-assisted acid digestion method. Both comparative methods were validated by analysis of the certified reference materials (NIST SRM-612 glass matrix, NIST SRM-2582 powdered paint and ERM-EC681k) and bias% for accuracy and RSD% for precision were calculated lower than 6.8% and 7.3%, respectively. The recovery ranges of laser ablation and microwave-assisted acid digestion method for Pb were found to be between 88.2-98.1% and 95.3-101.3%, respectively. The limits of detection values were determined as 0.162 mg kg(-1) for direct sampling in the ablation chamber and 0.002 ng mL(-1) for aqueous solutions. Correlation result of 16 samples (r=0.99) examined in both methods was satisfactory. In coating paint samples, 14.65% of 198 (n=29) did not comply with the 90 mg kg(-1) lead limit according to regulation. Validated quantitative laser ablation method may be preferred to quickly and reliably determine the Pb levels in other solid samples as well as coating paints.

  17. REE distribution in zircon from reference rocks of the Arctic region: Evidence from study by the LA-ICP-MS method

    NASA Astrophysics Data System (ADS)

    Nikolaev, A. I.; Drogobuzhskaya, S. V.; Bayanova, T. B.; Kaulina, T. V.; Lyalina, L. M.; Novikov, A. I.; Steshenko, E. N.

    2016-10-01

    The results of the LA-ICP-MS analysis of the concentrations of REEs, U, Th, and Hf in zircon from Paleo- and Neoarchean reference rocks of the Kola region (garnet-amphibole gneiss, basic and acid granulites, and granite pegmatite) are reported. A new methodology of the study of accessory zircons has been validated and modified. The accuracy of the results is confirmed by analysis of standard zircons Temora 1 and 91 500 and by comparison with the data obtained in other laboratories.

  18. LA-ICP-MS analysis of trace elements in glass spherules of the El'gygytgyn impact structure, Siberia

    NASA Astrophysics Data System (ADS)

    Adolph, Leonie; Deutsch, Alex

    2010-05-01

    The 3.58±0.04 Ma old El'gygytgyn impact structure (Central Chukotka, NE Siberia) with a diameter of 18 km (Gurov and Gurova 1979, Layer 2000) is one of only two terrestrial craters with a volcanic target; therefore, analysis of its target and impact lithologies is of basic interest for comparative planetology. Lake El'gygytgyn is a very valuable climate archive in the Arctic as it was neither covered by glaciers (Melles et al. 2007) nor has the lake ever fallen dry. Climate and impact research were the rationale for the ICDP drilling project that finished successfully in spring 2009. Impactites like melt rocks and breccias are rarely found in outcrops yet are present in the 80 m terrace of Lake El'gygytgyn (Gurov and Gurova 1979). Numerous investigations on petrography, shock metamorphism, and geochemistry of impactites from El'gygytgyn have been published so far (e.g. Gurov et al. 2007). We report the first trace element data for seven 30- to 760-μm-sized impact glass spherules that have been collected about10 km off the crater center from a terrace deposit of the Enmyvaam River outside the crater rim. The spherules are translucent with colors ranging from amber, dark brown to nearly black; they contain a few circular bubbles, schlieren, and very rarely mineral clasts and breccia fragments. Major elements were measured with the JEOL JXA 8600 MX Superprobe, 31 trace elements were analyzed with the Finnigan Element2 LA-ICP-MS with 5 Hz, 8-9 J/cm2 at with Si as internal, and NIST612 as external standard (Institut f. Mineralogie, WWU Münster). The spot size was 60 μm. All spherules show a very homogeneous major and trace element distribution yet clear differences exist between the samples in the SiO2 content (in weight percent) 53-68: four of the glasses are dacitic, two andesitic, and one basaltic-andesitic in composition. In addition, MgO (2.1-9.2), K2O (0.6-3.3), and (in ppm) Ni (317-1096), Co (25-79), Zr (100-169), Rb (18-107), and Ba (459-1092) display wide

  19. Trace-element study and uranium-lead dating of perovskite from the Afrikanda plutonic complex, Kola Peninsula (Russia) using LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Reguir, Ekaterina P.; Camacho, Alfredo; Yang, Panseok; Chakhmouradian, Anton R.; Kamenetsky, Vadim S.; Halden, Norman M.

    2010-11-01

    The U-Pb geochronology of perovskite is a powerful tool in constraining the emplacement age of silica-undersaturated rocks. The trace-element and U-Pb isotopic compositions of perovskite from clinopyroxenite and silicocarbonatite from the Afrikanda plutonic complex (Kola, Russia) were determined by laser-ablation inductively-coupled mass-spectrometry (LA-ICP-MS). In addition, the Sr isotopic composition of perovskite was measured by isotope-dilution mass-spectrometry to better constrain the relations between its host rocks. Perovskite from the two rock types shows a different degree of enrichment in Na, Mg, Mn, Pb, Fe, Al, V, rare-earth elements, Zr, Hf, Th, U and Ta. The perovskite 87Sr/86Sr values are within analytical uncertainty of one another and fall within the range of mantle values. The 206Pb/238U ages (corrected for common lead using 207Pb-method) of perovskite from silicocarbonatite statistically yield a single population with a weighted mean of 371 ± 8 Ma (2σ; MSWD = 0.071). This age is indistinguishable, within uncertainty, to the clinopyroxenite weighted mean 206Pb/238U age of 374 ± 10 Ma (2σ; MSWD = 0.18). Our data are in good agreement with the previous geochronological study of the Afrikanda complex. The observed variations in trace-element composition of perovskite from silicocarbonatite and clinopyroxenite indicate that these rocks are not related by crystal fractionation. The Sr isotopic ratios and the fact that the two rocks are coeval suggest that they were either produced from a single parental melt by liquid immiscibility, or from two separate magmas derived at different degrees of partial melting from an isotopically equilibrated, but modally complex mantle source.

  20. LA-ICP-MS heavy metal analyses of fish scales from sediments of the Oxbow Lake Certak of the Morava River (Czech Republic)

    NASA Astrophysics Data System (ADS)

    Holá, M.; Kalvoda, J.; Bábek, O.; Brzobohatý, R.; Holoubek, I.; Kanický, V.; Skoda, R.

    2009-07-01

    Heavy metal concentrations were studied in the scales of recent and subrecent (2-25 years old) fish buried in the oxbow lake sediments of the Morava River. The samples were taken from two cores up to 4-m deep and analysed using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and an electron microprobe analysis (EMPA). The results were compared with heavy metal concentrations of bulk samples of the embedding sediment. The study has revealed substantial differences in heavy metal contents existing between the recent and subrecent fish scales documenting an extreme rapidity of the diagenesis/fossilization processes. The most apparent features of the early fossilization include the quick loss of the mucous envelope, collagen and magnesium and an enormous increase in the heavy metal concentrations in particular iron, which is connected with a colour change. The variations in heavy metal contents in fish scales within a sample are attributed to variations in heavy metal content in the environment and variable amounts of organic matter in the embedding sediment. In contrast to the contamination of the embedding sediment, no general increase in heavy metal concentrations in fish scales was observed down to the cores. It is inferred that the rapid sorption stabilizes the biologic hydroxyapatite of the fish scales, which thus rapidly attain a thermodynamic equilibrium with the embedding water-saturated sediment. The results show that the processes of sorption, fossilization and stabilization of hydroxyapatite can act very quickly over a time scale of several years and represent thus a great advantage in the preservation of the original signals of the ancient environments.

  1. Comment on "Zircon U-Th-Pb dating using LA-ICP-MS: Simultaneous U-Pb and U-Th dating on 0.1 Ma Toya Tephra, Japan" by Hisatoshi Ito

    NASA Astrophysics Data System (ADS)

    Guillong, M.; Schmitt, A. K.; Bachmann, O.

    2015-04-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of eight zircon reference materials and synthetic zircon-hafnon end-members indicate that corrections for abundance sensitivity and molecular zirconium sesquioxide ions (Zr2O3+) are critical for reliable determination of 230Th abundances in zircon. Other polyatomic interferences in the mass range 223-233 amu are insignificant. When corrected for abundance sensitivity and interferences, activity ratios of (230Th)/(238U) for the zircon reference materials we used average 1.001 ± 0.010 (1σ error; mean square of weighted deviates MSWD = 1.45; n = 8). This includes the 91500 and Plešovice zircons, which were deemed unsuitable for calibration of (230Th)/(238U) by Ito (2014). Uranium series zircon ages generated by LA-ICP-MS without mitigating (e.g., by high mass resolution) or correcting for abundance sensitivity and molecular interferences on 230Th such as those presented by Ito (2014) are potentially unreliable.

  2. LA-ICP-MS Pb-U Dating of Young Zircons from the Kos-Nisyros Volcanic Centre, SE Aegean Arc (Greece)

    NASA Astrophysics Data System (ADS)

    Guillong, M.; Von Quadt, A.; Peytcheva, I.; Bachmann, O.

    2014-12-01

    Zircon Pb-U dating has become a key technique for answering many important questions in geosciences. This paper describes a new LA-ICP-MS approach. We show, using previously dated samples of a large quaternary rhyolitic eruption in the Kos-Nisyros volcanic centre (the 161 ka Kos Plateau Tuff), that the precision of our LA-ICP-MS method is as good as via SHRIMP, while ID-TIMS measurements confirm the accuracy. Gradational age distribution over >140 ka of the Kos zircons and the near-absence of inherited cores indicate near-continuous crystallisation in a growing magma reservoir with little input from wall rocks. Previously undated silicic eruptions from Nisyros volcano (Lower Pumice, Nikia Flow, Upper Pumice), which are stratigraphically constrained to have happened after the Kos Plateau Tuff, are dated to be younger than respectively 124 ± 35 ka, 111 ± 42 ka and 70 ± 24 ka. Samples younger than 1 Ma were corrected for initial thorium disequilibrium using a new formula that also accounts for disequilibrium in 230Th decay. Guillong, M. et al., 2014, JAAS, 29, p. 963-967; doi: 10.1039/c4ja00009a.

  3. Analysis of glass from the post-Roman settlement Tonovcov grad (Slovenia) by PIXE-PIGE and LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Šmit, Ž.; Milavec, T.; Fajfar, H.; Rehren, Th.; Lankton, J. W.; Gratuze, B.

    2013-09-01

    The combined PIXE-PIGE method was used for the analysis of 43 glass fragments from the archaeological site Tonovcov grad in western Slovenia, with 10 of these additionally being analysed by LA-ICP-MS. The glass objects were attributed to the Late Antique production of the 4th-7th c. AD, with two examples of early Roman glass and three glass beads, one of them presumably of oriental origin. The analysis showed typical natron-type glass, produced in the Levantine region around the river Belus, and a few examples of HIMT glass, which could be recognized also in several other recycled objects. Only one glass bead, found in Early Medieval context, was made of the ash of halophytic plants.

  4. LA-ICP-MS mapping of olivine from the Brahin and Brenham meteorites: Complex elemental distributions in the pallasite olivine precursor

    NASA Astrophysics Data System (ADS)

    McKibbin, Seann J.; O'Neill, Hugh St. C.; Mallmann, Guilherme; Halfpenny, Angela

    2013-10-01

    To investigate the early history of olivine from the Main-Group pallasites Brahin and Brenham, we have spatially mapped their trace-element distributions using laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICP-MS). Brahin olivine interiors contain ∼100-200 μm patches enriched in Cr, Al, Ti, V, Sc and Ga, separated by linear enrichments of P; these structures bear no relation to current crystal morphologies. Rather, cross-cutting relationships suggest they predate olivine-metal mixing. Brenham olivine also has internal variations for these elements. By contrast, Ni and Co concentrations in olivine from both meteorites decrease near crystal margins, as expected for freezing-in of profiles formed during diffusive re-equilibration with metal during cooling. Brenham olivine also has decreasing Al, Cr and Ti near the margin. Correlations between concentrations of Cr and Al exist for individual Brahin olivine grains, but do not hold over multiple grains, indicating a heterogeneous precursor. Al and Ti are correlated over multiple grains in Brahin, interpreted as Ti cations decorating pre-existing Al-defects. In Brenham olivine, similar geochemical trends exist, but the Cr-Al relationship probably represents both grain margin effects and pre-existing internal heterogeneity. The preservation of structure for elements which are normally fast diffusers in olivine hinges on coupled substitutions involving Al, which along with P diffuses much more slowly than most other elements under some conditions. Al concentrations in olivine are low and variable (3-33 ppm) which is inconsistent with crystallisation from a normal silicate melt; Al-in-olivine thermometers indicate that pallasite olivine was formed in a low-temperature environment. Following its delivery to the magma ocean/core-mantle boundary, Al-P systematics were not substantially modified. Assuming diffusivities for Al and P that are similar to Si (since they reside in the same crystallographic site

  5. Did the massive magnetite "lava flows" of El Laco (Chile) form by magmatic or hydrothermal processes? New constraints from magnetite composition by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

    2015-06-01

    The El Laco magnetite deposits consist of more than 98 % magnetite but show field textures remarkably similar to mafic lava flows. Therefore, it has long been suggested that they represent a rare example of an effusive Fe oxide liquid. Field and petrographic evidence, however, suggest that the magnetite deposits represent replacement of andesite flows and that the textures are pseudomorphs. We determined the trace element content of magnetite by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) from various settings at El Laco and compared them with magnetite from both igneous and hydrothermal environments. This new technique allows us to place constraints on the conditions under which magnetite in these supposed magnetite "lava flows" formed. The trace element content of magnetite from the massive magnetite samples is different to any known magmatic magnetite, including primary magnetite phenocrysts from the unaltered andesite host rocks at El Laco. Instead, the El Laco magnetite is most similar in composition to hydrothermal magnetite from high-temperature environments (>500 °C), such as iron oxide-copper-gold (IOCG) and porphyry-Cu deposits. The magnetite trace elements from massive magnetite are characterised by (1) depletion in elements considered relatively immobile in hydrothermal fluids (e.g. Ti, Al, Cr, Zr, Hf and Sc); (2) enrichment in elements that are highly incompatible with magmatic magnetite (rare earth elements (REE), Si, Ca, Na and P) and normally present in very low abundance in magmatic magnetite; (3) high Ni/Cr ratios which are typical of magnetite from hydrothermal environments; and (4) oscillatory zoning of Si, Ca, Mg, REE and most high field strength elements, and zoning truncations indicating dissolution, similar to that formed in hydrothermal Fe skarn deposits. In addition, secondary magnetite in altered, brecciated host rock, forming disseminations and veins, has the same composition as magnetite from the massive

  6. Paleoproterozoic age of the Zeya Group, Stanovoy Complex of the Dzhugdzhur-Stanovoy Superterrane (Central Asian mobile belt): Results of Sm-Nd isotopic and U-Th-Pb geochronological (LA-ICP-MS) analyses

    NASA Astrophysics Data System (ADS)

    Kotov, A. B.; Velikoslavinsky, S. D.; Kovach, V. P.; Sorokin, A. A.; Sorokin, A. P.; Skovitina, T. M.; Zagornaya, N. Yu.; Wang, K.-L.; Chung, S.-L.; Jahn, B.-M.

    2016-12-01

    Geochemical Sm-Nd isotope and U-Th-Pb geochronological (LA-ICP-MS) studies have demonstrated that the Zeya Group of the Stanovoy Complex of the Dzhugdzhur-Stanovoy Superterrane (Central Asian fold belt) is not Paleoarchean, as was previously thought, but Paleoproterozoic in age.

  7. Preparation of calibration materials for microanalysis of Ti minerals by direct fusion of synthetic and natural materials: experience with LA-ICP-MS analysis of some important minor and trace elements in ilmenite and rutile.

    PubMed

    Odegård, M; Mansfeld, J; Dundas, S H

    2001-08-01

    Calibration materials for microanalysis of Ti minerals have been prepared by direct fusion of synthetic and natural materials by resistance heating in high-purity graphite electrodes. Synthetic materials were FeTiO3 and TiO2 reagents doped with minor and trace elements; CRMs for ilmenite, rutile, and a Ti-rich magnetite were used as natural materials. Problems occurred during fusion of Fe2O3-rich materials, because at atmospheric pressure Fe2O3 decomposes into Fe3O4 and O2 at 1462 degrees C. An alternative fusion technique under pressure was tested, but the resulting materials were characterized by extensive segregation and development of separate phases. Fe2O3-rich materials were therefore fused below this temperature, resulting in a form of sintering, without conversion of the materials into amorphous glasses. The fused materials were studied by optical microscopy and EPMA, and tested as calibration materials by inductively coupled plasma mass spectrometry, equipped with laser ablation for sample introduction (LA-ICP-MS). It was demonstrated that calibration curves based on materials of rutile composition, within normal analytical uncertainty, generally coincide with calibration curves based on materials of ilmenite composition. It is, therefore, concluded that LA-ICP-MS analysis of Ti minerals can with advantage be based exclusively on calibration materials prepared for rutile, thereby avoiding the special fusion problems related to oxide mixtures of ilmenite composition. It is documented that sintered materials were in good overall agreement with homogeneous glass materials, an observation that indicates that in other situations also sintered mineral concentrates might be a useful alternative for instrument calibration, e.g. as alternative to pressed powders.

  8. History of individuals of the 18th/19th centuries stored in bones, teeth, and hair analyzed by LA-ICP-MS--a step in attempts to confirm the authenticity of Mozart's skull.

    PubMed

    Stadlbauer, Christina; Reiter, Christian; Patzak, Beatrix; Stingeder, Gerhard; Prohaska, Thomas

    2007-06-01

    A cranium stored in the Stiftung Mozarteum in Salzburg/Austria which is believed to be that of Mozart, and skeletal remains of suspected relatives which have been excavated from the Mozart family grave in the cemetery in Salzburg, have been subjected to scientific investigations to determine whether or not the skull is authentic. A film project by the Austrian television ORF in collaboration with Interspot Film on this issue was broadcast at the beginning of the "Mozart year 2006". DNA analysis could not clarify relationships among the remains and, therefore, assignment of the samples was not really possible. In our work this skull and excavated skeletal remains have been quantified for Pb, Cr, Hg, As, and Sb content by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to obtain information about the living conditions of these individuals. A small splinter of enamel (less than 1 mm(3)) from a tooth of the "Mozart cranium" was also available for investigation. Quantification was performed by using spiked hydroxyapatite standards. Single hair samples which are recorded to originate from Mozart have also been investigated by LA-ICP-MS and compared with hair samples of contemporary citizens stored in the Federal Pathologic-Anatomical Museum, Vienna. In general, Pb concentrations up to approximately 16 mug g(-1) were found in the bone samples of 18th century individuals (a factor of 7 to 8 higher than in recent samples) reflecting elevated Pb levels in food or beverages. Elevated Pb levels were also found in hair samples. The amount of Sb in the enamel sample of the "Mozart cranium" (approx. 3 mug g(-1)) was significantly higher than in all the other tooth samples investigated, indicating possible Sb ingestion in early childhood. Elevated concentrations of elements in single hair samples gave additional information about possible exposure of the individuals to heavy metals at a particular point in their life.

  9. "Invisible" gold and PGE elements in synthetic crystals of sphalerite and covellite: A EPMA, LA-ICP-MS and XAFS study

    NASA Astrophysics Data System (ADS)

    Tonkacheev, Dmitry; Chareev, Dmitry; Abramova, Vera; Tagirov, Boris

    2016-04-01

    Sphalerite and covellite are widespread minerals in the different genetic types of deposits and forms under the various conditions. The purpose of this work is to determine the possible range of concentration and chemical state of Au and PGE (Pt, Pd, Rh) in sphalerite (Zn,Fe) S and covellite (CuS). These minerals were synthesized using gas transport and salt flux techniques. The crystals of ZnS were grown using the gas transport method at 850°C and the salt flux one using NaCl/KCl, CsCl/NaCl/KCl, and LiCl/RbCl eutectic mixtures at 850, 645 and 470°C, respectively. CuS crystals were synthesized using the salt flux method in RbCl/LiCl melt at 470 and 340°C. The trace metal activity was always controlled by the presence of pure metal or its sulfide, and, therefore, the concentration of these elements in synthesized phases represent the maximum possible value for given T/f(S2) synthesis parameters. The LA-ICP-MS and/or EPMA techniques were used to determine the Au concentration in synthesized phases. The concentration of Au in sphalerite, synthesized at 850°C with admixture of Cd, Se, In, Fe, and Mn, reached 0.3wt%, whereas the sphalerite cell parameter extremely increased up to 5.4161Å relatively to 5.4060 Å for pure ZnS. It was found that the observed high Au concentration is caused by the presence of In (2091±46 ppm Au in sample with Fe and In in comparison with 14±7 for Se-bearing ZnS, 94±12 ppm for Fe-Mn-bearing sphalerite, and 96±46 for Fe-bearing sphalerite. The concentration of Au in Fe-bearing sphalerite synthesized at 645°C does not exceed 5 ppm. Therefore, increase of temperature results in the increase of Au concentration in sphalerite. The concentration of Au in another Fe-bearing-sphalerite series synthesized using gas transport method at 850°C various from 200 to 500 ppm and depends on the iron content. This fact could be related to the oxidation state or Fe in ZnS-FeS solid solution series. The concentration of Pt and Pd, Rh in sphalerite is

  10. [Progress in the application of laser ablation ICP-MS to surface microanalysis in material science].

    PubMed

    Zhang, Yong; Jia, Yun-hai; Chen, Ji-wen; Shen, Xue-jing; Liu, Ying; Zhao, Leiz; Li, Dong-ling; Hang, Peng-cheng; Zhao, Zhen; Fan, Wan-lun; Wang, Hai-zhou

    2014-08-01

    In the present paper, apparatus and theory of surface analysis is introduced, and the progress in the application of laser ablation ICP-MS to microanalysis in ferrous, nonferrous and semiconductor field is reviewed in detail. Compared with traditional surface analytical tools, such as SEM/EDS (scanning electron microscopy/energy dispersive spectrum), EPMA (electron probe microanalysis analysis), AES (auger energy spectrum), etc. the advantage is little or no sample preparation, adjustable spatial resolution according to analytical demand, multi-element analysis and high sensitivity. It is now a powerful complementary method to traditional surface analytical tool. With the development of LA-ICP-MS technology maturing, more and more analytical workers will use this powerful tool in the future, and LA-ICP-MS will be a super star in elemental analysis field just like LIBS (Laser-induced breakdown spectroscopy).

  11. Age and growth of endangered smalltooth sawfish (Pristis pectinata) verified with LA-ICP-MS analysis of vertebrae.

    PubMed

    Scharer, Rachel M; Patterson, William F; Carlson, John K; Poulakis, Gregg R

    2012-01-01

    Endangered smalltooth sawfish (Pristis pectinata) were opportunistically sampled in south Florida and aged by counting opaque bands in sectioned vertebrae (n=15). Small sample size precluded traditional age verification, but fish collected in spring and summer had translucent vertebrae margins, while fish collected in winter had opaque margins. Trends in Sr:Ca measured across vertebrae with laser ablation-inductively coupled plasma-mass spectrometry corresponded well to annual salinity trends observed in sawfish estuarine nursery habitats in south Florida, thus serve as a chemical marker verifying annual formation of opaque bands. Based on that finding and assumptions about mean birth date and timing of opaque band formation, estimated age ranged from 0.4 y for a 0.60 m total length (TL) male to 14.0 y for a 4.35 m TL female. Von Bertalanffy growth parameters computed from size at age data were 4.48 m for L(∞), 0.219 y(-1)for k, and -0.81 y for t(0). Results of this study have important implications for sawfish conservation as well as for inferring habitat residency of euryhaline elasmobranchs via chemical analysis of vertebrae.

  12. Age and Growth of Endangered Smalltooth Sawfish (Pristis pectinata) Verified with LA-ICP-MS Analysis of Vertebrae

    PubMed Central

    Scharer, Rachel M.; Patterson III, William F.; Carlson, John K.; Poulakis, Gregg R.

    2012-01-01

    Endangered smalltooth sawfish (Pristis pectinata) were opportunistically sampled in south Florida and aged by counting opaque bands in sectioned vertebrae (n = 15). Small sample size precluded traditional age verification, but fish collected in spring and summer had translucent vertebrae margins, while fish collected in winter had opaque margins. Trends in Sr:Ca measured across vertebrae with laser ablation-inductively coupled plasma-mass spectrometry corresponded well to annual salinity trends observed in sawfish estuarine nursery habitats in south Florida, thus serve as a chemical marker verifying annual formation of opaque bands. Based on that finding and assumptions about mean birth date and timing of opaque band formation, estimated age ranged from 0.4 y for a 0.60 m total length (TL) male to 14.0 y for a 4.35 m TL female. Von Bertalanffy growth parameters computed from size at age data were 4.48 m for L∞, 0.219 y−1for k, and −0.81 y for t0. Results of this study have important implications for sawfish conservation as well as for inferring habitat residency of euryhaline elasmobranchs via chemical analysis of vertebrae. PMID:23082225

  13. Evolution of garnet distribution, shape and composition in high-grade pelitic migmatites of Salvador da Bahia, Brazil: insights from LA-ICP-MS trace element mapping

    NASA Astrophysics Data System (ADS)

    Goncalves, Philippe; Raimondo, Tom; Santos de Souza, Jailma

    2016-04-01

    Garnet is a widely used mineral in metamorphic petrology and more particularly for thermobarometric modelling to reconstruct the P-T-t evolution of Earth's crust. This is due to its ubiquity in high grade rocks (T > 450°C), its occurrence in many assemblages of interest for thermobarometry, and mostly to its ability to preserve chemical zoning. Two types of zoning are distinguished: growth and diffusion zoning. Growth zoning reflects crystallisation coeval with changes in P-T conditions or bulk composition. This type of zoning is therefore particularly useful to unravel the P-T evolution of open systems and determine the growth mechanisms involved. However, growth zoning in major elements is commonly altered by processes such as volume diffusion, which is particularly efficient at high temperatures and for elements like Fe or Mg that have high diffusion coefficients. In such cases, information that relates to the environmental conditions of garnet growth is either totally or partially obliterated. To minimise the impact of this process on growth zoning and retain useful information, trace elements are more appropriate because of their lower diffusion coefficients compared to major elements. In this study, the distribution of trace elements in garnet has been imaged using an emerging LA-ICP-MS mapping technique. This is achieved by rastering of the focused laser beam in linear transects, which are then stitched together by post-acquisition processing to form a quantified or semi-quantified image of the trace element distribution, with excellent detection limits (ppb) over a wide isotopic range (7Li to 238U) and minimal sample preparation required. This technique has been applied to high-grade pelitic gneisses and migmatites from the Paleoproterozoic Itabuna-Salvador-Curaça belt (adjacent to the Farol da Bara, Salvador da Bahia, Brazil). Structurally, it is located in a steeply-dipping high strain zone that may have played a major role in the segregation and

  14. Determinations of Platinum-Group Element (PGE) Distributions Using Whole-rock, SEM, EMPA, Image Analysis, and LA-ICP-MS Techniques in the Kelly Lake Ni-Cu-PGE Deposit, Sudbury

    NASA Astrophysics Data System (ADS)

    Huminicki, M. A.; Cabri, L.; Sylvester, P. J.; Tubrett, M. N.

    2004-05-01

    The Kelly Lake deposit is a Ni-Cu-PGE offset-style deposit that occurs at the south end of the Copper Cliff Offset (CCO), Sudbury. The deposit consists of four ore bodies (710, 720, 725, and 740) that were first identified in 1997 and contain a published 10.5 million tonnes of ore at 1.77% Ni, 1.34% Cu, and 3.6 g/tonne combined Pt + Pd + Au. The ore bodies have a sub-vertical orientation and plunge to the south. The CCO consists of an inclusion-and sulfide-poor marginal zone of quartz diorite (QD) and an inclusion- and sulfide-rich core of QD. The sulfide assemblage is similar to other deposits along the CCO, comprising pentlandite (Pn), pyrrhotite (Po), and chalcopyrite (Ccp) with minor pyrite (Py) and trace amounts of galena [PbS]. The platinum-group mineral assemblage consists of michenerite [(Pd,Pt)BiTe], sperrylite [PtAs2], and microinclusions of hollingworthite [(Rh,Pt,Pd)AsS] and ruarsite [RuAsS], which are associated with the bismuth-telluride, tsumoite [BiTe] and the sulfarsenide, cobaltite-gersdorfitte [(Co,Fe)AsS-NiAsS]. The purpose of this study was to determine the distribution of the platinum-group elements (PGE) within the Kelly Lake ores. Analyses were carried out using a combination of: 1) lead and nickel-sulfide fire-assay for whole rock PGE abundances; 2) scanning-electron-microscopy (SEM) image analysis, quantitative energy dispersive X-ray spectrometry (EDXS), and quantitative electron probe microanalysis (EPMA) to determine size, shape, location, association, and mineral chemistry of discrete platinum-group minerals; and 3) laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to determine low-level PGE contents in solid solution and as microinclusions within the sulfides and sulfarsenides. SEM, EPMA, and LA-ICP-MS results indicate that the PGE occur: 1) primarily as discrete PGM (sperrylite and michenerite), 2) in solid-solution in cobaltite-gersdorfitte, and 3) as micro-inclusions of hollingworthite and ruarsite in

  15. LA-ICP-MS mineral chemistry of titanite and the geological implications for exploration of porphyry Cu deposits in the Jinshajiang - Red River alkaline igneous belt, SW China

    NASA Astrophysics Data System (ADS)

    Xu, Leiluo; Bi, Xianwu; Hu, Ruizhong; Tang, Yongyong; Wang, Xinsong; Xu, Yue

    2015-04-01

    The Jinshajiang-Red River alkaline igneous belt in the eastern Indian-Asian collision zone, of southwestern China, hosts abundant, economically important Cu-Mo-Au mineralization of Cenozoic age. Major- and trace-element compositions of titanites from representative Cu-mineralized intrusions determined by LA-ICP-MS show higher values for Fe2O3/Al2O3, ΣREE + Y, LREE/HREE, Ce/Ce*, (Ce/Ce*)/(Eu/Eu*), U, Th, Ta, Nb and Ga, and lower values for Al2O3, CaO, Eu/Eu*, Zr/Hf, Nb/Ta and Sr than those for titanites from barren intrusions. Different ΣREE + Y, LREE/HREE, U, Th, Ta and Nb values of titanites between Cu-mineralized and barren intrusions were controlled mainly by the coexisting melt compositions. However, different Sr concentrations and negative Eu anomalies of titanites between Cu-mineralized and barren intrusions were most probably caused by different degrees of crystallization of feldspar from melts. In addition, different Ga concentrations and positive Ce anomalies of titanites between Cu-mineralized and barren intrusions were most likely caused by different magmatic fO2 conditions. Pronounced compositional differences of titanites between Cu-mineralized and barren intrusions can provide a useful tool to help discriminate between ore-bearing and barren intrusions at an early stage of exploration, and, thus, have a potential application in exploration for porphyry Cu deposits in the Jinshajiang - Red River alkaline igneous belt, and to other areas.

  16. Coupling thermodynamic modeling and high-resolution in situ LA-ICP-MS monazite geochronology: evidence for Barrovian metamorphism late in the Grenvillian history of southeastern Ontario

    NASA Astrophysics Data System (ADS)

    McCarron, Travis; Gaidies, Fred; McFarlane, Christopher R. M.; Easton, R. Michael; Jones, Peter

    2014-12-01

    The Flinton Group is a greenschist to upper amphibolite facies package of metasediments in southeastern Ontario that was metamorphosed during the Ottawan Orogeny. Thermodynamic modeling of metapelitic mineral assemblages suggests an increase in peak conditions of metamorphism across the 40 km wide study area from 3.5 to 7.9 kbar and 540 to 715 °C. Garnet isopleth thermobarometry applied to the cores of compositionally zoned porphyroblasts reveals remarkably similar P-T conditions of initial crystallization at approximately 3.7-4.0 kbar and 512-520 °C, corresponding to a relatively high geothermal gradient of ca. 34-45 °C km-1. It is inferred from modeling and reaction textures that metamorphism was along Barrovian P-T paths. Major and trace element zoning in garnet from one sample records a complex growth history as evidenced by major and trace element zoning and the distribution of xenotime, allanite and monazite inclusions. High-resolution (6 μm) LA-ICP-MS U-Pb geochronology performed on monazite in the rock matrix and included in the outer 150 μm of garnet rim-ward of a Y annulus revealed an age of 976 ± 4 Ma. The age is interpreted to reflect monazite growth at the expense of allanite and apatite late in garnet's growth history over the P-T interval 4.5-6.8 kbar and 540-640 °C. This new age estimate for near peak metamorphism fits well into the regional framework but is significantly younger than previously reported ages for Ottawan metamorphism. Based on microstructures this new age suggests that compressional tectonics were operating much later in the history of the Grenville of southeastern Ontario than previously thought.

  17. Trace element distribution in silicate phases from the cumulate mafic xenoliths of Puy Beaunit (French Massif Central): A LA-ICP-MS study

    NASA Astrophysics Data System (ADS)

    Demaiffe, D.; Berger, J.; Femenias, O.; Coussaert, N.

    2003-04-01

    A large diversity of xenoliths is present in the scoria cones of the quaternary Puy Beaunit (French Massif Central). Mafic xenoliths are abundant, they are mainly gabbronorites with minor pyroxenites and anorthositic gabbros. It has been shown recently that they derived from a deep layered complex emplaced at the crust-mantle boundary during Late Permian (257+/- 6Ma). These rocks still partly show magmatic structures. However, sub-solidus recrystallisation and pyrometamorphic overprinting (while the xenoliths were taken up by the lava) have partly blurred the magmatic primary textures. The xenoliths now have polygonal and coronitic textures, so intercumulus phases cannot be easily identified. The abundance of orthopyroxene (generally missing in alkaline series), the low content of REE and trace elements and the nearly flat spidergram profiles suggest that these xenoliths are of subalkaline affinity. They commonly show mm- to cm- scale layering indicative of a cumulate origin. Positive (in whole rock plagioclase-rich gabbros) and negative (in pyroxene-rich gabbros) Eu anomalies also argue for a cumulate origin. The trace element contents (REE, Zr, Hf, Rb, Sr, Nb, Ta, Ba) of the main silicate phases (plagioclase, orthopyroxene, clinopyroxene and the very fine-grained coronites) have been obtained by LA-ICP-MS. Two processes control the REE content of these mafic xenoliths: 1) the degree of differentiation, which is indicated by the Mg# of the cumulus orthopyroxene; 2) the proportion of trapped interstitial liquid which is indicated by the content of highly incompatible elements (U, Th, Zr and Rb) in whole rock analyses. Plagioclases and orthopyroxenes have relatively low REE contents compared to clinopyroxene and coronitic association suggesting that they are the cumulus phases. High REE and trace element contents of clinopyroxenes and of the very fine-grained coronites point to an intercumulus origin. Moreover, in situ REE patterns show that the very fine

  18. Combining fs LA-ICP-MS, FIB and STXM-NEXAFS Methods for in-situ High-Spatial-Resolution Rock Varnish Analyses at the nm to µm Scale

    NASA Astrophysics Data System (ADS)

    Macholdt, D.; Andreae, M. O.; Jochum, K. P.; Kappl, M.; Kilcoyne, A. L. D.; Müller, M.; Pöhlker, C.; Stoll, B.; Weber, B.; Weigand, M.; Weis, U.

    2014-12-01

    Since over 200 years a number of studies debate the origin of the black or red, up to 250 µm thick coatings on desert rocks, referred to as rock varnish. The main components of varnish are poorly crystallized Mn and Fe oxides and clay minerals. Both biological and geological processes have been suggested for the genesis. We used a combination of 200 nm-femtosecond LA-ICP-MS, focused ion beam (FIB) slicing and scanning transmission X-ray microscopy - near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS) for the high-spatial-resolution analysis of rock varnish from different locations (Negev, Israel; Knersvlakte, South Africa; Death Valley and Mojave Desert, California). Femtosecond LA-ICP-MS was used for the quantitative determination of major and trace element concentrations. In-situ measurements were conducted on thick sections with the advantages of non-matrix matched calibration, low ablation depth of ~10 µm for laser spot sizes of 10-40 µm and low detection limits of trace elements (< 0.01 - 1 µg g-1). Our results demonstrate that elements, such as Mn, Co, Pb, Ni and Cu, are highly enriched in varnish relative to the upper continental crust (up to a factor of 1000). Differences between varnishes from the various locations can be observed especially for the Mn/Fe (0.4-25.6), Mn/Ba (3-363) and Ni/Co (0.03-1.8) ratios. The REE patterns differ with LaN/YbN = 2-14 and positive Ce anomalies (Ce/Ce* = 1.1 - 9.1). To study the internal structures of varnish, 100 - 200 nm thick FIB slices were prepared to perform mappings of Fe, Mn, O, N, CO3, K, Ca, and C at the nm scale. In addition, the oxidation stages of Mn and Fe were identified. Banded internal structures of Mn and organic C can be observed in some samples, and cavities that are partly filled by C and Mn rich material. Some coatings tend to incorporate bigger dust grains (> 1 µm), while others only show very fine grained material (< 0.1 µm). The results of the combined microanalytical

  19. Magmatic evolution of the differentiated ultramafic, alkaline and carbonatite intrusion of Vuoriyarvi (Kola Peninsula, Russia). A LA-ICP-MS study of apatite

    NASA Astrophysics Data System (ADS)

    Brassinnes, S.; Balaganskaya, E.; Demaiffe, D.

    2005-11-01

    The nature of the petrogenetic links between carbonatites and associated silicate rocks is still under discussion (i.e., [ Gittins J., Harmer R.E., 2003. Myth and reality of the carbonatite-silicate rock "association". Period di Mineral. 72, 19-26.]). In the Paleozoic Kola alkaline province (NW Russia), the carbonatites are spatially and temporally associated to ultramafic cumulates (clinopyroxenite, wehrlite and dunite) and alkaline silicate rocks of the ijolite-melteigite series [ Kogarko, L.N., 1987. Alkaline rocks of the eastern part of the Baltic Shield (Kola Peninsula). In: Fitton, J.G., and Upton, B.G.J. (eds). Alkaline igneous rocks. Geol. Soc. Special Publication 30, 531-544; Kogarko, L.N., Kononova, V.A., Orlova, M.P., Woolley, A.R., 1995. Alkaline rocks and carbonatites of the world. Part 2. Former USSR. Chapman and Hall, London, 225 pp; Verhulst, A., Balaganskya, E., Kirnarsky, Y., Demaiffe, D., 2000. Petrological and geochemical (trace elements and Sr-Nd isotopes) characteristics of the Paleozoic Kovdor ultramafic, alkaline and carbonatite intrusion (Kola Peninsula, NW Russia). Lithos 51, 1-25; Dunworth, E.A., Bell, K., 2001. The Turiy Massif, Kola Peninsula, Russia; isotopic and geochemical evidence for a multi-source evolution. J. Petrol. 42, 377-405; Woolley, A.R., 2003. Igneous silicate rocks associated with carbonatites: their diversity, relative abundances and implications for carbonatite genesis. Period. di Mineral. 72, 9-17)]. In the small (≈ 20 km 2) Vuoriyarvi massif, apatite is typically a liquidus phase during the magmatic evolution and so it can be used to test genetic relationships. Trace elements contents have been obtained for both whole rocks and apatite (by LA-ICP-MS). The apatites define a single continuous chemical evolution marked by an increase in REE and Na (belovite-type of substitution, i.e., 2Ca 2+ = Na + + REE 3+). This evolution possibly reflects a fractional crystallisation process of a single batch of isotopically

  20. Effects of hydrothermal alteration on Pb in the active PACMANUS hydrothermal field, ODP Leg 193, Manus Basin, Papua New Guinea: A LA-ICP-MS study

    NASA Astrophysics Data System (ADS)

    Beaudoin, Yannick; Scott, Steven D.; Gorton, Michael P.; Zajacz, Zoltan; Halter, Werner

    2007-09-01

    The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350 °C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are

  1. Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

    NASA Astrophysics Data System (ADS)

    Holwell, David A.; Keays, Reid R.; McDonald, Iain; Williams, Megan R.

    2015-12-01

    The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu-PGE-Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190-700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do

  2. Temporal and Spatial Fluctuations in Ancestral Northern Cascade Arc Magmatism from New LA-ICP-MS U-Pb Zircon Dating

    NASA Astrophysics Data System (ADS)

    McCallum, I. S.; Mullen, E.; Jean-Louis, P.; Tepper, J. H.

    2015-12-01

    Mt. Baker and the adjacent Chilliwack batholith (MBC focus) in NW Washington preserve the longest magmatic record in the Cascade Arc, providing an excellent natural laboratory for examining the spatial, temporal and geochemical evolution of Cascade magmatism and links to tectonic processes. We present new U-Pb zircon LA-ICP-MS ages for 14 samples from MBC and neighboring regions of the north Cascades. The new results are up to 8 Myr different from previous K-Ar ages, illustrating the need for new age determinations in the Cascades. A maximum age of 34.74±0.24 Ma (2σ) (Post Creek stock) is consistent with 35-40 Ma ages for arc inception in the southern Cascades. The most voluminous MBC plutons cluster at 32-29 Ma, consistent with an early flare-up that also coincides with intrusion of the Index batholith farther south (2 samples at 33.26±0.19, 33.53±0.15 Ma). This flare-up is absent in the northernmost Cascades where the oldest pluton (Fall Creek stock) is 6.646±0.046 Ma, 4 Myr younger than previously cited. Earliest Cascade magmatism is progressively younger to the north of MBC, possibly tracing the northerly passage of the slab edge. MBC activity was continuous to 22.75±0.17 Ma (Whatcom Arm), marking the initiation of an 11 Myr hiatus. Magmatism resumed at 11.33±0.08 Ma (Indian Creek) and continued to the modern Mt. Baker cone, defining a pattern of southwesterly migration over ~55 km that may be attributable to slab rollback and arc rotation (e.g. Wells & McCaffrey 2013). Uniformity of the rate and direction of migration implies that rollback and rotation began at least 11 Myr ago. Post-hiatus magmas show distinct geochemical and petrologic characteristics including a major Pb isotopic shift. The 2.430±0.016 Ma Lake Ann stock contains 4.2 Ma zircon antecrysts, recording prolonged activity in that area. The 1.165±0.013 Ma Kulshan caldera ignimbrite contains ~200 Ma inherited zircons that may provide the first direct record of Wrangellian basement beneath

  3. Sampling strategies for the analysis of glass fragments by LA-ICP-MS Part I. Micro-homogeneity study of glass and its application to the interpretation of forensic evidence.

    PubMed

    Trejos, Tatiana; Almirall, José R

    2005-08-15

    The authors have previously reported the use of laser ablation ICP-MS as a powerful analytical tool for elemental analysis of glass. LA is a simpler, faster and less intrusive sample introduction method than the conventional solution ICP-MS. Due to the minute amount of material removed in LA ( approximately 300ng, 50mum crater size), the analyst should be aware of special sampling considerations such as characterization of the glass fragments originating from the "known" source, fragment size and selection of the area and surface of ablation. The purpose of this work was to evaluate the micro-homogeneity of the elemental composition of glass samples commonly found in crime scenes like containers, architectural windows and windshields. The set of glasses under study was comprised of 56 fragments originated from glass containers, 28 fragments from automobile windshields and 20 fragments from architectural windowpanes. All fragments were selected with a size smaller than 2mm(2) in order to simulate the typical glass fragments transferred from the crime scenarios. A Nd:YAG laser, 266nm, flat top beam profile was used in single point mode sampling 50mum spot size for 50s at 10Hz (500 shots). In this study, (29)Si was used as an internal standard and the standard reference material, SRM NIST 612, was used as a single point external calibrator. In addition, SRM 621 was used as another control standard for the containers set and SRM 1831 for the automobile and architectural window sets due to their very similar matrix with the samples of interest. For each set of glasses, the mean values and standard deviation of 10 replicates (n=10) of a single fragment were compared with the values obtained from 10 (n=10) different fragments of glass within the area of interest in order to evaluate whether or not the variation within a glass was bigger than the variation due to the method. In addition, a subset of tempered glasses was evaluated to perform an elemental composition profile

  4. Application of dried-droplets deposited on pre-cut filter paper disks for quantitative LA-ICP-MS imaging of biologically relevant minor and trace elements in tissue samples.

    PubMed

    Bonta, Maximilian; Hegedus, Balazs; Limbeck, Andreas

    2016-02-18

    In this work, a novel calibration approach for minor and trace element quantification in LA-ICP-MS imaging of biological tissues is presented. Droplets of aqueous standard solutions are deposited onto pre-cut pieces of filter paper, allowed to dry, and sputtered with a thin gold layer for use as pseudo-internal standard. Analysis of the standards using LA-ICP-MS is performed using radial line-scans across the filters. In contrast to conventionally used preparation of matrix-matched tissue standards, the dried-droplet approach offers a variety of advantages: The standards are easy to prepare, no characterization of the standards using acid digestion is required, no handling of biological materials is necessary, and the concentration range, as well the number of investigated analytes is almost unlimited. The proposed quantification method has been verified using homogenized tissue standards with known analyte concentrations before being applied to a human malignant mesothelioma biopsy from a patient who had not received any chemotherapeutic treatment. Elemental distribution images were acquired at a lateral resolution of 40 μm per pixel, limits of detection ranging from 0.1 μg g(-1) (Mn, Ni, Cu, Zn) to 13.2 μg g(-1) (K) were reached.

  5. Trace Element Study of MORB Glasses from 14¡ã-16¡ãN along Mid-Atlantic Ridge by LA-ICP- MS

    NASA Astrophysics Data System (ADS)

    Barzoi, C. A.; Casey, J. F.; Gao, Y.; Lapen, T.

    2007-12-01

    A comparison of 20 MORB glasses from 14°-16° N along the Mid-Atlantic Ridge using both solution-based and in situ laser ablation-based ICP-MS trace element analyses on the same samples was conducted. Li, Be, Sc, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Tb, Gd, Dy, Ho, Er, Tm, Yb,Lu, Hf, Ta, Pb, Th, and U were analyzed using the Varian 810 quadrupole ICP-MS. The instrument features a 90 degree ion mirror and low noise double-off-axis quadrupole that allows high sensitivity and low backgrounds. Precision in term of relative standard deviation (RSD) of the measurements for both methods based on repeated analyses of USGS BIR-1G and BHVO-2G glass standards and Max Planck KL-2G glass standard is within 5 % for all trace elements with the exception of Pb, which averaged 12 %. Measured trace element abundances are within 2% of recommended standard values using both solution and laser ablation methods. Comparison between the analyte concentrations obtained by solution-based ICP-MS and in situ microanalysis by laser ablation reveals little systematic differences in abundances(<5% for all elements). The two-method correlation and strong repeatability of the results indicate that rapid in situ trace element analysis by laser ablation ICP-MS is likely to become a preferred method of trace element analysis for MORB glasses. Our geochemical results and previous studies of MORB glasses in the region of the MAR between 14°-16°N show that basalts are characterized isotopic and incompatible element enrichment.The nature of the enrichment has been the topic of significant discussion and speculation because a specific mantle plume is not well defined in the region. Likewise the magma supply is probably small in the region as the magmatic crust is interpreted to be very thin in most of the area studied. Integrated studies of major element, trace element, and isotopic variations among basalts, gabbroic rocks and igneous and residual ultramafic

  6. Comparative tissue distribution of metals in birds in Sweden using ICP-MS and laser ablation ICP-MS.

    PubMed

    Ek, Kristine H; Morrison, Gregory M; Lindberg, Peter; Rauch, Sébastien

    2004-08-01

    Cadmium, copper, lead, palladium, platinum, rhodium, and zinc profiles were investigated along feather shafts of raptor and other bird species by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The distribution of external versus internal metal contamination of feathers was investigated. The species examined were peregrine falcon (Falco peregrinus), sparrowhawk ( Accipiter nisus), willow grouse (Lagopus lagopus), and house sparrow (Passer domesticus) in Sweden. For habitat comparisons, total Cu, Pb, Zn, and Cd concentrations were analyzed by ICP-MS in feathers of the examined species as well as captive peregrine falcon. For investigation of metal distribution and correlation in different biological materials of raptors, total concentrations of Cu, Pb, Cd, and Zn were also investigated by ICP-MS in feathers, eggs, blood, feces, liver, and kidney of wild peregrine falcon from southwestern Sweden. Laser ablation of feathers revealed that Pb contamination is both external and internal, Zn contamination is internal, and Cd and Cu contamination is predominantly internal, with a few externally attached particles of high concentration. Pb, Cu, and Cd signal intensities were highest in urban habitats and contamination was mainly external in feathers. The background signal intensity of Zn was also higher in birds from urban habitats. The laser ablation profile of PGE (Pt, Pd, Rh) demonstrated that PGE contamination of feathers consists almost exclusively of externally attached PGE-containing particles, with little evidence of internally deposited PGE.Generally, total metal concentrations in feathers were highest in sparrowhawk and house sparrow due to their urban habitat. Total Cu, Zn, and Cd concentrations were highest in liver and kidney due to binding to metallothionein, while the total Pb concentration was highest in feces due to the high excretion rate of Pb. A decreasing temporal trend for Pb in feathers, showing that Pb levels in feathers have

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

    PubMed

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

    2016-09-01

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

  8. Characterizing Carbonates from the Sheep Pass Formation, Nevada Using Laser Ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Piccione, G.; Rasbury, T.; Davis, D. M.; Druschke, P.; Hanson, A. D.; Parrish, R. R.; Austin-Giddings, W.

    2014-12-01

    Laser ablation plasma mass spectrometry allows for rapid high spatial resolution sampling, which is favorable for geochemically variable samples such as carbonates. This method also allows characterization of samples through the evaluation of elements, element ratios, and isotope ratios. Pairing LA ICP-MS with paragenetic studies provides the ability to geochemically characterize physically distinguishable fluid events that formed new phases. This is particularly useful for analysis of vein filling minerals, which can then be attributed to a tectonic or magmatic event. Coupling elemental analyses with U-Pb dating allows us to not only date the timing of mineralization and its associated tectonic activity, but also to better characterize the fluids in order to understand where they came from and what they may have interacted with. A suite of carbonates from the basal member of the Sheep Pass Formation in east-central Nevada was analyzed using LA ICP-MS, yielding U-Pb ages that are in agreement with both the ages found using ID TIMS and the known age of that member. An age was also attained for fluorite from a vein that cuts the dated Sheep Pass member. This age is distinctly younger than the lacustrine carbonates and is consistent with evidence that the major bounding faults of this basin have experienced multiple phases of movement.

  9. Laser ablation ICP-MS applications using the timescales of geologic and biologic processes

    NASA Astrophysics Data System (ADS)

    Ridley, W. I.

    2003-04-01

    Geochemists commonly examine geologic processes on timescales of 10^4--10^9 years, and accept that often age relations, e.g., chemical zoning in minerals, can only be measured in a relative sense. The progression of a geologic process that involves geochemical changes may be assessed using trace element microbeam techniques, because the textural, and therefore spatial context, of the analytical scheme can be preserved. However, quantification requires appropriate calibration standards. Laser ablation ICP-MS (LA-ICP-MS) is proving particularly useful now that appropriate standards are becoming available. For instance, trace element zoning patterns in primary sulfides (e.g., pyrite, sphalerite, chalcopyrite, galena) and secondary phases can be inverted to examine relative changes in fluid composition during cycles of hydrothermal mineralization. In turn such information provides insights into fluid sources, migration pathways and depositional processes. These studies have only become possible with the development of appropriate sulfide calibration standards. Another example, made possible with the development of appropriate silicate calibration standards, is the quantitative spatial mapping of REE variations in amphibolite-grade garnets. The recognition that the trace and major elements are decoupled provides a better understanding of the various sources of elements during metamorphic re-equilibration. There is also a growing realization that LA-ICP-MS has potential in biochemical studies, and geochemists have begun to turn their attention in this direction, working closely with biologists. Unlike many geologic processes, the timescales of biologic processes are measured in years to centuries and are frequently amenable to absolute dating. Examples that can be cited where LA-ICP-MS has been applied include annual trace metal variations in tree rings, corals, teeth, bones, bird feathers and various animal vibrissae (sea lion, walrus, wolf). The aim of such studies is

  10. In-situ U/Pb rutile dating by LA-ICP-MS: 208Pb correction and prospects for thermochronological applications

    NASA Astrophysics Data System (ADS)

    Zack, T.; Stockli, D. F.; Luvizotto, G. L.; Barth, M. G.; Wolfe, M. R.; Hinton, R. W.; Berndt-Gerdes, J.; Kooijman, E.

    2009-12-01

    The advent of rutile thermometry brought an increasing interest in understanding rutile formation and its temporal evolution. Here we report progress on several fronts of in situ U-Pb rutile geochronology: (1) Matrix matching, necessary for robust in situ dating is fullfilled by calibrating and testing rutile standards (R10 and R19), including the presentation of new TIMS ages for the rutile standard R19. (2) Common lead correction is routinely applied via 208Pb, which is possible due to extremely low Th/U ratios (usually <0.003) in most rutiles. Employing a 213 nm Nd:YAG laser coupled to a quadrupole ICP-MS and using R10 as a primary standard, rutile U/Pb ages for the other rutile standard and four rutile-bearing metamorphic rocks always agree better than 2% with the reported TIMS ages and other dating studies from the same localities. The methods outlined in this contribution should find wide application in thermochronological studies that require age information of single spots, e.g., single-crystal zoning and texturally-controlled dating. With this information we are able to address the effect of shielding of inclusion phases by robust host minerals.

  11. Rare Earth Element Mapping of Garnet by Laser Ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Koenig, A. E.; Koenig, A. E.; Magloughlin, J. F.; Ridley, W. I.

    2001-12-01

    The introduction of the electron microprobe brought tremendous advancement to our understanding of mineral forming reactions, thermobarometry and the patterns and controls of major element zoning. Today, the application of laser ablation ICP-MS (LA-ICP-MS) is providing the same advancements, but at the trace element scale. While considerable attention has been paid to the behavior of trace elements in a crystal-melt system, the number of studies addressing trace elements in metamorphic minerals is few. We have developed methods using LA-ICP-MS to rapidly construct quantitative trace element maps of geologic (minerals, corals, coal, etc.) and non-geologic (tree rings, sheep horns, fish scales, metals, etc.) materials. Experimental determination of trace element partitioning and the parameters that control it are determined almost exclusively on experimental melt products and natural glasses. With this study we demonstrate that insight into the behavior of the trace elements during metamorphic mineral growth is now readily obtainable. Garnets from the Nason terrane, North Cascades, WA, USA have been analyzed in order to study trace element heterogeneity. In the Nason terrane, almandine-rich garnets in amphibolite facies rocks all possess distinct enhanced HREE compatibility in the cores with varying degrees of complex zoning towards the rim. A distinct trace-element-enriched annulus is present in nearly all garnets studied. Annuli enriched in the HREEs and Y are common, but annuli enriched only in the LREEs are also present. We suggest the annuli are the result of the breakdown of REE-rich minerals such as monazite, apatite and/or xenotime. The HREE zoning patterns from rim to core can be used to model the changing mechanism for growth zoning. While it is clear that various mechanisms operate during the entire growth history, it appears that intercrystalline diffusion is the dominant mechanism producing HREE zoning in the early stages of garnet growth.

  12. Siderophile Element Profile Measurements in Iron Meteorites Using Laser Ablation ICP-MS

    NASA Technical Reports Server (NTRS)

    Watson, H. C.; Watson, E. B.; McDonough, W. F.

    2005-01-01

    Understanding the behaviour of siderophile elements during cooling of iron meteorites can lead to insight into the general thermal histories of the meteorites as well as their respective parent bodies. Traditionally trace element analyses in meteorites have been done using techniques that only measure the average concentration in each phase. With these methods, all of the spatial information with respect to the distribution of an element within one phase is lost. Measuring concentration profiles of trace elements in meteorites is now possible, with the advent of high-resolution analytical techniques such as laser ablation, inductively coupled plasma mass spectrometry (LA-ICP-MS) with spatial resolution <20 microns. [e.g. 1,2] and secondary ion mass spectrometry [3]. These profiles can give more insight into both the partitioning and diffusive behavior of siderophile elements in metal systems relevant to iron meteorites, as well as parent body cooling rates.

  13. Distribution and solubility limits of trace elements in hydrothermal black smoker sulfides: An in-situ LA-ICP-MS study

    NASA Astrophysics Data System (ADS)

    Wohlgemuth-Ueberwasser, Cora C.; Viljoen, Fanus; Petersen, Sven; Vorster, Clarisa

    2015-06-01

    The key for understanding the trace metal inventory of currently explored VHMS deposits lies in the understanding of trace element distribution during the formation of these deposits on the seafloor. Recrystallization processes already occurring at the seafloor might liberate trace elements to later hydrothermal alteration and removement. To investigate the distribution and redistribution of trace elements we analyzed sulfide minerals from 27 black smoker samples derived from three different seafloor hydrothermal fields: the ultramafic-hosted Logatchev hydrothermal field on the Mid-Atlantic Ridge, the basaltic-hosted Turtle Pits field on the mid-atlantic ridge, and the felsic-hosted PACMANUS field in the Manus basin (Papua New Guinea). The sulfide samples were analyzed by mineral liberation analyser for the modal abundances of sulfide minerals, by electron microprobe for major elements and by laser ablation-inductively coupled plasma-mass spectrometry for As, Sb, Se, Te, and Au. The samples consist predominantly of chalcopyrite, sphalerite, pyrite, galena and minor isocubanite as well as inclusions of tetrahedrite-tennantite. Laser ablation spectra were used to evaluate the solubility limits of trace elements in different sulfide minerals at different textures. The solubility of As, Sb, and Au in pyrite decreases with increasing degree of recrystallization. When solubility limits are reached these elements occur as inclusions in the different sulfide phases or they are expelled from the mineral phase. Most ancient VHMS deposits represent felsic or bimodal felsic compositions. Samples from the felsic-hosted PACMANUS hydrothermal field at the Pual ridge (Papua New Guinea) show high concentrations of Pb, As, Sb, Bi, Hg, and Te, which is likely the result of an additional trace element contribution derived from magmatic volatiles. Co-precipitating pyrite and chalcopyrite are characterized by equal contents of Te, while chalcopyrite that replaced pyrite (presumably

  14. Location and speciation of gadolinium and yttrium in roots of Zea mays by LA-ICP-MS and ToF-SIMS.

    PubMed

    Saatz, Jessica; Stryhanyuk, Hryhoriy; Vetterlein, Doris; Musat, Niculina; Otto, Matthias; Reemtsma, Thorsten; Richnow, Hans H; Daus, Birgit

    2016-09-01

    Increasing production of rare earth elements (REE) might lead to future contamination of the environment. REE have been shown to accumulate in high concentrations in roots of plants. Plant experiments with Zea mays exposed to a nutrient solution containing gadolinium (Gd) or yttrium (Y) with 10 mg L(-1) Gd or Y were carried out to investigate this accumulation behaviour. Total concentrations of 3.17 g kg(-1) and 8.43 g kg(-1) of Gd and Y were measured in treated plant roots. Using a novel combination of laser ablation mass spectrometry and time-of-flight secondary ion mass spectrometry, imaging of location and concentration of Gd and Y was carried out in root thin sections of treated roots. Single spots of elevated REE concentration were found at the epidermis, while inside the cortex, weak signals of Gd(+) and Y(+) were aligning with the root cell structures. The composition of Gd-containing secondary ions proves an REE-oxide phase accumulated at the epidermis, limiting REE availability for further uptake.

  15. Evaluating the Age of Buried Ice in Antarctica Using Ashfall Deposits: New Insights from Deposit Morphology, Grain Shape, and LA-ICP-MS Trace-Element Geochemistry

    NASA Astrophysics Data System (ADS)

    Lewis, A. R.; Marchant, D. R.

    2003-12-01

    Dating of buried ice in the western Dry Valleys region relies on 40Ar/39Ar analysis of ashfall deposits within sublimation tills that rest directly on stagnant glacier ice. The oldest ice so dated is >8.1 Ma. The fundamental assumption is that dated ashes are in-situ and have not been transported from surface deposits elsewhere in the Dry Valleys region. Given that the surface of sublimation tills shows well-developed patterned ground, the presumption of ground stability and long-term preservation of in-situ ashfall is questioned. As a test of ground stability, we examined ash-deposit morphology, grain shape, and glass-shard trace-element geochemistry from several ashfall deposits used to provide limiting ages on buried ice and tills in the western Dry Valleys. Detailed field analyses show that ashfall that collects in sublimation tills over buried ice occurs in one of three morphologic settings: surface troughs that delineate sand-wedge polygons, void spaces in gravel-and-cobble lags that overlie active sand wedges, and 1 to 2-cm-wide thermal contraction cracks. Post-depositional sublimation of underlying ice may distort initial deposit morphology through uneven surface lowering. Microscopic analyses of concentrated ashfall deposits that lack detrital sand grains show highly angular glass shards that preserve delicate hair-like spires and thin bubble-wall vesicles. Grain edges are sharp with no chipped, fractured, or pitted surfaces. In contrast, ash deposits containing detrital sand grains show subangular to subrounded shard morphologies with concave fractures and pits on grain edges, all of which are suggestive of abrasion during transport. In such deposits, grains preserving delicate bubble walls and hair-like spires are conspicuously absent. Laser ablation-inductively coupled plasma-mass spectrometry shows that glass shards within each ashfall deposit have uniform trace-element geochemical signatures. If ashfall were eroded and transported after initial

  16. Provenance of lateritic bauxite deposits in the Wuchuan-Zheng'an-Daozhen area, Northern Guizhou Province, China: LA-ICP-MS and SIMS U-Pb dating of detrital zircons

    NASA Astrophysics Data System (ADS)

    Gu, Jing; Huang, Zhilong; Fan, Hongpeng; Ye, Lin; Jin, Zhongguo

    2013-07-01

    The provenance of the large and super-large scale bauxite deposits developed in the Wuchuan-Zheng'an-Daozhen (WZD) alumina metallogenic province in the Yangtze Block of South China is poorly understood. LA-ICP-MS and SIMS U-Pb dating of detrital zircons from bauxite ores and the underlying Hanjiadian Group in the WZD area provide new constrains on the provenance of the WZD bauxite and provide new insight on the bauxite ore-forming process. The ages of the detrital zircons in the bauxites and the zircons in the Hanjiadian Group are similar suggesting that the bauxites are genetically related to the Hanjiadian sediments. The detrital zircon populations of the four samples studied show four primary age peaks: 2600-2400 Ma, 1900-1700 Ma, 1300-700 Ma and 700-400 Ma. The age distribution of detrital zircons indicates that they are probably derived from various sources including Neoproterozoic, Mesoproterozoic, Paleoproterozoic, Archean and some minor Paleozoic sources. The most abundant age population contains a continuous range of ages from 1300 to 700 Ma, ages consistent with subduction-related magmatic activities (1000-740 Ma) along the western margin of the Yangtze Block and the worldwide Grenville orogenic events (1300-1000 Ma). Thus, it is suggested that the main provenances of the WZD bauxite and the Hanjiadian Group are the Neoproterozoic igneous rocks in the western Yangtze Block and the Grenville-age igneous rocks in the southern Cathaysia Block. In addition, this work verifies that the global Grenville orogenic events and subduction-related magmatic activities associated with the Yangtze Block had a significant influence on the formation of the WZD bauxite deposits.

  17. Tectonic attribution of the Langshan area in western Inner Mongolia and implications for the Neoarchean-Paleoproterozoic evolution of the Western North China Craton: Evidence from LA-ICP-MS zircon U-Pb dating of the Langshan basement

    NASA Astrophysics Data System (ADS)

    Wang, Zeng-Zhen; Han, Bao-Fu; Feng, Li-Xia; Liu, Bo; Zheng, Bo; Kong, Ling-Jie

    2016-09-01

    The Langshan area in western Inner Mongolia, China, is situated on the conjunction of the Alxa Block in the west, the northern North China Craton (NCC) in the east, and the Central Asian Orogenic Belt in the north, but its tectonic attribution has long been in debate, because the Alxa Block may be an independent Precambrian block from the NCC and the boundary between the two blocks may lie along the Bayanwulashan, to the west of the Langshan, instead of around the Helanshan area, to the east of the Langshan. In this study, new LA-ICP-MS zircon U-Pb ages of four gneisses, one amphibolite, and three granites, combined with previously published age data from Langshan basement rocks, indicate that the Langshan area may be subdivided into the Main Langshan, to the north of a series of NNW-trending faults, and the Southern Langshan in the south. The Main Langshan basement rocks were mainly formed during Neoarchean-Paleoproterozoic, with five major stages of 2.7 Ga (2686 Ma), 2.6 Ga (2619-2563 Ma), 2.5 Ga (2534-2491 Ma), 1.95 Ga (1969-1938 Ma), and 1.7 Ga (1672 Ma). These stages are largely consistent with the major tectonothermal events of the northern NCC during Neoarchean-Paleoproterozoic but significantly different from the principal formation period (ca. 2.5-1.9 Ga) of Alxa basement rocks. The Southern Langshan is characterized by the presence of late Paleoproterozoic ( 1.9 Ga) and Neoproterozoic ( 0.9 Ga) rocks, and the latter is consistent with the Neoproterozoic magmatism in central Alxa Block, which might be formed in a orogenesis-related compressional environment, in contrast to contemporaneous rift-related extensional tectonic setting within the NCC. Therefore, the Main Langshan and the Southern Langshan are most likely closely related to the northern NCC and the Alxa Block, respectively.

  18. Advances in Quantitative Analyses and Reference Materials Related to Laser Ablation ICP-MS: A Look at Methods and New Directions

    NASA Astrophysics Data System (ADS)

    Koenig, A. E.; Ridley, W. I.

    2009-12-01

    The role of laser ablation ICP-MS (LA-ICP-MS) continues to expand both in geological sciences and other fields. As the technique continues to gain popularity, so too does the need for good reference materials and methods development and validation. Matrix matched reference materials (RMs) are required for calibration and quality control of LA-ICP-MS analyses. New advances in technology such as <200nm lasers and femtosecond lasers have reduced the dependence on matrix matching to some degree, but general matrix matching is still preferred. Much work has revolved around the available RMs such as the NIST 61x silicate glasses and several series of basaltic composition glasses such as the USGS natural basaltic glasses BCR-2g and synthetic basaltic glasses, the GS series (e.g. GSD-1g). While many quantitative hurdles have been recognized by analogous techniques such as EPMA and SIMS, some of these hurdles have not been fully addressed or validated for some cases of LA-ICP-MS. Trace element mapping by LA-ICP-MS is rapidly becoming more widespread for samples. Here relative differences in raw signal can be easily and rapidly obtained. However as too often is the case the magnitude of the relative differences in raw intensity are a function of different ablation yields, sample density or other factors. Methods of quantification for trace element mapping will be presented. The USGS has been developing microanalytical RMs intended for LA-ICP-MS for several years. The widely popular basaltic rock powders BCR-2, BIR-1 and BHVO-2 have all been successfully converted to homogeneous glasses suitable for LA-ICP-MS and have been in use by many workers. The newer synthetic basaltic glass GS series consists of 4 glasses of basaltic composition artificially doped at nominal concentrations of almost of trace elements at 400, 40, 4 and < 1 ppm. Additional developments in non-silcate or basaltic materials include the previously released MASS-1 Cu, Fe, Zn sulfide calibration RM (Wilson et

  19. Characterization of depositional age and structure of sedimentary successions by U-Pb TIMS and LA-ICP-MS dating of volcanic horizons and detrital zircons: an example from the western Trondheim Nappe Complex, Scandinavian Caledonides

    NASA Astrophysics Data System (ADS)

    Gasser, Deta; Grenne, Tor; Corfu, Fernando; Eivind Augland, Lars

    2016-04-01

    Revealing the absolute depositional age of non-fossiliferous sedimentary successions represents a long-lasting challenge in Earth Sciences. Lacking age control hampers the correct interpretation of the temporal evolution of depositional systems, and, if deformed, of the architecture of fold-and-thrust belts. Dating of detrital zircons within clastic sedimentary successions has over the past decades become a popular method to approximate the absolute depositional age and to characterize the source areas of such rocks. If combined with other geochronological information, such as dating of contemporaneous volcanic horizons, a much better resolution of the stratigraphy and structure of non-fossiliferous sedimentary successions can be achieved. The western Trondheim nappe complex in the central Scandinavian Caledonides is a classical area in this respect. On top of Late Cambrian to Early Ordovician ophiolitic fragments, various volcanic, volcano-clastic and clastic successions tell a complex story of island-arc formation, ocean closure and continent collision. Several famous fossil horizons indicate deposition during the Middle to Upper Ordovician (ca. 470-445 Ma), but large areas lack an absolute age control and several contrasting stratigraphic schemes and structural interpretations have been presented in the past. In this contribution we present the results of LA-ICP-MS detrital U-Pb zircon dating of clastic horizons as well as U-Pb TIMS zircon dating of volcanic horizons and magmatic clasts in conglomerates in order to characterize the depositional age and structure of the western Trondheim nappe complex in more detail. Together with field observations, including way up criteria, the zircon data enable significant revisions of existing stratigraphic and structural models. At least four (volcano-)sedimentary successions can be distinguished above the ca. 480-485 Ma greenstones: (1) ca. 470-463 Ma shales, limestones and andesitic porphyrites (Hølonda and Fanabekken

  20. U-Pb LA-ICP-MS detrital zircon ages from the Cambrian of Al Qarqaf Arch, central-western Libya: Provenance of the West Gondwanan sand sea at the dawn of the early Palaeozoic

    NASA Astrophysics Data System (ADS)

    Altumi, Muftah Mahmud; Elicki, Olaf; Linnemann, Ulf; Hofmann, Mandy; Sagawe, Anja; Gärtner, Andreas

    2013-03-01

    Detrital zircons from various stratigraphic levels of the sandstone-dominated Cambrian Hasawnah Formation of the Al Qarqaf Arch type area (central-western Libya, Saharan Metacraton area) were geochronologically investigated for the first time by LA-ICP-MS techniques for U, Th, and Pb isotopes. Of 720 analyzed grains, 329 were concordant. Of the total, about 60% of the U-Pb zircon ages are Neoproterozoic and earliest Cambrian and cluster at c. 700-680, 670-650, 615-610, 590, 570-560, and c. 540-525 Ma. These zircon populations are interpreted as detrital material derived from the Pan-African and possibly to a smaller proportion from the Cadomian orogen situated marginal to northwestern Gondwana. A few slightly older Neoproterozoic ages (c. 950-750 Ma) point to rifting events related to the dispersal of the Rodinia supercontinent. A minority of zircons became formed during the configuration of Rodinia and cluster around the Mesoproterozoic-Neoproterozoic boundary (1039 ± 11, 1006 ± 12 and 993 ± 13 Ma). Further, some early Mesoproterozoic zircon ages had been found (1592 ± 39 and 1475 ± 20 Ma). The potential source area for the Mesoproterozoic zircons is interpreted to have been far distant from the Al Qarqaf Arch, probably concealed within the Arabian-Nubian Shield or situated in Chad, or in the Congo and Tanzania cratons. There is still no evidence for the existence of massive Mesoproterozoic crust in the Saharan Metacraton area. A considerable proportion (28%) of zircons represents Palaeoproterozoic populations at c. 2.4-2.3 Ga, and c. 2.2-1.6 Ga. Less than 5% of all zircons are Archaean in age (c. 3.4-3.25 Ga, c. 2.95-2.7 Ga, c. 2.6-2.5 Ga). A potential source area for Palaeoproterozoic and Archaean zircon grains is the West African Craton and the western part of the Saharan Metacraton. The best candidates for the main source region for the sandstones of the Hasawnah Formation in the Al Qarqaf Arch type area are the Neoproterozoic-early Cambrian orogens of

  1. Quantitative imaging of gold and silver nanoparticles in single eukaryotic cells by laser ablation ICP-MS.

    PubMed

    Drescher, Daniela; Giesen, Charlotte; Traub, Heike; Panne, Ulrich; Kneipp, Janina; Jakubowski, Norbert

    2012-11-20

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was utilized for spatially resolved bioimaging of the distribution of silver and gold nanoparticles in individual fibroblast cells upon different incubation experiments. High spatial resolution was achieved by optimization of scan speed, ablation frequency, and laser energy. Nanoparticles are visualized with respect to cellular substructures and are found to accumulate in the perinuclear region with increasing incubation time. On the basis of matrix-matched calibration, we developed a method for quantification of the number of metal nanoparticles at the single-cell level. The results provide insight into nanoparticle/cell interactions and have implications for the development of analytical methods in tissue diagnostics and therapeutics.

  2. Laser-ablation ICP-MS as a tool for whole rock trace element analyses on fused powders

    NASA Astrophysics Data System (ADS)

    Girard, G.; Rooney, T. O.

    2013-12-01

    Here we present an accurate and precise technique for routine trace element analysis of geologic materials by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We focus on rock powders previously prepared for X-ray fluorescence by fusion in a Li2B4O7 flux, and subsequently quenched in a Pt mold to form a glass disk. Our method allows for the analysis up to 30 trace elements by LA-ICP-MS using a Photon-Machines Analyte G2 193 nm excimer laser coupled to a Thermo-Fisher Scientific ICAP Q quadrupole ICP-MS. Analyses are run as scans on the surface of the disks. Laser ablation conditions for which trace element fractionation effects are minimal have been empirically determined to be ~ 4 J m-2 fluence, at 10 Hz , and 10 μm s-1 scan speed, using a 110 μm laser beam size. Ablated material is carried into the ICP-MS by a He carrier at a rate of 0.75 L min-1. Following pre-ablation to remove surface particles, samples are ablated for 200 s, of which 140 s are used for data acquisition. At the end of each scan, a gas blank is collected for 30 s. Dwell times for each element vary between 15 and 60 μs, depending on abundance and instrument sensitivity, allowing 120 readings of each element during the data acquisition time window. To correct for variations in the total volume of material extracted by the laser, three internal standards are used, Ca, Fe and Zr. These elements are routinely analyzed by X-ray fluorescence by the Geoanalytical laboratory at Michigan State University with precision and accuracy of <5%. The availability of several internal standards allows for better correction of possible persisting laser ablation fractionation effects; for a particular trace element, we correct using the internal standard that best reproduces its ablation behavior. Our calibration is based on a combination of fused powders of US Geological Survey and Geological Survey of Japan rock standards, NIST SRM 612 glass, and US Geological Survey natural and

  3. Trace isotope analysis of Ricinus communis seed core for provenance determination by laser ablation-ICP-MS.

    PubMed

    Bagas, Christina K; Scadding, Rachel L; Scadding, Cameron J; Watling, R John; Roberts, Warren; Ovenden, Simon P B

    2017-01-01

    The castor bean plant, Ricinus communis, grows wild throughout many regions of Australia. The seeds of the plant contain the schedule 1 chemical agent ricin, a type II ribosomal inhibiting protein. Currently there are limited analytical techniques that can be applied in analysis of the seeds to establish attribution. In this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the analysis of seeds collected from 68 plants across 38 locations around Australia. Of the 92 elemental isotopes measured, fifteen ((24)Mg, (27)Al, (44)Ca, (53)Cr, (55)Mn, (57)Fe, (60)Ni, (65)Cu, (66)Zn, (75)As, (85)Rb, (88)Sr, (98)Mo, (138)Ba and (202)Hg) yielded data that were relevant to all collection sites. Data were further analysed using multivariate statistical analysis which facilitated the potential for the identification of unique provenance isotopes. Furthermore, this analysis indicated that (59)Co was present at significant levels in Victorian and Sydney specimens only.

  4. Sediment profiles of less commonly determined elements measured by Laser Ablation ICP-MS.

    PubMed

    Dolor, Marvourneen K; Helz, George R; McDonough, William F

    2009-01-01

    Anthropogenic influences on trace element profiles in dated sediments from estuaries have been often documented, with the vast majority of studies focusing on a short list of high-abundance trace elements. Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) provides a new approach that minimizes sample preparation and contamination while yielding data on a much larger list of elements simultaneously. We present concentrations and enrichment factor profiles for 22 elements at a locality that is 50 km southeast of Baltimore, the principal industrial city on Chesapeake Bay. Samples representing deposition over almost the entire 20th century were obtained from two archived cores collected 20 years apart. The following elements exhibit profiles consistent with a strong anthropogenic influence, i.e. enrichment after 1920 followed by decline after ca.1980, possibly reflecting increased regulatory efforts: Mn, Co, Cu, Zn, Ag, Cd, In, Sn, Sb, Te, Tl, Pb and Bi. As expected, the redox-sensitive elements: Mo, Re and U have similar profiles to one another. Previously, the potentially hazardous elements, Ag, In, Sb, Te, Tl and Bi, have been measured only rarely in estuarine sediments and never in Chesapeake Bay. Our discovery that their profiles track those of well-known pollutants underscores a need to investigate their sources, transport and biogeochemical behavior. Several rarely determined trace elements, Ga, Ge and Nb, exhibit trendless profiles, as do the major elements, Ti and Fe.

  5. A laser ablation ICP-MS based method for multiplexed immunoblot analysis: applications to manganese-dependent protein dynamics of photosystem II in barley (Hordeum vulgare L.).

    PubMed

    de Bang, Thomas Christian; Petersen, Jørgen; Pedas, Pai Rosager; Rogowska-Wrzesinska, Adelina; Jensen, Ole Noerregaard; Schjoerring, Jan Kofod; Jensen, Poul Erik; Thelen, Jay J; Husted, Søren

    2015-08-01

    Manganese (Mn) constitutes an essential co-factor in the oxygen-evolving complex of photosystem II (PSII). Consequently, Mn deficiency reduces photosynthetic efficiency and leads to changes in PSII composition. In order to study these changes, multiplexed protein assays are advantageous. Here, we developed a multiplexed antibody-based assay and analysed selected PSII subunits in barley (Hordeum vulgare L.). A selection of antibodies were labelled with specific lanthanides and immunoreacted with thylakoids exposed to Mn deficiency after western blotting. Subsequently, western blot membranes were analysed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), which allowed selective and relative quantitative analysis via the different lanthanides. The method was evaluated against established liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) methods, based on data-dependent acquisition (DDA) and selected reaction monitoring (SRM). Manganese deficiency resulted in a general decrease in PSII protein abundances, an effect that was shown to be reversible upon Mn re-supplementation. Specifically, the extrinsic proteins PsbP and PsbQ showed Mn-dependent changes in abundances. Similar trends in the response to Mn deficiency at the protein level were observed when comparing DDA, SRM and LA-ICP-MS results. A biologically important exception to this trend was the loss of PsbO in the SRM analysis, which highlights the necessity of validating protein changes by more than one technique. The developed method enables a higher number of proteins to be multiplexed in comparison to existing immunoassays. Furthermore, multiplexed protein analysis by LA-ICP-MS provides an analytical platform with high throughput appropriate for screening large collections of plants.

  6. Trace elemental analysis of glass and paint samples of forensic interest by ICP-MS using laser ablation solid sample introduction

    NASA Astrophysics Data System (ADS)

    Almirall, Jose R.; Trejos, Tatiana; Hobbs, Andria; Furton, Kenneth G.

    2003-09-01

    The importance of small amounts of glass and paint evidence as a means to associate a crime event to a suspect or a suspect to another individual has been demonstrated in many cases. Glass is a fragile material that is often found at the scenes of crimes such as burglaries, hit-and-run accidents and violent crime offenses. Previous work has demonstrated the utility of elemental analysis by solution ICP-MS of small amounts of glass for the comparison between a fragment found at a crime scene to a possible source of the glass. The multi-element capability and the sensitivity of ICP-MS combined with the simplified sample introduction of laser ablation prior to ion detection provides for an excellent and relatively non-destructive technique for elemental analysis of glass fragments. The direct solid sample introduction technique of laser ablation (LA) is reported as an alternative to the solution method. Direct solid sampling provides several advantages over solution methods and shows great potential for a number of solid sample analyses in forensic science. The advantages of laser ablation include the simplification of sample preparation, thereby reducing the time and complexity of the analysis, the elimination of handling acid dissolution reagents such as HF and the reduction of sources of interferences in the ionization plasma. Direct sampling also provides for essentially "non-destructive" sampling due to the removal of very small amounts of sample needed for analysis. The discrimination potential of LA-ICP-MS is compared with previously reported solution ICP-MS methods using external calibration with internal standardization and a newly reported solution isotope dilution (ID) method. A total of ninety-one different glass samples were used for the comparison study using the techniques mentioned. One set consisted of forty-five headlamps taken from a variety of automobiles representing a range of twenty years of manufacturing dates. A second set consisted of forty

  7. Mass spectrometry imaging (MSI) of metals in mouse spinal cord by laser ablation ICP-MS.

    PubMed

    Becker, J Sabine; Kumtabtim, Usarat; Wu, Bei; Steinacker, Petra; Otto, Markus; Matusch, Andreas

    2012-03-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been developed as a powerful MS imaging (MSI) tool for the direct investigation of element distributions in biological tissues. Here, this technique was adapted for the analysis of native mouse spinal cord cryosections of 3.1 mm × 1.7 mm by implementing a new conventional ablation system (NWR-213) and improving the spatial resolution from 120 μm to 65 μm in routine mode. Element images of the spinal cord are provided for the first time and the metalloarchitecture was established using a multimodal atlas approach. Furthermore, the spatial distribution of Rb was mapped for the first time in biological tissue. Metal concentrations were quantified using matrix-matched laboratory standards and normalization of the respective ion intensities to the average (13)C ion intensity of standards and samples as a surrogate of slice thickness. The "butterfly" shape of the central spinal grey matter was visualized in positive contrast by the distributions of Fe, Mn, Cu and Zn and in negative contrast by C and P. Mg, Na, K, S and Rb showed a more homogenous distribution. The concentrations averaged throughout grey matter and white matter were 8 and 4 μg g(-1) of Fe, 3 and 2 μg g(-1) of Cu, 8 and 5 μg g(-1) of Zn, 0.4 and 0.2 μg g(-1) of Mn. The carbon concentration in white matter exceeded that of grey matter by a factor of 1.44. Zn and Cu at 9 and 4 μg g(-1), respectively, were particularly enriched in the laminae I and II, in line with the high synaptic and cellular density there. Surprisingly Zn but not Cu was enriched in the central channel. Rb occurred at 0.3 μg g(-1) with a distribution pattern congruent to that of K. The coefficients of variation were 6%, 5%, 8% and 10% for Fe, Cu, Zn and Mn, respectively, throughout three different animals measured on different days. These MSI analyses of healthy wild type spinal cords demonstrate the suitability of the established techniques for

  8. Determination of trace elements in zeolites by laser ablation ICP-MS.

    PubMed

    Pickhardt, C; Brenner, I B; Becker, J S; Dietze, H J

    2000-09-01

    Laser ablation inductively coupled plasma mass spectrometry using a quadrupole-based mass spectrometer (LA-ICP-QMS) was applied for the analysis of powdered zeolites (microporous aluminosilicates) used for clean-up procedures. For the quantitative determination of trace element concentrations three geological reference materials, granite NIM-G, lujavrite NIM-L and syenite NIM-S, from the National Institute for Metallurgy (South Africa) with a matrix composition corresponding to the zeolites were employed. Both the zeolites and reference materials were fused with a lithium borate mixture to increase the homogeneity and to eliminate mineralogical effects. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS relative sensitivity coefficients (RSCs) of chemical elements and calibration curves were measured using the geostandards. The experimentally obtained RSCs are in the range of 0.2-6 for all elements of interest. Calibration curves for trace elements were measured without and with Li or Ti as internal standard element. With a few exceptions the regression coefficients of the calibration curves are better than 0.993 with internal standardization. NIM-G granite reference material was employed to evaluate the accuracy of the technique. Therefore, the measured concentrations were corrected with RSCs which were determined using lujavrite reference material NIM-L. This quantification method provided analytical results with deviations of 1-11% from the recommended and proposed values in granite reference material NIM-G, except for Co, Cs, La and Tb. The relative standard deviation (RSD) of the determination of the trace element concentration (n = 5) is about 1% to 6% using Ti as internal standard element. Detection limits of LA-ICP-QMS in the lower microg/g range (from 0.03 microg/g for Lu, Ta and Th to 7.3 microg/g for Cu, with the exception of La) have been achieved for all elements of interest. Under the laser ablation

  9. New Possibilities for the Accurate in Situ Determination of Chalcophile and Siderophile Trace Elements by Laser Ablation Collision and Reaction Cell ICP-MS

    NASA Astrophysics Data System (ADS)

    Mason, P. R.

    2004-05-01

    Our knowledge of how chalcophile and siderophile elements partition in minerals is limited, mainly due to the lack of suitable techniques for their accurate in situ determination. Host minerals (e.g. sulphides) are typically of small size (<30 μ m) and highly heterogeneous in composition, requiring analysis of high spatial resolution. Concentrations of chalcophile elements in silicates and oxides are low (sub μ gg-1) and thus challenging to measure. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), offering high sensitivity and good spatial resolution (10-100 μ m) is thus highly suited for this purpose. Unfortunately, the widespread use of this technique has been limited by enhanced problems specific to chalcophile and siderophile elements. These include inaccuracy due to the presence of spectral interferences, elemental fractionation during ablation/ionization and the lack of suitable calibration standards. Polyatomic spectral interferences, present either as a background component (e.g. O2+, ArAr+) or based around the recombination of matrix elements with argon (e.g. ArS+, ArNi+) hinder accurate analysis. These depend upon the relative concentrations of major matrix components and trace elements to be measured and are significant in many relevant minerals (e.g. sulphides). The use of a collision and reaction cells in ICP-MS is a new method for selective interference attenuation, significantly improving detection limits for elements such as Fe, S and Se by between 1 and 4 orders of magnitude. ArNi+ and ArCu+ interferences in sulphides can be attenuated by at least an order of magnitude leading to improved accuracy for the measurement of the Platinum Group elements Rh and Ru. Sulphur isotopes can be measured interference-free at m/z=32 and 34 by eliminating background O2+. These improvements open up new possibilities for the use of LA-ICP-MS in trace element and isotopic studies at the lowest concentration levels or where sample

  10. Laser ablation ICP-MS and traditional micromorphological techniques applied to the study of different genetic horizons in thin sections: soil genesis and trace element distribution

    NASA Astrophysics Data System (ADS)

    Scarciglia, Fabio; Barca, Donatella; de Rosa, Rosanna; Pulice, Iolanda; Vacca, Andrea

    2010-05-01

    This work focuses on an innovative methodological approach to investigate in situ chemical composition of trace and rare earth (REE) elements in discrete soil features from different soil horizons: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied to clay coatings, pedogenic matrix and skeletal parent rock fragments in thin sections, coupled with traditional pedological investigations, specially clay mineralogy and micromorphology. Analyses were performed on 80 μm-thick sections obtained from undisturbed soil samples, which represent three reddish argillic (Bt) horizons from an Alfisol developed on late Pleistocene slope deposits and three brown organic-mineral (A) horizons from an Entisol formed on Holocene aggrading fluvial sediments in the Muravera area (southeast Sardinia, Italy). Validation of the LA-ICP-MS technique provides in situ accurate and reproducible (RSD 13-18%) analysis of low concentration trace elements in the studied soil samples (0.001-0.1 ppm). Our results showed a high reliability of this method on soil thin sections and revealed that concentrations of trace and rare earth elements in the different portions of a soil profile can be used to investigate their distribution, as a response to soil-forming processes. A general trend of increase of most trace elements from rock fragments to (both clayey and organic-rich) soil matrix, to clay coatings in argillic horizons is clearly highlighted. On this basis a prominent role of pedogenetic processes in element fractionation and distribution during weathering can be supposed. In particular, element adsorption onto reactive sites of organic matter and clay particles (and possibly Fe-oxyhydroxides) and clay illuviation appear the main pedogenetic processes able to promote element enrichment after their release from the weathering of primary minerals. As clay coatings exhibit the highest concentration of trace elements, and specifically of REEs, and represent the most

  11. DURIP - Acquisition of an Inductively-Coupled Plasma Mass Spectrometer with Laser Ablation Source for Surface Characterization

    DTIC Science & Technology

    2010-12-24

    allows low interference which reduces common polyatomic interferences on As, Se, Cr, V and Fe, thus achieving lower detection limits in the plasma...Formerly Varian) 820 ICP-MS Ion Optics Soft Landed Hf on Si SEM Image of ablation track 178Hf LA-ICP-MS transient signals showing spatially resolved Hf on surface (left) and in defects (right)

  12. Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS for isotope analysis of long-lived radionuclides

    NASA Astrophysics Data System (ADS)

    Becker, J. Sabine

    2005-04-01

    For a few years now inductively coupled plasma mass spectrometry has been increasingly used for precise and accurate determination of isotope ratios of long-lived radionuclides at the trace and ultratrace level due to its excellent sensitivity, good precision and accuracy. At present, ICP-MS and also laser ablation ICP-MS are applied as powerful analytical techniques in different fields such as the characterization of nuclear materials, recycled and by-products (e.g., spent nuclear fuel or depleted uranium ammunitions), radioactive waste control, in environmental monitoring and in bioassay measurements, in health control, in geochemistry and geochronology. Especially double-focusing sector field ICP mass spectrometers with single ion detector or with multiple ion collector device have been used for the precise determination of long-lived radionuclides isotope ratios at very low concentration levels. Progress has been achieved by the combination of ultrasensitive mass spectrometric techniques with effective separation and enrichment procedures in order to improve detection limits or by the introduction of the collision cell in ICP-MS for reducing disturbing interfering ions (e.g., of 129Xe+ for the determination of 129I). This review describes the state of the art and the progress of ICP-MS and laser ablation ICP-MS for isotope ratio measurements of long-lived radionuclides in different sample types, especially in the main application fields of characterization of nuclear and radioactive waste material, environmental research and health controls.

  13. LA ICP MS and Ion Probe U-Pb dating of igneous and metasedimentary units in the NE Pontides, NE Turkey: evidence of Peri-Gondwanan terrane accretion, Late Palaeozoic magmatism/metamorphism and Early Mesozoic extension along the S Eurasian margin

    NASA Astrophysics Data System (ADS)

    Ustaömer, Timur; Robertson, Alastair H. F.; Gerdes, Axel; Ayda Ustaömer, P.

    2010-05-01

    The Artvin area is critical to an understanding of the tectonic development of the S margin of Eurasia and Tethys to the south. We have supplemented recent MTA mapping with 1/25,000-scale mapping of a critical area, combined with integrated stratigraphical, sedimentary, geochemical and geochronological studies. Here, we focus on U-Pb zircon dating of igneous and detrital zircons derived from basement units of the Pontide Autocthon and from overlying slice complexes, carried out by LA ICP MS at Frankfurt University and by Ion Probe at Edinburgh University. The Eastern Pontide Autocthon is overlain by north-vergent thrust sheets, mostly of continental margin origin, whereas Mesozoic (Neotethyan) ophiolites form the uppermost thrust sheet. The Autochton basement (Çamlıkaya pluton) is mainly tonalite, cut by granitic dykes. Both intrusions are of within-plate type, without a chemically identifiable subduction influence. The pluton yielded a concordant age of 330.4 ± 4.2 Ma (Visean), while crosscutting dykes gave an age of 156.3 ± 2.0 Ma (Oxfordian). The overlying lower slice complex (Slice 1) begins with a low-grade meta-clastic basement unit, intruded by coarse-grained granite. Detrital zircons from the meta-clastics yielded late Neoproterozoic (579-700), early Neoproterozoic (0.9 Ga) and Kibaran/Grenvillian (1.1-1.3 Ga) zircon populations. The oldest known zircon has an age of 2719 Ma. Slice 2 above this (Demirkent Intrusive Complex) is represented by foliated amphibolites, cut by granitic veins and, together, cut by swarms of basic-silicic dykes that postdate regional metamorphism and related deformation. A granitic vein yielded a concordia age of 325.4 ± 2.8 Ma (Visean-Serpukhovian). Slice 2 was intruded by two small tonalitic bodies, one of which yielded a concordant age of 179.8 ± 1 Ma (Toarcian). Slice 3 above this begins with granulite-facies gneiss and schist (Karadağ Metamorphics). A representative 1 m-wide meta-granitic stock within paragneiss

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

    NASA Astrophysics Data System (ADS)

    Subedi, Kiran; Trejos, Tatiana; Almirall, José

    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.

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

    SciTech Connect

    Witte, Travis

    2011-01-01

    This dissertation provides a general introduction to Inductively coupled plasma-mass spectrometry (ICP-MS) and laser ablation (LA) sampling, with an examination of analytical challenges in the employment of this technique. It discusses the origin of metal oxide ions (MO+) in LA-ICP-MS, as well as the effect of introducing helium and nitrogen to the aerosol gas flow on the formation of these polyatomic interferences. It extends the study of polyatomic ions in LA-ICP-MS to metal argide (MAr+) species, an additional source of possible significant interferences in the spectrum. It describes the application of fs-LA-ICP-MS to the determination of uranium isotope ratios in particulate samples.

  16. Multivariate classification of edible salts: Simultaneous Laser-Induced Breakdown Spectroscopy and Laser-Ablation Inductively Coupled Plasma Mass Spectrometry Analysis

    NASA Astrophysics Data System (ADS)

    Lee, Yonghoon; Nam, Sang-Ho; Ham, Kyung-Sik; Gonzalez, Jhanis; Oropeza, Dayana; Quarles, Derrick; Yoo, Jonghyun; Russo, Richard E.

    2016-04-01

    Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), both based on laser ablation sampling, can be employed simultaneously to obtain different chemical fingerprints from a sample. We demonstrated that this analysis approach can provide complementary information for improved classification of edible salts. LIBS could detect several of the minor metallic elements along with Na and Cl, while LA-ICP-MS spectra were used to measure non-metallic and trace heavy metal elements. Principal component analysis using LIBS and LA-ICP-MS spectra showed that their major spectral variations classified the sample salts in different ways. Three classification models were developed by using partial least squares-discriminant analysis based on the LIBS, LA-ICP-MS, and their fused data. From the cross-validation performances and confusion matrices of these models, the minor metallic elements (Mg, Ca, and K) detected by LIBS and the non-metallic (I) and trace heavy metal (Ba, W, and Pb) elements detected by LA-ICP-MS provided complementary chemical information to distinguish particular salt samples.

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

    NASA Astrophysics Data System (ADS)

    Kaiser, J.; Galiová, M.; Novotný, K.; Červenka, R.; Reale, L.; Novotný, J.; Liška, M.; Samek, O.; Kanický, V.; Hrdlička, A.; Stejskal, K.; Adam, V.; Kizek, R.

    2009-01-01

    Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) were utilized for mapping the accumulation of Pb, Mg and Cu with a resolution up to 200 μm in a up to cm × cm area of sunflower ( Helianthus annuus L.) leaves. The results obtained by LIBS and LA-ICP-MS are compared with the outcomes from Atomic Absorption Spectrometry (AAS) and Thin-Layer Chromatography (TLC). It is shown that laser-ablation based analytical methods can substitute or supplement these techniques mainly in the cases when a fast multi-elemental mapping of a large sample area is needed.

  18. Comparison of laser ablation-inductively coupled plasma-mass spectrometry and micro-X-ray fluorescence spectrometry for elemental imaging in Daphnia magna.

    PubMed

    Gholap, Deepti S; Izmer, Andrei; De Samber, Björn; van Elteren, Johannes T; Selih, Vid S; Evens, Roel; De Schamphelaere, Karel; Janssen, Colin; Balcaen, Lieve; Lindemann, Inge; Vincze, Laszlo; Vanhaecke, Frank

    2010-04-01

    Visualization of elemental distributions in thin sections of biological tissue is gaining importance in many disciplines of biological and medical research. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and scanning micro-X-ray fluorescence spectrometry (micro-XRF) are two widely used microanalytical techniques for elemental mapping. This article compares the capabilities of the two techniques for imaging the distribution of selected elements in the model organism Daphnia magna in terms of detection power and spatial resolution. Sections with a thickness of 10 and 20 microm of the fresh water crustacean Daphnia magna were subjected to LA-ICP-MS and micro-XRF analysis. The elemental distributions obtained for Ca, P, S and Zn allow element-to-tissue correlation. LA-ICP-MS and micro-XRF offer similar limits of detection for the elements Ca and P and thus, allow a cross-validation of the imaging results. LA-ICP-MS was particularly sensitive for determining Zn (LOD 20 microg g(-1), 15 microm spot size) in Daphnia magna, while the detection power of micro-XRF was insufficient in this context. However, LA-ICP-MS was inadequate for the measurement of the S distributions, which could be better visualized with micro-XRF (LOD 160 microg g(-1), 5 s live time). Both techniques are thus complementary in providing an exhaustive chemical profiling of tissue samples.

  19. Advances in the measurement of sulfur isotopes using laser ablation MC-ICP- MS

    NASA Astrophysics Data System (ADS)

    Ridley, W. I.; Pribil, M. J.; Koenig, A. E.; Fayek, M.; Slack, J. F.

    2008-05-01

    Although sulfur is poorly ionized in an argon plasma, there are many applications for sulfur isotope analysis using an ICP source. Studies using a desolvation system (DSN) and an aqueous source of sulfur, where the sulfur is complexed with a cation to form a sulfur salt, e.g., calcium or sodium to provide a stable delivery of sulfur through the sample introduction system indicate that precision (~ 0.3 per mil) and accuracy are maintained at sulfur concentrations as low as 1 mg/L. Based on this data, solid sampling of sulfides and sulfates can provide an adequate amount supply of sulfur to an ICP source, even allowing for the relatively poor transport efficiency of laser ablation systems. The main limitations on accuracy and precision are the initial sampling volume, principally a function of spot size and laser fluence and the decreased instrument sensitivity resulting from the pseudo- medium or high resolution mode of analysis required to eliminate polyatomic isobaric interferences. These factors, in turn, determine the minimal grain size necessary for analysis. There are also fit-for-purpose considerations. For instance, many base metal sulfide systems have large variations in sulfur isotope composition, so that precision as poor as one per mil can still provide useful information. Here, we describe the methodology used at the USGS for laser ablation analysis of sulfides and sulfates using a second generation MC-ICP-MS and demonstrate the accuracy of the method based upon a grain-by-grain comparison of laser ablation and ion microprobe sulfur isotope data. A laser ablation MC-ICP-MS study of base metal mineralization at Dry Creek deposit, east-central Alaska demonstrates that the range in sulfur isotope composition of pyrite, sphalerite and galena, based on analysis of individual grains, is almost twice that reported for any other individual VMS deposit. Analysis on the microscopic scale thus provides additional insights into the potential sources of sulfur for

  20. Development of a non-denaturing 2D gel electrophoresis protocol for screening in vivo uranium-protein targets in Procambarus clarkii with laser ablation ICP MS followed by protein identification by HPLC-Orbitrap MS.

    PubMed

    Xu, Ming; Frelon, Sandrine; Simon, Olivier; Lobinski, Ryszard; Mounicou, Sandra

    2014-10-01

    Limited knowledge about in vivo non-covalent uranium (U)-protein complexes is largely due to the lack of appropriate analytical methodology. Here, a method for screening and identifying the molecular targets of U was developed. The approach was based on non-denaturing 1D and 2D gel electrophoresis (ND-PAGE and ND-2D-PAGE (using ND-IEF as first dimension previously described)) in conjunction with laser ablation inductively coupled plasma mass spectrometry (LA-ICP MS) for the detection of U-containing proteins. The proteins were then identified by µbore HPLC-Orbitrap MS/MS. The method was applied to the analysis of cytosol of hepatopancreas (HP) of a model U-bioaccumulating organism (Procambarus clarkii). The imaging of uranium in 2D gels revealed the presence of 11 U-containing protein spots. Six protein candidates (i.e. ferritin, glyceraldehyde-3-phosphate dehydrogenase, triosephosphate isomerase, cytosolic manganese superoxide dismutase (Mn-SOD), glutathione S transferase D1 and H3 histone family protein) were then identified by matching with the data base of crustacea Decapoda species (e.g. crayfish). Among them, ferritin was the most important one. This strategy is expected to provide an insight into U toxicology and metabolism.

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

    PubMed

    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

  2. Geochemistry of the Spor Mountain rhyolite, western Utah, as revealed by laser ablation ICP-MS, cathodoluminescence, and electron microprobe analysis

    NASA Astrophysics Data System (ADS)

    Dailey, S. R.; Christiansen, E. H.; Dorais, M.; Fernandez, D. P.

    2015-12-01

    The Miocene topaz rhyolite at Spor Mountain in western Utah hosts one of the largest beryllium deposits in the world and was responsible for producing 85% of the beryllium mined worldwide in 2010 (Boland, 2012). The Spor Mountain rhyolite is composed primarily of Ca-poor plagioclase (An8), sodic sanidine (Or40), Fe-rich biotite (Fe/(Fe+Mg)>0.95; Al 1.2-1.4 apfu), and Ti-poor quartz, along with several trace-element rich accessory phases including zircon, monazite, thorite, columbite, and allanite. Cathodoluminescence (CL) studies of quartz show oscillatory zoning, with 80% of the examined crystals displaying euhedral edges and slightly darker rims. CL images were used to guide laser ablation (LA) ICP-MS analysis of quartz, along with analyses of plagioclase, sanidine, biotite, and glass. Ti concentrations in quartz are 20±6 ppm; there is no quantifiable variation of Ti from core to rim within the diameter of the laser spot (53 microns). Temperatures, calculated using Ti in quartz (at 2 kb, aTiO2=0.34), vary between 529±10 C (Thomas et al., 2011), 669±13 C (Huang and Audetat, 2012), and 691±13 C (Wark and Watson, 2006). Two feldspar thermometry yield temperatures of 686±33 C (Elkins and Grove, 1990) and 670±41 C (Benisek et al., 2010). Zr saturation temperatures (Watson and Harrison, 1983) average 711±28 C. Analysis of the glass reveal the Spor Mountain rhyolite is greatly enriched in rare elements (i.e. Li, Be, F, Ga, Rb, Nb, Mo, Sn, and Ta) compared to average continental crust (Rudnick and Gao, 2003). Be in the glass can have as much as 100 ppm, nearly 50 times the concentration in continental crust. REE partition coefficients for sanidine are 2 to 3 times higher in the Spor Mountain rhyolite when compared to other silicic magmas (Nash and Crecraft, 1985; Mahood and Hildreth, 1983), although plagioclase tends to have lower partition coefficients; biotite has lower partition coefficients for LREE and higher partition coefficients for HREE. The patterns of

  3. Precious metal enrichment at low-redox in terrestrial native Fe-bearing basalts investigated using laser-ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Howarth, Geoffrey H.; Day, James M. D.; Pernet-Fisher, John F.; Goodrich, Cyrena A.; Pearson, D. Graham; Luo, Yan; Ryabov, Viktor V.; Taylor, Lawrence A.

    2017-04-01

    Primary native Fe is a rare crystallizing phase from terrestrial basaltic magmas, requiring highly reducing conditions (fO2 ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), are lowest in the Bühl basalt, (∼0.05 ppm), intermediate in the Disko Island basalts (4-8 ppm), and highest the Siberian Khungtukun and Dzhaltul intrusions (10-30 ppm). These differences demonstrate that, while native Fe formation is the result of carbonaceous crustal assimilation, HSE enrichment is not ubiquitous during this process. The Siberian occurrences are characterized by Pt PGE (PPGE: Pt, Pd) enrichment relative to the Ir PGE (IPGE: Rh, Ru, Ir, Os), consistent with models of early stage fractionation of olivine, chromite and metallic IPGE in staging magma reservoirs, prior to the addition of C-rich crustal materials in the shallow crust. Relative to Noril'sk Ni-Cu-PGE sulfide ores

  4. High Spatial Resolution Analysis of Carbonates by In Situ Excimer Laser Ablation MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Shuttleworth, S.; Lloyd, N.; Douthitt, C.

    2012-12-01

    Speleothems are important climate archives. The time resolution of the paleochlimate proxies depends on the growth rates and the precision limitation of the analytical instrumentation [1]. As a consequence, for speleothems, better analytical precision combined with better spatial resolution will always be the goal, driven by a need to probe the timing and duration of climate events [1]. The Thermo Scientific NEPTUNE Plus with Jet Interface option offers unparalleled MC-ICP-MS sensitivity for heavy elements. An ion yield of >3 % has previously been reported for uranium solutions introduced by desolvating nebulizer[2]. For laser ablation Hf, the Jet Interface with N2 addition significantly improved sensitivity, which allowed precise and accurate 176Hf/177Hf ratios to be calculated using a spot size of just 25 μm diameter [3]. A Thermo Scientific NEPTUNE Plus with Jet Interface option was coupled with a Photon Machines excimer laser ablation system. This system features a short pulse width (4ns) 193 nm excimer laser and the HELEX 2 volume sample cell. The 193nm wavelength has been shown to reduce the particle size distribution of the aerosol produced by the laser ablation process [4] and this in turn has been shown to help minimize the effects of fractionation by ensuring that particles are in a size range so as to avoid incomplete vaporization and ionization in the plasma [5]. In this work we investigate U-Th dating of carbonates. Accurate LA U-Th isotope measurements on carbonates with U concentrations smaller than 1 μg/g are difficult due to small ion beams [1]. Hoffman et. al. [1] noted individual LA U-Th ratio precisions of about 2% (2 sigma) on a 134 ka sample with 134 μg/g U concentration. In this work we apply a combination of the high sampling efficiency two volume cell plus mixed gas plasmas to further enhance the capability. [1] Hoffman, D.L., et al. (2009). Chemical Geology. 259 253-261 [2] Bouman, C., et al. (2009). Geochim. Cosmochim. Acta. 73

  5. Speciation of iodine-containing proteins in Nori seaweed by gel electrophoresis laser ablation ICP-MS.

    PubMed

    Romarís-Hortas, V; Bianga, J; Moreda-Piñeiro, A; Bermejo-Barrera, P; Szpunar, J

    2014-09-01

    An analytical approach providing an insight into speciation of iodine in water insoluble fraction of edible seaweed (Nori) was developed. The seaweed, harvested in the Galician coast (Northwestern Spain), contained 67.7±1.3 μg g(-1) iodine of which 25% was water soluble and could be identifies as iodide. Extraction conditions of water insoluble residue using urea, NaOH, SDS and Triton X-100 were investigated. The protein pellets obtained in optimized conditions (after precipitation of urea extracts with acetone), were digested with trypsin and protease XIV. Size exclusion chromatography-ICP-MS of both enzymatic digests demonstrated the occurrence of iodoaminoacids putatively present in proteins. Intact proteins could be separated by gel electrophoresis after an additional extraction of the protein extract with phenol. Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS PAGE) with laser ablation ICP-MS detection of (127)I indicated the presence of iodine in protein bands corresponding to molecular masses of 110 kDa, 40 kDa, 27 kDa, 20 kDa and 10 kDa. 2D IEF-SDS PAGE with laser ablation ICP-MS (127)I imaging allowed the detection of 5 iodine containing protein spots in the alkaline pI range.

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

    USGS Publications Warehouse

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

    2009-01-01

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

  7. [Progress in combination of gel electrophoresis and laser ablation inductively coupled plasma mass spectrometry for trace elements determination in proteins].

    PubMed

    Wang, Ying; Guo, Yan-li; Yuan, Hong-lin; Wei, Yong-feng; Yan, Hong-tao; Chen, Hui-hui

    2012-01-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has become a very efficient and sensitive trace, ultratrace, and surface analytical technique for the in situ study of the concentration and distribution of the elements in life sciences with high spatial resolution. It is being used more and more frequently in biological, medical materials and protein research, which will lead to a better understanding of physiology and pathology process in cells and tissues. The present review mainly introduces the strategies of combination of gel electrophoresis (GE) with LA-ICP-MS for the quantification of trace elements in proteins, including the proteins separation, elements detection and calibration methods. The paper emphasizes the basic conditions of the proteins separation, focusing on the stability of proteins during GE and the treatment methods of staining and drying of the gel to enable successful detection of the elements by LA-ICP-MS. In addition, the application of GE-LA-ICP-MS in phosphoproteins, selenoproteins and metal-binding proteins is introduced in detail. The prospects and challenge for this technique are discussed as well for further study.

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

    PubMed

    Giussani, Barbara; Monticelli, Damiano; Rampazzi, Laura

    2009-03-02

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

  9. 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.

    PubMed

    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.

  10. Lengthy Ultrahigh-Pressure Metamorphism demonstrated by laser ablation split-stream ICP-MS

    NASA Astrophysics Data System (ADS)

    Kylander-Clark, A. R.; Hacker, B. R.; Ginsburg, A. A.; Spencer, K.

    2011-12-01

    There is much disagreement about the maximum duration of ultrahigh-pressure (UHP) events. Some have argued for >20 Myr timescales based on geochronology, whereas others have countered that such conclusions are unsound because of the likelihood of inherited age components or because the long reach of thermal conduction is likely to induce melting and assimilation of the UHP terrane into the mantle. To assess these two possibilities we analyzed accessory minerals from eclogites and HP gneisses in the Western Gneiss Region of Norway using laser ablation split-stream (LASS) ICP-MS. LASS allows concurrent collection of trace, rare-earth element (REE), and U-Th-Pb data to directly link metamorphic conditions with the age of each spot analysis. Zircons from eclogite yield garnet-stable U-Pb ages (as shown by depressed HREE signatures) from as early as ~450 Ma, to as late as ~400 Ma; the bulk of these ages span 425-402 Ma. Monazites from grt-ky gneisses yield U-Pb and Th-Pb ages from 425-386 Ma and HREE, Eu*, Y and Sr contents that imply garnet growth and feldspar breakdown from 425-405 Ma, similar to the data of eclogite zircons. Monazite ages younger than 400 Ma contain elevated HREE and lower Sr contents, implying garnet breakdown and feldspar growth. The age and element data of the youngest, retrograde monazites are consistent with zircon LASS data from late-stage leucosomes, dikes, and stocks, which have U-Pb ages of 407-392 Ma and elevated HREEs. Titanite data complement the late-stage, garnet-poor zircon and monazite ages (~400-380 Ma), indicating up to 20 Myr of exhumation from the most profound depths. In summary, these LASS data force the interpretation that subduction of the Baltica craton was well underway by 425 Ma and reached its maximum depth prior to the onset of exhumation and rise to amphibolite-facies depths at ~405 Ma. Exhumation, melting, and metamorphic growth continued through at least 386 Ma.

  11. LA-ICP-MS Study of Trace Elements in the Chanuskij Metal

    NASA Technical Reports Server (NTRS)

    Petaev, Michail I.

    2005-01-01

    This progress report covers work done during the second year of the 3-year proposal. During this year we resolved many issues relevant to the analytical technique developed by us for measuring trace elements in meteoritic metals. This technique was used to measure concentrations of Fe, Ni, Co, Cr, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sb, W, Re, Os, Ir, Pt, and Au in eight large (120 - 160 microns) metal grains from both "igneous" and "metamorphic" lithologies of the Chanuskij silicate inclusions. The first application of OUT technique to metal grains from thin sections showed some limitations. Small thickness of metal grains in the thin section limited the signal to 3-4 time-slices instead of 10- 1 1 ones in polished sections of iron meteorites studied before.

  12. Femtosecond laser ablation-based mass spectrometry: An ideal tool for stoichiometric analysis of thin films

    PubMed Central

    LaHaye, Nicole L.; Kurian, Jose; Diwakar, Prasoon K.; Alff, Lambert; Harilal, Sivanandan S.

    2015-01-01

    An accurate and routinely available method for stoichiometric analysis of thin films is a desideratum of modern materials science where a material’s properties depend sensitively on elemental composition. We thoroughly investigated femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs-LA-ICP-MS) as an analytical technique for determination of the stoichiometry of thin films down to the nanometer scale. The use of femtosecond laser ablation allows for precise removal of material with high spatial and depth resolution that can be coupled to an ICP-MS to obtain elemental and isotopic information. We used molecular beam epitaxy-grown thin films of LaPd(x)Sb2 and T′-La2CuO4 to demonstrate the capacity of fs-LA-ICP-MS for stoichiometric analysis and the spatial and depth resolution of the technique. Here we demonstrate that the stoichiometric information of thin films with a thickness of ~10 nm or lower can be determined. Furthermore, our results indicate that fs-LA-ICP-MS provides precise information on the thin film-substrate interface and is able to detect the interdiffusion of cations. PMID:26285795

  13. Femtosecond laser ablation-based mass spectrometry. An ideal tool for stoichiometric analysis of thin films

    DOE PAGES

    LaHaye, Nicole L.; Kurian, Jose; Diwakar, Prasoon K.; ...

    2015-08-19

    An accurate and routinely available method for stoichiometric analysis of thin films is a desideratum of modern materials science where a material’s properties depend sensitively on elemental composition. We thoroughly investigated femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs-LA-ICP-MS) as an analytical technique for determination of the stoichiometry of thin films down to the nanometer scale. The use of femtosecond laser ablation allows for precise removal of material with high spatial and depth resolution that can be coupled to an ICP-MS to obtain elemental and isotopic information. We used molecular beam epitaxy-grown thin films of LaPd(x)Sb2 and T´-La2CuO4 to demonstrate themore » capacity of fs-LA-ICP-MS for stoichiometric analysis and the spatial and depth resolution of the technique. Here we demonstrate that the stoichiometric information of thin films with a thickness of ~10 nm or lower can be determined. Furthermore, our results indicate that fs-LA-ICP-MS provides precise information on the thin film-substrate interface and is able to detect the interdiffusion of cations.« less

  14. Femtosecond laser ablation-based mass spectrometry. An ideal tool for stoichiometric analysis of thin films

    SciTech Connect

    LaHaye, Nicole L.; Kurian, Jose; Diwakar, Prasoon K.; Alff, Lambert; Harilal, Sivanandan S.

    2015-08-19

    An accurate and routinely available method for stoichiometric analysis of thin films is a desideratum of modern materials science where a material’s properties depend sensitively on elemental composition. We thoroughly investigated femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs-LA-ICP-MS) as an analytical technique for determination of the stoichiometry of thin films down to the nanometer scale. The use of femtosecond laser ablation allows for precise removal of material with high spatial and depth resolution that can be coupled to an ICP-MS to obtain elemental and isotopic information. We used molecular beam epitaxy-grown thin films of LaPd(x)Sb2 and T´-La2CuO4 to demonstrate the capacity of fs-LA-ICP-MS for stoichiometric analysis and the spatial and depth resolution of the technique. Here we demonstrate that the stoichiometric information of thin films with a thickness of ~10 nm or lower can be determined. Furthermore, our results indicate that fs-LA-ICP-MS provides precise information on the thin film-substrate interface and is able to detect the interdiffusion of cations.

  15. Laser ablation ICP-MS screening of corals for diagenetically affected areas applied to Tahiti corals from the last deglaciation

    NASA Astrophysics Data System (ADS)

    Hathorne, Ed C.; Felis, Thomas; James, Rachael H.; Thomas, Alex

    2011-03-01

    Fossil corals are unique archives of past seasonal climate variability, providing vital information about seasonal climate phenomena such as ENSO and monsoons. However, submarine diagenetic processes can potentially obscure the original climate signals and lead to false interpretations. Here we demonstrate the potential of laser ablation ICP-MS to rapidly detect secondary aragonite precipitates in fossil Porites colonies recovered by Integrated Ocean Drilling Program (IODP) Expedition 310 from submerged deglacial reefs off Tahiti. High resolution (100 μm) measurements of coralline B/Ca, Mg/Ca, S/Ca, and U/Ca ratios are used to distinguish areas of pristine skeleton from those afflicted with secondary aragonite. Measurements of coralline Sr/Ca, U/Ca and oxygen isotope ratios, from areas identified as pristine, reveal that the seasonal range of sea surface temperature in the tropical south Pacific during the last deglaciation (14.7 and 11 ka) was similar to that of today.

  16. Laser ablation ICP-MS measurements of trace metals in Douglas-fir: a preliminary analysis with submonthly temporal resolution

    NASA Astrophysics Data System (ADS)

    Wilkins, D. E.; Kohn, M. J.; Hinz, E.

    2008-12-01

    Tree-ring cores were collected from a long-lived Douglas-fir (Pseudotsuga menziesii) at Double Springs Pass in the Lost River Range of central Idaho. The tree-rings were dated to 16XX - a minimum age as the pith was not reached during coring because of internal decay. Three sections of the core - with date ranges of 1642-67, 1823-61, and 1971-2005 - were removed for laser ablation ICP-MS analysis. Samples were analyzed by using an Element2 high resolution ICP-MS operating with mass resolution (m/ Δm) of 400, and a New Wave Nd-YAG 213 nm laser system, with a spot size of 40 μm, a repetition rate of 20 Hz, and a fluence of 9-10 J/cm2. Intensities of Ca, Fe, Co, Ni, Cu, Zn, As, Sr, and Ba were collected in continuous traverses with a scan speed of 20 μm/sec, providing an effective spatial resolution of ~40 μm (~2s/analysis), or roughly a 1 to 2 week temporal resolution. Late wood ablated significantly better than early wood, leading to a clear annual signal in background-corrected intensities. Strong correlations occur among Ca-Sr±Ba, which generally exhibit low-amplitude variations, and among Ni-Cu- Zn, which generally exhibit high-amplitude variations. For some annual cycles, all data vary sympathetically, but in others the maxima in Ni-Cu-Zn vs. Ca-Sr are offset by several months. Most importantly, some elements, especially Co and As, exhibit long-term, possibly decadal variations, that may relate to climate factors such as the Pacific Decadal Oscillation. These data hold promise both for chemo-dendrochronology in wood that lacks obvious tree rings, and for characterizing climate variability in the late Holocene.

  17. Online monitoring of nanoparticles formed during nanosecond laser ablation

    NASA Astrophysics Data System (ADS)

    Nováková, Hana; Holá, Markéta; Vojtíšek-Lom, Michal; Ondráček, Jakub; Kanický, Viktor

    2016-11-01

    The particle size distribution of dry aerosol originating from laser ablation of glass material was monitored simultaneously with Laser Ablation - Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) analysis and two aerosol spectrometers - Fast Mobility Particle Sizer (FMPS) and Aerodynamic Particle Sizer (APS). The unique combination of LA-ICP-MS and FMPS offers the possibility of measuring the particle size distribution every 1 s of the ablation process in the size range of 5.6-560 nm. APS extends the information about particle concentration in the size range 0.54-17 μm. Online monitoring of the dry aerosol was performed for two ablation modes (spot and line with a duration of 80 s) with a 193 nm excimer laser system, using the glass reference material NIST 610 as a sample. Different sizes of laser spot for spot ablation and different scan speeds for line ablation were tested. It was found that the FMPS device is capable of detecting changes in particle size distribution at the first pulses of spot laser ablation and is suitable for laser ablation control simultaneously with LA-ICP-MS analysis. The studied parameters of laser ablation have an influence on the resulting particle size distribution. The line mode of laser ablation produces larger particles during the whole ablation process, while spot ablation produces larger particles only at the beginning, during the ablation of the intact layer of the ablated material. Moreover, spot ablation produces more primary nano-particles (in ultrafine mode size range < 100 nm) than line ablation. This effect is most probably caused by a reduced amount of large particles released from the spot ablation crater. The larger particles scavenge the ultrafine particles during the line ablation mode.

  18. Laser ablation ICP-MS profiling and semiquantitative determination of trace element concentrations in desert tortoise shells: Documenting the uptake of elemental toxicants

    USGS Publications Warehouse

    Seltzer, M.D.; Berry, K.H.

    2005-01-01

    The outer keratin layer (scute) of desert tortoise shells consists of incrementally grown laminae in which various bioaccumulated trace elements are sequestered during scute deposition. Laser ablation ICP-MS examination of laminae in scutes of dead tortoises revealed patterns of trace elemental distribution from which the chronology of elemental uptake can be inferred. These patterns may be of pathologic significance in the case of elemental toxicants such as arsenic, which has been linked to both shell and respiratory diseases. Laser ablation transects, performed along the lateral surfaces of sectioned scutes, offered the most successful means of avoiding exogenous contamination that was present on the scute exterior. Semiquantitative determination of elemental concentrations was achieved using sulfur, a keratin matrix element, as an internal standard. The results presented here highlight the potential of laser ablation ICP-MS as a diagnostic tool for investigating toxic element uptake as it pertains to tortoise morbidity and mortality.

  19. Simultaneous in situ determination of U-Pb and Sm-Nd isotopes in monazite by laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Goudie, Dylan J.; Fisher, Christopher M.; Hanchar, John M.; Crowley, James L.; Ayers, John C.

    2014-06-01

    are presented for in situ simultaneous determination of U-Pb and Sm-Nd isotopes in monazite using the Laser Ablation Split-Stream (LASS) method. This method uses a laser ablation system coupled to a magnetic-sector inductively coupled plasma mass spectrometer (HR) (ICP-MS) for measuring U-Pb isotopes and a multicollector (MC) ICP-MS for measuring Sm-Nd isotopes. Ablated material is split using a Y-connector and transported simultaneously to both mass spectrometers. In addition to Sm and Nd isotopes, the MC-ICP-MS is configured to also acquire Ce, Nd, Sm, Eu, and Gd elemental abundances. This approach provides age, tracer isotope, and trace element data in the same ablation volume, reducing sampling problems associated with fine-scale zoning in accessory minerals and minimizing the material needed for ablation. Precision and accuracy of the U-Pb method (and the precision of the Sm-Nd method) is demonstrated with results from well-characterized monazite reference materials. The LASS results agree within uncertainty with the isotope dilution thermal ionization mass spectrometry (ID-TIMS) U-Pb dates. The accuracy of the Sm-Nd method is assessed by comparing the LA-MC-ICP-MS results with ID-TIMS determinations on a well-characterized, in-house monazite reference material. The LASS method is then applied to monazite from the Birch Creek Pluton in the White Mountains of California as a case study to illustrate the utility of this method for solving geologic problems. The U-Pb ages and Sm-Nd isotopic data from the LASS method support the conclusions drawn from previous results that monazite can record timing and information about the source region(s) of hydrothermal fluids.

  20. In situ trace-element analysis of individual silicate melt inclusions by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS)

    NASA Astrophysics Data System (ADS)

    Taylor, R. P.; Jackson, S. E.; Longerich, H. P.; Webster, J. D.

    1997-07-01

    This paper reports the successful application of laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS) to the in situ analysis of a diverse suite of twenty trace elements including Zr, Hf, Nb, Ta, Y, and REEs, in individual silicate melt inclusions in phenocrysts from Fantale volcano, Ethiopia. The UV laser, a frequency quadrupled Nd: YAG operating at 266 nm, significantly improves the ablation characteristics of minerals that do not absorb strongly at near-IR wavelengths (e.g., quartz and feldspar). Furthermore, it allows for a significant reduction in ablation pit size to ca. 10 μm, thereby permitting numerous applications that require high-resolution sampling. Multiple ablations in individual melt inclusions in the size range 10-50 μm demonstrate both the effectiveness of the technique and the generally homogeneous character of the inclusions. Comparison of the LAM-ICP-MS data for international reference material RGM-1 (a rhyolite), with recommended values, indicates an analytical precision of <10% for most of the trace elements determined in this study. The trace element abundances of the Fantale melt inclusions, determined by LAM-ICP-MS, are typical of those of pantellerites (i.e., peralkaline rhyolites), and are consistent with their origin as tiny volumes of melt trapped in quartz and alkali-feldspar phenocrysts during the final stage of fractional crystallization of the host peralkaline magma.

  1. In situ analysis of silicon isotopes using UV-femtosecond laser ablation MC-ICP- MS

    NASA Astrophysics Data System (ADS)

    Chmeleff, J.; Horn, I.; Steinhoefel, G.; von Blanckenburg, F.

    2006-12-01

    Here we present results from the development of a novel in situ approach to measure accurate and precise ^{30}Si/^{28}Si and ^{29}Si/^{28}Si ratios in minerals and glasses. Silicon is the most abundant non- volatile element in the solar system and after oxygen, the second most abundant in upper crust. It is the dominant solute in rivers that drain our continents, supplying 80% of the dissolved Si entering the oceans. Weathering of continents is thus providing material for the formation of clays and soils, and nutrients for the aquatic biosphere. The ratios of stable silicon isotopes fingerprint many of these processes, and them ^{30}Si/^{28}Si ratios in terrestrial reservoirs (represented as δ ^{30}Si) range from -4 to +3 per mil. To date, most silicon isotope studies have been measured by gas source MS or, more recently, MC- ICPMS after sample decomposition and Si purification. While SIMS studies have presented the first in situ- measurements, laser ablation stable isotope ratio analysis is an obvious alternative. However, principle limitations of the ablation physics introduced by the nanosecond lasers traditionally employed have prevented the measurement of accurate isotope ratios. Our in-house built 196nm UV-femtosecond laser ablation system coupled to high-resolution MC-ICPMS avoids these difficulties (Horn et al. 2006, GCA 70). We have developed an in situ-method for precise and rapid measurements of ^{29}Si/^{28}Si and ^{30}Si/^{28}Si ratios in silicates at a spatial resolution of 50 micrometers. Sample-standard bracketing is used to correct for the mass discrimination and the possible drift occurring between two measurements. δ^{30}Si is calculated with NIST NBS28 (synthetic quartz sand) as bracketing standard. Two international standards were measured and compared: IRMM017 (pure metal) gives a δ^{29}Si of -0.680±0.030 (2 sigma n=25) per mil and δ^{30}Si of -1.32±0.040 (2 sigma n=25) per mil against NBS28, which is in accordance with previous

  2. Elemental fractionation in 785 nm picosecond and femtosecond laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Shaheen, M. E.; Gagnon, J. E.; Fryer, B. J.

    2015-05-01

    Elemental fractionation and ICP-MS signal response were investigated for two different pulse width laser beams originating from the same laser system. Femtosecond and picosecond laser beams at pulse widths of 130 fs and 110 ps, respectively, and wavelength of 785 nm were used to ablate NIST 610 synthetic glass and SRM 1107 Naval Brass B at the same spot for 800 to 1000 laser pulses at different repetition rates (5 to 50 Hz). Elemental fractionation was found to depend on repetition rate and showed a trend with femtosecond laser ablation that is opposite to that observed in picosecond laser ablation for most measured isotopes. ICP-MS signal intensity was higher in femtosecond than picosecond LA-ICP-MS in both NIST 610 and naval brass when ablation was conducted under the same fluence and repetition rate. The differences in signal intensity were partly related to differences in particle size distribution between particles generated by femtosecond and picosecond laser pulses and the consequent differences in transport and ionization efficiencies. The main reason for the higher signal intensity resulting from femtosecond laser pulses was related to the larger crater sizes compared to those created during picosecond laser ablation. Elemental ratios measured using 66Zn/63Cu, 208Pb/238U, 232Th/238U, 66Zn/232Th and 66Zn/208Pb were found to change with the number of laser pulses with data points being more scattered in picosecond than femtosecond laser pulses. Reproducibility of replicate measurements of signal intensities, fractionation and elemental ratios was better for fs-LA-ICP-MS (RSD ~ 3 to 6%) than ps-LA-ICP-MS (RSD ~ 7 to 11%).

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

    PubMed

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

    2011-08-01

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

  4. Imaging of Cu, Zn, Pb and U in human brain tumor resections by laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Zoriy, M. V.; Dehnhardt, M.; Reifenberger, G.; Zilles, K.; Becker, J. S.

    2006-11-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to produce images of element distribution in 20 [mu]m thin tissue sections of primary human brain tumors (glioblastoma multiforme--GBM) and adjacent non-neoplastic brain tissue. The sample surface was scanned (raster area ~1 cm2) with a focused laser beam (wavelength 266 nm, diameter of laser crater 50 [mu]m, and laser power density 1 x 109 W cm-2). The laser ablation system was coupled to a double-focusing sector field ICP-SFMS. Ion intensities of 63Cu+, 64Zn+, 208Pb+, and 238U+ were measured by LA-ICP-MS within the tumor area and the surrounding region invaded by GBM as well as in control tissue. The quantitative determination of copper, zinc, lead and uranium distribution in brain tissues by LA-ICP-MS was performed using prepared matrix-matched laboratory standards doped with these elements of interest. The limits of detection (LODs) obtained for Cu and Zn were 0.34 and 0.14 [mu]g g-1, respectively, while LODs of 12.5 and 6.9 ng g-1 were determined for Pb and U. The concentration and distribution of selected elements are compared between the control tissues and regions affected by GBM. A correlation was found between LA-ICP-MS and receptor-autoradiographic results. As receptor-autoradiographic techniques, a labeling for A1AR and the pBR was employed. Regarding the A1AR, we used the specific A1 adenosine receptor (A1AR)-ligand, 3H-CPFPX [3H-cyclopentyl-3-(3-fluoropropyl)-1-propylxanthine], which has been shown to specifically label the invasive zone around GBMs. The peripheral benzodiazepine receptor was labeled with 3H-Pk11195 [3H-1-(2-chlorphenyl)-N-methyl-N-(1-methylpropyl)-3-isoquinoline-carboxamide].

  5. Boron Isotopes Analyses of Carbonates, Phosphates and Silicates by Laser Ablation MC-ICP-MS: the Influence of Sample Matrix

    NASA Astrophysics Data System (ADS)

    Gerdes, A.

    2013-12-01

    Methods for in-situ analyses of boron isotopes by laser ablation MC-ICP-MS, although presented by 3 labs over the last years, are still not routinely applied despite of the growing interest in B isotopes, e.g. in palaeoclimate research. This study evaluates the ability to analyse boron isotopes by laser ablation at levels down to 0.2 ppm in biogenic carbonates as well as in various minerals (e.g., calcit, garnet, cpx, apatite, hematite, quartz, diamond ...) and natural and synthetic glass (NIST, USGS, and MPI-DING). Mounted and polished samples were ablated in a two-volume Helix cell using a RESOlution 193nm Excimer laser coupled to a Thermo-Finnigan Neptune (No. 1, build in 2000). Due to high sensitivity isotope signals were detected using Faraday collectors (1011 Ohm resistors). Analyses were performed as static spots over 25s with diameters of 235 to 7 μm depending on boron concentration, which yield typical 11B signals of about 0.04 (≤ 1ppm; e.g., cherts) to >0.6 V (3wt.%; tourmaline). Therefore, sample amount consumed during analyses range from 1 nanogram to 10 microgram with total analysed B content in the range of 5 to 1000 picogram. For correction of drift and mass fractionation soda-lime glass NIST-612 or NIST-610 were analysed every 30min. The applied method yields for various materials a typical analytical precision and reproducibility (1σ) of the 11B/10B of about 0.5‰ or better at boron concentration of more than 2 ppm. The effect of various parameters such as gas background, surface contamination, cross contamination, spot size, laser energy, and depth drilling will be discussed briefly. However, crucial for in-situ analyse is the evaluation of the accuracy and the influence of the sample matrix on it. Approaches to test this are still hampered by the lack of well-characterized low-B (e.g. <20ppm) reference materiel of different sample matrix. Nevertheless, in contrast to previous studies an effect of sample matrix on the boron isotope ratio was

  6. Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

    PubMed

    Konegger-Kappel, Stefanie; Prohaska, Thomas

    2016-01-01

    Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from

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

    NASA Astrophysics Data System (ADS)

    Galiová, M.; Kaiser, J.; Novotný, K.; Novotný, J.; Vaculovič, T.; Liška, M.; Malina, R.; Stejskal, K.; Adam, V.; Kizek, R.

    2008-12-01

    Single-pulse Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass-Spectrometry (LA-ICP-MS) were applied for mapping the silver and copper distribution in Helianthus Annuus L. samples treated with contaminant in controlled conditions. For Ag and Cu detection the 328.07 nm Ag(I) and 324.75 nm Cu(I) lines were used, respectively. The LIBS experimental conditions (mainly the laser energy and the observation window) were optimized in order to avoid self-absorption effect in the measured spectra. In the LA-ICP-MS analysis the Ag 107 and Cu 63 isotopes were detected. The capability of these two analytical techniques for high-resolution mapping of selected trace chemical elements was demonstrated.

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

    PubMed

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

    2014-09-01

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

  9. Investigation of Small-Scale Age Inversions in Stalagmites Using in Situ 230Th/U-Dating By Laser Ablation-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Jochum, K. P.; Lin, Y.; Scholz, D.; Weis, U.; Stoll, B.; Andreae, M. O.

    2014-12-01

    Post-depositional U loss or addition in stalagmites lead to increasing/decreasing (230Th/238U) activity ratios and thus to older/younger 230Th/U-ages, respectively. In order to determine potential small-scale age inversions, we determined 230Th, 234U, and 238U isotope abundances in a stalagmite from the Hüttenbläserschachthöhle, western Germany, applying a high-spatial-resolution in-situ LA-MC-ICP-MS technique. This sample has the advantage that - because of its aragonitic composition - the U content is high (several µg g-1) and that large-scale age inversions have been previously detected by solution MC-ICP-MS. Due to the low intensity of 230Th (20 - 80 cps), we carefully optimized the operating parameters of the 213 nm Nd:YAG laser, such as scan speed (4 µm s-1), ablation time (1000 s), spot size (110 µm), and pulse repetition rate (20 Hz). We obtained a repeatability (RSE) of about 0.6 % - 0.9 % for 230Th/238U. The isotope ratios were corrected for instrumental biases using an external carbonate reference material (i.e., a flowstone in secular equilibrium). Including all sources of analytical uncertainty, we obtain a total age error (2 SE) of ca. 8 ka for a 215 ka old sample. Repeated dating of the same layers of the stalagmite yields a reproducibility of ca. 4 %. The LA-MC-ICPMS ages agree with the solution MC-ICP-MS ages within the analytical uncertainty. The high spatial resolution enables to detect small, but significant age inversions, which could not be detected by solution MC-ICP-MS. These inversions can be explained by diagenesis of speleothem CaCO3, which may play an important role for the alteration of speleothem ages.

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

    PubMed

    Corzo, Ruthmara; Subedi, Kiran; Trejos, Tatiana; Almirall, José R

    2016-05-01

    Improvements in printing technology have exacerbated the problem of document counterfeiting, prompting the need for analytical techniques that better characterize inks for forensic analysis and comparisons. In this study, 319 printing inks (toner, inkjet, offset, and Intaglio) were analyzed directly on the paper substrate using scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). As anticipated, the high sensitivity of LA-ICP-MS pairwise comparisons resulted in excellent discrimination (average of ~ 99.6%) between different ink samples from each of the four ink types and almost 100% correct associations between ink samples known to originate from the same source. SEM-EDS analysis also resulted in very good discrimination for different toner and intaglio inks (>97%) and 100% correct association for samples from the same source. SEM-EDS provided complementary information to LA-ICP-MS for certain ink types but showed limited utility for the discrimination of inkjet and offset inks.

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

    SciTech Connect

    Saetveit, Nathan Joe

    2008-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  13. [High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

    PubMed

    Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

    2013-05-01

    In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

  14. Microanalytical isotope ratio measurements and elemental mapping using laser ablation ICP-MS for tissue thin sections: zinc tracer studies in rats.

    PubMed

    Urgast, Dagmar S; Ou, Ou; Gordon, Margaret-Jane; Raab, Andrea; Nixon, Graeme F; Kwun, In-Sook; Beattie, John H; Feldmann, Jörg

    2012-01-01

    The kinetics of zinc absorption, metabolism and excretion is extensively studied by nutritionists. Stable isotopes of zinc can be used to identify body zinc compartments that have different turnover kinetics. Since the compartments might belong to physiological subsections of different organs, there is a need for microsampling analysis to determine isotope ratios of the trace element zinc in tissue samples. Here, we study the feasibility to use laser ablation coupled to quadrupole ICP-MS for the determination of zinc tracers given to rats at different time points with the aim to generate isotope ratio bioimages of heart tissue. A double tracer ((70)Zn and (67)Zn) experiment with rats was designed to label the exchangeable zinc pool as well as the stable zinc pool. The isotope ratios determined by laser ablation ICP-MS were evaluated by additional measurements of tissue digests. Accumulated tracers which made up more than 0.1% of total zinc could be identified in the tissues of the treated rats. It was established that at least 50 measurements from the microsampling were necessary to distinguish between controls and a tracer treated rat resulting in reduced resolution of the bioimage. With the parameters used, features in the tissue thin sections of at least 250 μm(2) in size are necessary to detect the incorporation of a tracer. When different time points have to be measured, higher precisions are required and therefore a larger area needs to be ablated (1 mm(2)). Using the bioimages and pool measurements from one physiological feature, it was possible to show that the aorta cell walls incorporate the zinc tracer at the different time points.

  15. Self-aliquoting micro-grooves in combination with laser ablation-ICP-mass spectrometry for the analysis of challenging liquids: quantification of lead in whole blood.

    PubMed

    Nischkauer, Winfried; Vanhaecke, Frank; Limbeck, Andreas

    2016-08-01

    We present a technique for the fast screening of the lead concentration in whole blood samples using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The whole blood sample is deposited on a polymeric surface and wiped across a set of micro-grooves previously engraved into the surface. The engraving of the micro-grooves was accomplished with the same laser system used for LA-ICP-MS analysis. In each groove, a part of the liquid blood is trapped, and thus, the sample is divided into sub-aliquots. These aliquots dry quasi instantly and are then investigated by means of LA-ICP-MS. For quantification, external calibration against aqueous standard solutions was relied on, with iron as an internal standard to account for varying volumes of the sample aliquots. The (208)Pb/(57)Fe nuclide ratio used for quantification was obtained via a data treatment protocol so far only used in the context of isotope ratio determination involving transient signals. The method presented here was shown to provide reliable results for Recipe ClinChek® Whole Blood Control levels I-III (nos. 8840-8842), with a repeatability of typically 3 % relative standard deviation (n = 6, for Pb at 442 μg L(-1)). Spiked and non-spiked real whole blood was analysed as well, and the results were compared with those obtained via dilution and sectorfield ICP-MS. A good agreement between both methods was observed. The detection limit (3 s) for lead in whole blood was established to be 10 μg L(-1) for the laser ablation method presented here. Graphical Abstract Micro-grooves are filled with whole blood, dried, and analyzed by laser ablation ICP-mass spectrometry. Notice that the laser moves in perpendicular direction with regard to the micro-grooves.

  16. ICP-MS Workshop

    SciTech Connect

    Carman, April J.; Eiden, Gregory C.

    2014-11-01

    This is a short document that explains the materials that will be transmitted to LLNL and DNN HQ regarding the ICP-MS Workshop held at PNNL June 17-19th. The goal of the information is to pass on to LLNL information regarding the planning and preparations for the Workshop at PNNL in preparation of the SIMS workshop at LLNL.

  17. Tungsten carbide precursors as an example for influence of a binder on the particle formation in the nanosecond laser ablation of powdered materials.

    PubMed

    Holá, Markéta; Mikuska, Pavel; Hanzlíková, Renáta; Kaiser, Jozef; Kanický, Viktor

    2010-03-15

    A study of LA-ICP-MS analysis of pressed powdered tungsten carbide precursors was performed to show the advantages and problems of nanosecond laser ablation of matrix-unified samples. Five samples with different compositions were pressed into pellets both with silver powder as a binder serving to keep the matrix unified, and without any binder. The laser ablation was performed by nanosecond Nd:YAG laser working at 213 nm. The particle formation during ablation of both sets of pellets was studied using an optical aerosol spectrometer allowing the measurement of particle concentration in two size ranges (10-250 nm and 0.25-17 microm) and particle size distribution in the range of 0.25-17 microm. Additionally, the structure of the laser-generated particles was studied after their collection on a filter using a scanning electron microscope (SEM) and the particle chemical composition was determined by an energy dispersive X-ray spectroscope (EDS). The matrix effect was proved to be reduced using the same silver powdered binder for pellet preparation in the case of the laser ablation of powdered materials. The LA-ICP-MS signal dependence on the element content present in the material showed an improved correlation for Co, Ti, Ta and Nb of the matrix-unified samples compared to the non-matrix-unified pellets. In the case of W, the ICP-MS signal of matrix-unified pellets was influenced by the changes in the particle formation.

  18. A new approach for calibration of laser ablation inductively coupled plasma mass spectrometry using thin layers of spiked agarose gels as references.

    PubMed

    Stärk, H-J; Wennrich, Rainer

    2011-02-01

    Calibration of analytical methods using laser ablation for sample introduction is often problematic. The availability of matrix-adapted standard materials is a crucial factor in the analysis of biological samples in particular. In this work a method for preparation of thin-film references for LA-ICP-MS is presented which is inexpensive, relatively simple and generally practicable. Aqueous solutions of agarose spiked with defined amounts of the analytes were cast on a carrier and then dried. When the thin-film references were characterized the average thickness of the films was 0.03 mm in the centre of the film and the relative standard deviation was 8%. Nebulization ICP-MS analysis after acid digestion of the agarose film was used to investigate the effectiveness of the spiking procedure. Recovery of the spiked elements was frequently in the range 90-110% (for rare earth elements 97-102%). Laser ablation ICP-MS analysis was used to investigate the distribution of the spiked elements in the film. When the laser was scanned across the gel the measured intensities were not constant, but had a peak-shaped profile with a flat top. Use of this flat-top region for analytical purposes, after its characterization by laser ablation ICP-MS, is proposed. Analysis of cell cultures was carried out by direct laser ablation-ICP-MS with the calibration method described. The results were in accordance with values previously achieved by nebulization ICP-MS.

  19. 2D elemental mapping of sections of human kidney stones using laser ablation inductively-coupled plasma-mass spectrometry: Possibilities and limitations

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  20. Laser ablation methods for analysis of urinary calculi: Comparison study based on calibration pellets

    NASA Astrophysics Data System (ADS)

    Štěpánková, K.; Novotný, K.; Vašinová Galiová, M.; Kanický, V.; Kaiser, J.; Hahn, D. W.

    2013-03-01

    Methods based on laser ablation, such as Laser-Induced Breakdown Spectroscopy (LIBS) and Laser-Ablation Inductively Coupled Plasma Mass/Optical Emission Spectrometry (LA-ICP-MS/OES) are particularly suitable for urinary calculi bulk and micro analysis. Investigation of spatial distribution of matrix and trace elements can help to explain their emergence and growth. However, quantification is still very problematic and these methods are often used only for qualitative elemental mapping. There are no commercially available standards, which would correspond to the urinary calculi matrix. Internal standardization is also difficult, mainly due to different crystalline phases in one kidney stone. The aim of this study is to demonstrate the calibration capabilities and examine the limitations of laser ablation based techniques. Calibration pellets were prepared from powdered human urinary calculi with phosphate, oxalate and urate matrix. For this comparative study, the most frequently used laser-ablation based analytical techniques were chosen, such as LIBS and LA-ICP-MS. Moreover, some alternative techniques such as simultaneous LIBS-LA-ICP-OES and laser ablation LA-LIBS were also utilized.

  1. A rapid isotope ratio analysis protocol for nuclear solid materials using nano-second laser-ablation time-of-flight ICP-MS.

    PubMed

    Bürger, S; Riciputi, L R

    2009-11-01

    The analysis of the isotopic composition of nuclear or non-nuclear solid materials is performed in a variety of fields, e.g., for quality assurance in the production of nuclear fuels, as signatures in forensics, nuclear safeguards, and non-proliferation control, in material characterization, geology, and archeology. We have investigated the capability of laser ablation (New Wave Research, 213 nm) coupled to time-of-flight (TOF) ICP-MS (GBC OptiMass 8000) as a rapid analytical protocol for multi-isotope screening of nuclear and non-nuclear solid samples. This includes natural and non-natural isotopic compositions for elements including Cu, Zr, Mo, Cd, In, Ba, Ta, W, Re, Pt, Pb, and U, in pure metals, alloys, and glasses. Without correcting for mass bias (mass fractionation), an overall precision and accuracy of about 4% (1 sigma) can be achieved by minimizing the deposited laser power and thus fractionation (mass removal based on thermal properties). The precision and accuracy in combination with literally no or minimized sample preparation enables a rapid isotope screening of solid samples that is of particular interest to support nuclear forensic and safeguard analysis.

  2. Laser-Ablation Sampling for Accurate Analysis of Sulfur in Edible Salts.

    PubMed

    Lee, Yonghoon; Chirinos, Jose; Gonzalez, Jhanis; Oropeza, Dayana; Zorba, Vassilia; Mao, Xianglei; Yoo, Jonghyun; Russo, Richard E

    2017-04-01

    We evaluated the performance of laser ablation analysis techniques such as laser-induced breakdown spectroscopy (LIBS), laser ablation inductively coupled optical emission spectrometry (LA-ICP-OES), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), in comparison with that of ICP-OES using aqueous solutions for the quantification of sulfur (S) in edible salts from different geographical origins. We found that the laser ablation based sampling techniques were not influenced by loss of S, which was observed in ICP-OES with aqueous solutions for a certain salt upon their dissolution in aqueous solutions, originating from the formation of volatile species and precipitates upon their dilution in water. Although detection of S using direct laser sampling with LA-ICP-MS has well-known isobaric and polyatomic interferences, LIBS and LA-ICP-OES showed good accuracy in the detection of S for all salts. LIBS also provided the ability to identify the dominant chemical form in which S is present in salts. Correlation between S and oxygen, observed in LIBS spectra, provided chemical information about the presence of S(2-) or [Formula: see text], which are associated with the origin and quality of edible salts.

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

    PubMed

    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%.

  4. Elemental analysis of glass by laser ablation inductively coupled plasma optical emission spectrometry (LA-ICP-OES).

    PubMed

    Schenk, Emily R; Almirall, José R

    2012-04-10

    The elemental analysis of glass evidence has been established as a powerful discrimination tool for forensic analysts. Laser ablation inductively coupled plasma optical emission spectrometry (LA-ICP-OES) has been compared to laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and energy dispersive micro X-ray fluorescence spectroscopy (μXRF/EDS) as competing instrumentation for the elemental analysis of glass. The development of a method for the forensic analysis of glass coupling laser ablation to ICP-OES is presented for the first time. LA-ICP-OES has demonstrated comparable analytical performance to LA-ICP-MS based on the use of the element menu, Al (Al I 396.15 nm), Ba (Ba II 455.40 nm), Ca (Ca II 315.88 nm), Fe (Fe II 238.20 nm), Li (Li I 670.78 nm), Mg (Mg I 285.21 nm), Sr (Sr II 407.77 nm), Ti (Ti II 368.51 nm), and Zr (Zr II 343.82 nm). The relevant figures of merit, such as precision, accuracy and sensitivity, are presented and compared to LA-ICP-MS. A set of 41 glass samples was used to assess the discrimination power of the LA-ICP-OES method in comparison to other elemental analysis techniques. This sample set consisted of several vehicle glass samples that originated from the same source (inside and outside windshield panes) and several glass samples that originated from different vehicles. Different match criteria were used and compared to determine the potential for Type I and Type II errors. It was determined that broader match criteria is more applicable to the forensic comparison of glass analysis because it can reduce the affect that micro-heterogeneity inherent in the glass fragments and a less than ideal sampling strategy can have on the interpretation of the results. Based on the test set reported here, a plus or minus four standard deviation (± 4s) match criterion yielded the lowest possibility of Type I and Type II errors. The developed LA-ICP-OES method has been shown to perform similarly to LA-ICP-MS in the

  5. Copper mobility in the Eastern Creek Volcanics, Mount Isa, Australia: evidence from laser ablation ICP-MS of iron-titanium oxides

    NASA Astrophysics Data System (ADS)

    Gregory, Melissa J.

    2006-10-01

    The Palaeoproterozoic Eastern Creek Volcanics are a series of copper-rich tholeiitic basalts which occur adjacent to the giant sediment-hosted Mount Isa copper deposit in Queensland, Australia. The volcanic rocks are often cited as the source of metals for the deposit. New laser ablation ICP-MS analyses of iron-titanium oxides from the basalts provide evidence for the local mobilisation of copper during regional greenschist facies metamorphism. This interpretation is based on the observation that copper-bearing magmatic titanomagnetite was destabilised during greenschist facies metamorphism, and the new magnetite which crystallised was copper poor. Petrological observations, regional geochemical signatures and geochemical modelling suggest that the mobilised copper was concentrated in syn-metamorphic epidote-rich alteration zones, creating a pre-concentration of copper before the main mineralisation event at Mount Isa. Geochemical modelling demonstrates this process is enhanced by the addition of CO2 from adjacent carbonate-rich sediments during metamorphic devolatilisation. Regional geochemical data illustrate elevated copper concentrations in epidote-rich zones (high CaO), but where these zones are overprinted by potassic alteration (high K2O), copper is depleted. A two-stage model is proposed whereby after metamorphic copper enrichment in epidote-titanite alteration zones, an oxidised potassium-rich fluid leached copper from the epidote-altered metabasalts and deposited it in the overlying sedimentary rocks to form the Mount Isa copper deposit. This ore-forming fluid is expressed regionally as potassium feldspar-rich veins and locally as biotite-rich alteration, which formed around major fluid conduits between the metabasalt metal source rocks and the overlying deposit host sequence. This model is consistent with the remobilisation of copper from mafic source rocks, as has been found at other world-class copper deposits.

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

    NASA Astrophysics Data System (ADS)

    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.

  7. A quantitative approach for Cd, Cu, Fe and Mn through laser ablation imaging for evaluating the translocation and accumulation of metals in sunflower seeds.

    PubMed

    Pessôa, Gustavo de S; Lopes Júnior, Cícero A; Madrid, Katherine C; Arruda, Marco A Z

    2017-05-15

    The uptake and accumulation of Cd in sunflower seeds represents an important pathway for imputing potentially toxic metals into human and animal food. In this way, bioimaging of Cd and micronutrients (Cu, Fe and Mn) in the seeds of sunflower grown in soil contaminated with Cd are performed. For this task, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used in quantitative approach, considering four groups: precursor, control, Cd-low (50mg) and Cd-high (700mg). For attaining our proposals, ICP-MS (nebulizer and auxiliary flow rates and radiofrequency power) and LA (laser intensity, frequency and spot size) parameters were optimized, and the analytical signal improved to 197%, 217%, 232%, and 283%, for (57)Fe, (112)Cd, (55)Mn and (63)Cu, respectively. The accuracy of proposed method using LA-ICP-MS is evaluated comparing the CRM results (Tomato leaves, NIST SRM 1573a). No difference is found at 95% confidence level. Regarding Cd accumulation in sunflower seeds, the results indicated that cadmium is translocated to seeds, and the cotyledons showed the highest concentration (Cd-high group), ranging from 10 to 20µgg(-1). Considering both total concentration and the distribution in the seeds, Cd uptake is responsible to the homeostasis misbalance of micronutrients, which play an essential role in the sunflower metabolism. Such results highlight the importance of bioimaging evaluation, in the translocation and accumulation of metals, contributing to expand the information available of this culture.

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

    NASA Astrophysics Data System (ADS)

    Sajnóg, Adam; Hanć, Anetta; Makuch, Krzysztof; Koczorowski, Ryszard; Barałkiewicz, Danuta

    2016-11-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for in-situ quantitative analysis of oral mucosa of patients before and after implantation with titanium implants and a closing screw based on Ti6Al4V alloy. Two calibration strategies were applied, both were based on matrix matched solid standards with analytes addition. A novel approach was the application of powdered egg white proteins as a matrix material which have a similar composition to the examined tissue. In the another approach, certified reference material Bovine Muscle ERM-BB184 was used. The isotope 34S was found to be the most appropriate as an internal standard since it is homogenously distributed in the examined tissues and resulted in lower relative standard deviation values of signal of analytes of interest. Other isotopes (13C, 26Mg, 43Ca) were also evaluated as potential internal standards. The analytical performance parameters and microwave digestion of solid standards followed by solution nebulization ICP-MS analysis proved that both calibration methods are fit for their intended purpose. The LA-ICP-MS analysis on the surface of tissues after the implantation process revealed an elevated content of elements in comparison to the control group. Analytes are distributed inhomogeneously and display local maximal content of Ti up to ca. 900 μg g- 1, Al up to ca. 760 μg g- 1 and for V up to 160 μg g- 1.

  9. Determination of Os by isotope dilution-inductively coupled plasma-mass spectrometry with the combination of laser ablation to introduce chemically separated geological samples

    NASA Astrophysics Data System (ADS)

    Sun, Yali; Ren, Minghao; Xia, Xiaoping; Li, Congying; Sun, Weidong

    2015-11-01

    A method was developed for the determination of trace Os in geological samples by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) with the combination of chemical separation and preconcentration. Samples are digested using aqua regia in Carius tubes, and the Os analyte is converted into volatile OsO4, which is distilled and absorbed with HBr. The HBr solution is concentrated for further Os purification using the microdistillation technique. The purified Os is dissolved in 10 μl of 0.02% sucrose-0.005% H3PO4 solution and then evaporated on pieces of perfluoroalkoxy (PFA) film, resulting in the formation of a tiny object (< 3 × 104 μm2 superficial area). Using LA-ICP-MS measurements, the object can give Os signals at least 100 times higher than those provided by routine solution-ICP-MS while successfully avoiding the memory effect. The procedural blank and detection limit in the developed technique are 3.0 pg and 1.8 pg for Os, respectively when 1 g of samples is taken. Reference materials (RM) are analyzed, and their Os concentrations obtained by isotope dilution are comparable to reference or literature values. Based on the individual RM results, the precision is estimated within the range of 0.6 to 9.4% relative standard deviation (RSD), revealing that this method is applicable to the determination of trace Os in geological samples.

  10. Elemental analysis of coal by tandem laser induced breakdown spectroscopy and laser ablation inductively coupled plasma time of flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Dong, Meirong; Oropeza, Dayana; Chirinos, José; González, Jhanis J.; Lu, Jidong; Mao, Xianglei; Russo, Richard E.

    2015-07-01

    The capabilities and analytical benefits of combined LIBS and LA-ICP-MS were evaluated for the analysis of coal samples. The ablation system consisted of a Nd:YAG laser operated 213 nm. A Czerny-turner spectrograph with ICCD detector and time-of-flight based mass spectrometer were utilized for LIBS and ICP-MS detection, respectively. This tandem approach allows simultaneous determination of major and minor elements (C, Si, Ca, Al, Mg), and trace elements (V, Ba, Pb, U, etc.) in the coal samples. The research focused on calibration strategies, specifically the use of univariate and multivariate data analysis on analytical performance. Partial least square regression (PLSR) was shown to minimize and compensate for matrix effects in the emission and mass spectra improving quantitative analysis by LIBS and LA-ICP-MS, respectively. The correlation between measurements from these two techniques demonstrated that mass spectral data combined with LIBS emission measurements by PLSR improved the accuracy and precision for quantitative analysis of trace elements in coal.

  11. Comparison of laser-ablation and solution-mode ICP-MS techniques for measuring speleothem 87Sr/86Sr values

    NASA Astrophysics Data System (ADS)

    Wortham, B. E.; Wong, C. I.; Montanez, I. P.; Silva, L. C. R.; Rasbury, T.; Glessner, J. J.

    2015-12-01

    Reconstructing past changes in precipitation amount is critical to delineating controls on paleovegetation dynamics in South America. Although speleothem, lake, and ice core δ18O records from the region serve as a proxy of monsoon intensity, δ18O values do not serve as a direct proxy of local precipitation amount. To address this, we are developing a reconstruction of past moisture conditions using 87Sr/86Sr values measured in a fast growing speleothem (~2 mm/yr) from the central Brazilian savanna for which a late Holocene (0-1.8 ka) δ18O record has previously been developed. Speleothem 87Sr/86Sr values reflect the degree of water-rock interaction, as dictated by water residence time, and are used to interpret relative moisture conditions. In this study, we explore the potential of developing a high-resolution speleothem 87Sr/86Sr record using laser-ablation multi-collector ICP-MS by comparing analyses generated using both laser- and solution-mode techniques. Laser-mode techniques allow for sampling of individual speleothem lamina, which provides a higher resolution record than solution-mode techniques and eliminates the potential of contamination from conventional drilling. Preliminary results from a younger portion of the speleothem yield a laser-mode (averaged) value of 0.72294 ± 0.00046 (reproduced with parallel scans) and a solution mode value of 0.72338 ± 0.00002 suggesting that these methods provide analogous 87Sr/86Sr values. However, the preliminary results on an older portion of this speleothem have solution- mode derived values of 0.72239 ± 0.00001 and 0.72166 ± 0.00001, with corresponding laser-mode values of 0.72188 ± 0.00029 and 0.72102 ± 0.00037, respectively. Suggesting that in the older portion of the speleothem, laser-mode techniques do not yield analogous solution-mode 87Sr/86Sr values. These differences in different areas of the speleothem highlight the need for method development and further testing.

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

    PubMed

    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.

  13. Analysis of glass fragments by laser ablation-inductively coupled plasma-mass spectrometry and principal component analysis.

    PubMed

    Bajic, Stanley J; Aeschliman, David B; Saetveit, Nathan J; Baldwin, David P; Houk, R S

    2005-09-01

    Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is used to differentiate glass samples with similar optical and physical properties based on trace elemental composition. Laser ablation increases the number of elements that can be used for differentiation by eliminating problems commonly associated with dissolution and contamination. In this study, standard residential window and tempered glass samples that could not be differentiated by refractive index or density were successfully differentiated by LA-ICP-MS. The primary analysis approach used is Principal Component Analysis (PCA) of the complete mass spectrum. PCA, a multivariate analysis technique, provides rapid analysis of samples without time-consuming pair-wise comparison of calibrated analyses or prior knowledge of the elements present in the samples. Probabilities for positive association of the individual samples are derived from PCA. Utilization of the Q-statistic with PCA allowed us to distinguish all samples within the set to a certainty greater than the 99% confidence interval.

  14. Iron isotope compositions and origins of pyrites from the Turee Creek Group, Western Australia: the contribution of high-resolution femtosecond Laser Ablation -MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    d'Abzac, F.; Beard, B. L.; Williford, K. H.; Valley, J. W.; Van Kranendonk, M. J.; Johnson, C.

    2013-12-01

    The Paleoproterozoic Great Oxidation Event (GOE) records a transition from an anoxic environment to a O2-bearing atmosphere, but its timing and duration remain unclear. High-spatial-resolution S isotope analyses by SIMS have shown that pyrite grains in the ~2.4Gy diamictites of the Meteorite Bore Member (MBM; Turee Creek Group, Western Australia), deposited during the GOE, contain evidence for a complex depositional and paragenetic history, including microbial sulfate reduction under low atmospheric O2 yet high seawater sulfate concentrations. The pyrites show various morphologies: euhedral, subhedral, anhedral, rounded, and zoned, where low- δ34S rounded cores may have high-δ34S euhedral/subhedral overgrowths [1]. New in-situ Fe isotope data by femtosecond laser ablation (fs-LA) analysis using Multi Collector ICP-MS on 118 pyrite grains within five rock samples previously analyzed for S isotopes documents δ56Fe values between -2.3‰ and +2.3‰. Transitional cherts at the base of the MBM record the highest δ56Fe values, >0.7‰. Within the upper mudstones/sandstones deposits, anhedral, rounded grains and zoned pyrite cores have a wide range of δ56Fe from -2.3‰ to +1.1‰ whereas euhedral grains and grains overgrowths have mainly positive δ56Fe values, up to +1.34‰, spread over narrower ranges in each sample (<1‰). Non-euhedral grains and rounded grain cores of likely detrital origin have highly scattered δ56Fe values, indicating a range of different sources. Although very low δ56Fe values suggest a source of biologically reduced Fe [2], they can be obtained by precipitation of FeS from low-δ56Fe seawater Fe2+ [3], or might reflect a kinetic signature during pyritization of FeS [4]. High-δ56Fe in pyrite overgrowths and authigenic grains likely reflects precipitation from a hydrothermal fluid (δ56Fe~0.0‰) at T>100°C [5, 6], in agreement with [1]. The δ34S gradient of highly negative to positive values from zoned pyrites cores to rims is well

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

    SciTech Connect

    Havrilla, George Joseph; McIntosh, Kathryn Gallagher; Judge, Elizabeth; Dirmyer, Matthew R.; Campbell, Keri; Gonzalez, Jhanis J.

    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.

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

    PubMed

    Tanaka, Kazuya; Takahashi, Yoshio; Shimizu, Hiroshi

    2007-02-05

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

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

    PubMed

    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.

  18. Silurian U-Pb zircon age (LA-ICP-MS) of granitoids from the Zelenodol Cu-porphyry deposit, Southern Urals

    NASA Astrophysics Data System (ADS)

    Grabezhev, A. I.; Ronkin, Yu. L.; Puchkov, V. N.; Shardakova, G. Yu.; Azovskova, O. B.; Gerdes, A.

    2016-01-01

    The Zelenodol porphyry Cu-(Au, Mo) deposit located about 65 km SSW of the city of Chelyabinsk is confined to the western part of the West Uralian Volcanogenic Megazone. The concordant U-Pb age of zircons from ore-bearing island-arc diorite porphyryis 418.3 Â ± 2.9 Ma.

  19. New Sakmarian ages for the Rio Bonito formation (Paraná Basin, southern Brazil) based on LA-ICP-MS U-Pb radiometric dating of zircons crystals

    NASA Astrophysics Data System (ADS)

    Cagliari, Joice; Lavina, Ernesto Luiz Correa; Philipp, Ruy Paulo; Tognoli, Francisco Manoel Wohnrath; Basei, Miguel Angelo Stipp; Faccini, Ubiratan Ferrucio

    2014-12-01

    Two ash fall beds (tonstein) sampled from the post-glacial Permian deposits of the Paraná Basin have provided new U-Pb radiometric age constraints for this stratigraphic interval. The zircon grains were recovered from tonstein layers interbedded with fine-grained and carbonaceous lithologies in the middle portion of the Rio Bonito Formation. In both samples, the dominant population is interpreted as generated by explosive volcanism, as having formed immediately before the eruption. Based on 238U/206Pb, the selected zircon grains from the dominant population have weighted mean ages of 290.6 ± 2.8 Ma and 281.7 ± 3.2 Ma, corresponding to the Sakmarian and Kungurian ages in the Cisuralian epoch, respectively. These ages constrain the time of the deposition of the tonstein horizons and have important stratigraphic implications for the Late Paleozoic evolution of both the Paraná Basin and the southwestern region of Gondwana. The results presented here and the radiometric data already published suggest that deposition of the post-glacial coal-bearing deposits of the Rio Bonito Formation was probably initiated before the Early Permian. Thus, we infer that the climate had already ameliorated by this period in order to allow for the formation and accumulation of peat in this region of Gondwana.

  20. New data about structure and time of formation of the Khamar-Daban terrane: U-Pb LA-ICP-MS zircon ages

    NASA Astrophysics Data System (ADS)

    Shkol'nik, S. I.; Stanevich, A. M.; Reznitskii, L. Z.; Savelieva, V. B.

    2016-01-01

    This paper provides new data on the age of detrital zircons from metaterrigenous rocks of the Khamardaban Group (Kornilovskaya and Shubutuiskaya formations) which crown the succession of the Khamar-Daban terrain. It was established that the accumulation of the protoliths of both formations occurred in the interval between the Late Riphean and Early Ordovician. In this case, there is a difference between sequences of Shubutuiskaya and Kornilovskaya formations due to a sharp change in a provenance area and depositional conditions, which is a consequence of the change in the paleogeodynamic environment. In addition, this indicates the tectonic juxtaposition of these sequences and probability of accumulation of deposits of the Shubutuiskaya Formation within Dzhida island arc system.

  1. Geochemical and Lu/Hf isotopic (LA-ICP-MS) signature of detrital zircons from sandstones of the basal levels of the Riphean stratotype

    NASA Astrophysics Data System (ADS)

    Romanyuk, T. V.; Kuznetsov, N. B.; Maslov, A. V.; Belousova, E. A.; Krupenin, M. T.; Ronkin, Yu. L.; Gorozhanin, V. M.; Gorozhanina, E. N.

    2014-11-01

    This paper presents the results of selective study of trace elements (29 analyses) and the Lu/Hf isotopic system (41 analyses) in preliminarily dated (U-Pb) detrital zircons (dZrs) from sandstones of the Ai Formation of the Burzyan Group of the Bashkirian Anticlinorium, which compose the basal horizons of the typical Riphean section of the Southern Urals. The statistically processed trace-element patterns of dZrs showed that "diorites" were dominant over "syenites" among the source rocks of dZrs. The rock types estimated by trace-element patterns for the cores and rims of two large grains ("diorite" and "syenite") coincided. The analysis of the Lu/Hf isotopic system of dZrs revealed a wide dispersion of the ɛHf value from +7.1 to -20.1 at the T {DM/C} model age of the substrate from 2.25 to 3.95 Ga. Four grains (in one case with the core and rim studied) from the population of the large transparent cherry zircons (TCZ) are characterized by the "syenitic" rock type and extremely ancient T {DM/C} values of 3.22, 3.45, 3.64, 3.66, and 3.75 Ga at ages of zircons of 2486, 2784, 2873, 1977, and 1984 Ma, respectively. Two "dioritic" grains from the TCZ population have significantly distinct parameters: 2.37 and 2.51 Ga at 2049 and 2057 Ma, respectively. It is evident that this specific population of dZrs was formed with a significant contribution of very ancient crustal material, which became active under "syenitic" magmatism and provided the T {DM/C} value of >3.5 Ga. Numerous juvenile dZrs form a compact cluster, which correspond to the rocks of the southern part of the Volga-Sarmatian orogen (age of 2.1-2.0 Ga, T {DM/C} = 2.1-2.4 Ga). The complexes of the entire the Volga-Uralia, the Volga-Sarmatian orogen, and adjacent areas could be the provenance areas for the Ai sandstones in contrast to the northeastern areas of the East-European Platform with dominant "granitic" source rocks and T {DM/C} values lower than 3.5 Ga.

  2. Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals) in coal samples.

    PubMed

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

    2007-10-01

    A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for (35)Cl+ to more than 6 x 10(5) cps for (238)U+ for 1 microg of trace element per gram of coal sample. Detection limits vary from 450 ng g(-1) for chlorine and 18 ng g(-1) for sulfur to 9.5 pg g(-1) for mercury and 0.3 pg g(-1) for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis.

  3. Metal imaging on surface of micro- and nanoelectronic devices by laser ablation inductively coupled plasma mass spectrometry and possibility to measure at nanometer range.

    PubMed

    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%.

  4. Elemental bioimaging of nanosilver-coated prostheses using X-ray fluorescence spectroscopy and laser ablation-inductively coupled plasma-mass spectrometry.

    PubMed

    Blaske, Franziska; Reifschneider, Olga; Gosheger, Georg; Wehe, Christoph A; Sperling, Michael; Karst, Uwe; Hauschild, Gregor; Höll, Steffen

    2014-01-07

    The distribution of different chemical elements from a nanosilver-coated bone implant was visualized, combining the benefits of two complementary methods for elemental bioimaging, the nondestructive micro X-ray fluorescence (μ-XRF), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Challenges caused by the physically inhomogeneous materials including bone and soft tissues were addressed by polymer embedding. With the use of μ-XRF, fast sample mapping was achieved obtaining titanium and vanadium signals from the metal implant as well as phosphorus and calcium signals representing hard bone tissue and sulfur distribution representing soft tissues. Only by the use of LA-ICP-MS, the required high sensitivity and low detection limits for the determination of silver were obtained. Metal distribution within the part of cancellous bone was revealed for silver as well as for the implant constituents titanium, vanadium, and aluminum. Furthermore, the detection of coinciding high local zirconium and aluminum signals at the implant surface indicates remaining blasting abrasive from preoperative surface treatment of the nanosilver-coated device.

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

    PubMed

    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.

  6. Current developments in laser ablation-inductively coupled plasma-mass spectrometry for use in geology, forensics, and nuclear nonproliferation research

    SciTech Connect

    Messerly, Joshua D.

    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

  7. In situ sulfur isotopes (δ(34)S and δ(33)S) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS.

    PubMed

    Fu, Jiali; Hu, Zhaochu; Zhang, Wen; Yang, Lu; Liu, Yongsheng; Li, Ming; Zong, Keqing; Gao, Shan; Hu, Shenghong

    2016-03-10

    The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis

  8. Direct imaging of elemental distributions in tissue sections by laser ablation mass spectrometry.

    PubMed

    Shariatgorji, Mohammadreza; Nilsson, Anna; Bonta, Maximilian; Gan, Jinrui; Marklund, Niklas; Clausen, Fredrik; Källback, Patrik; Loden, Henrik; Limbeck, Andreas; Andrén, Per E

    2016-07-15

    We present a strategy for imaging of elements in biological tissues using laser ablation (LA) mass spectrometry (MS), which was compared to laser ablation inductively coupled plasma (LA-ICP) MS. Both methods were adopted for quantitative imaging of elements in mouse kidney, as well as traumatic brain injury model tissue sections. MS imaging (MSI) employing LA provides quantitative data by comparing signal abundances of sodium from tissues to those obtained by imaging quantitation calibration standards of the target element applied to adjacent control tissue sections. LA-ICP MSI provided quantitative data for several essential elements in both brain and kidney tissue sections using a dried-droplet approach. Both methods were used to image a rat model of traumatic brain injury, revealing accumulations of sodium and calcium in the impact area and its peripheral regions. LA MSI is shown to be a viable option for quantitative imaging of specific elements in biological tissue sections.

  9. Combined application of a laser ablation-ICP-MS assay for screening and ESI-FTICR-MS for identification of a Cd-binding protein in Spinacia oleracea L. after exposure to Cd.

    PubMed

    Polatajko, Aleksandra; Feldmann, Ingo; Hayen, Heiko; Jakubowski, Norbert

    2011-10-01

    We have studied the binding of the toxic element Cd to plant proteins and have used for this purpose spinach (Spinacia oleracea L.) plants treated with 50 μM Cd(II) as a model system. Laser ablation ICP-MS has been applied for the screening of Cd-binding proteins after separation by native anodal polyacrylamide gel electrophoresis (AN-PAGE) and electroblotting onto membranes. The main Cd-carrying protein band was isolated and investigated by nano-electrospray ionization-Fourier transform ion cyclotron resonance (FTICR) mass spectrometry after tryptic digestion. By this procedure, the main Cd-binding protein was identified as ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO). The latter enzyme has been discussed in the literature to be affected in its activity by oxidative stress induced by Cd. However, in this paper it is demonstrated for the first time that RuBisCO directly binds Cd and thus may be directly altered by this toxic element. A commercially available protein standard was used to verify direct binding of Cd(II) to the protein, even without metabolisation. The resulting metal-protein complex was shown to be stable enough to survive AN-PAGE separation and electroblotting. By the use of size exclusion chromatography coupled with ICP-MS it was demonstrated that the RuBisCO protein standard shows similar metal binding properties to Cd. Furthermore, essential elements such as Mn(II), Fe(II) and Cu(II), which are known to possibly replace the RuBisCO activator Mg(II), were investigated in addition to Zn(II). Again, similar binding properties in comparison to the plant protein were observed.

  10. Capabilities of femtosecond laser ablation ICP-MS for the major, minor, and trace element analysis of high alloyed steels and super alloys.

    PubMed

    Wiltsche, Helmar; Günther, Detlef

    2011-02-01

    Femtosecond laser ablation inductively coupled plasma mass spectrometry was used for the quantification of 23 metallurgical relevant elements in unalloyed, alloyed and highly alloyed steels, and super alloys. It was shown that by using scanning mode ablation with large ablation spot diameters (250 μm), stable and representative sampling can be achieved for the majority of elements, except for bismuth and lead. For Bi and Pb up to 46%, temporal relative standard deviation (TRSD) was encountered, whereas for most other elements, the TRSDs were below 10%. Calibration with matrix-matched and non-matrix-matched standards provided similar agreement within the uncertainty of the certified values. However, the non-matrix-matched standard-based quantification was more influenced by interferences rather than ablation- or excitation-related matrix effects. The method was validated using 34 certified reference materials. (52)Cr, (51)V, or (55)Mn were used as internal standards due to the fact that the Fe concentration was not certified for the majority of reference materials. The determined concentrations for major and minor elements indicate that the total matrix internal standardization (100 wt.%) is applicable, which requires no knowledge about the steel samples prior to analysis.

  11. Laser Ablation/Ionisation Mass Spectrometry: Sensitive and Quantitative Chemical Depth Profiling of Solid Materials.

    PubMed

    Riedo, Andreas; Grimaudo, Valentine; Moreno-García, Pavel; Neuland, Maike B; Tulej, Marek; Broekmann, Peter; Wurz, Peter

    2016-01-01

    Direct quantitative and sensitive chemical analysis of solid materials with high spatial resolution, both in lateral and vertical direction is of high importance in various fields of analytical research, ranging from in situ space research to the semiconductor industry. Accurate knowledge of the chemical composition of solid materials allows a better understanding of physical and chemical processes that formed/altered the material and allows e.g. to further improve these processes. So far, state-of-the-art techniques such as SIMS, LA-ICP-MS or GD-MS have been applied for chemical analyses in these fields of research. In this report we review the current measurement capability and the applicability of our Laser Ablation/Ionisation Mass Spectrometer (instrument name LMS) for the chemical analysis of solids with high spatial resolution. The most recent chemical analyses conducted on various solid materials, including e.g. alloys, fossils and meteorites are discussed.

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

    SciTech Connect

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

    2010-05-01

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

  13. Laser ablation inductively coupled plasma mass spectrometry: A new technique for the determination of trace and ultra-trace elements in silicates

    SciTech Connect

    Perkins, W.T.; Pearce, N.J.G.; Jeffries, T.E. )

    1993-01-01

    This paper describes recent work applying a laser ablation system coupled to an inductively coupled plasma mass spectrometer (LA-ICP-MS) for the direct analysis of solid geological materials. This work demonstrates the potential of LA-ICP-MS for the determination of a wide range of petrogenetically important trace and ultra-trace elements (including for example REE, Hf, Ta, Nb, Th, U) following a routine method of sample preparation. Powdered geological materials have been prepared as both pressed powder disks and fused glasses; both common methods of sample preparation for X-ray fluorescence (XRF) analysis. The solid materials were sampled by ablation using a pulsed Nd:YAG laser operating at 1,064 nm. Analyses can be produced at approximately 10 samples per hour. This instrumental method has limits of detection at or close to those in chondritic meteorites and gives linear calibrations over four orders of magnitude. The accuracy of the technique has been evaluated using reference materials to calibrate the instrument and treating Geological Survey of Japan basalts JB-1a, JB-2, and JB-3 as unknowns.' Detection limits are better than routine XRF analysis and compare favorably with Instrumental Neutron Activation Analysis. Laser ablation overcomes the problems of sample dissolution employed in standard wet chemical techniques, whilst the fused glasses provide homogeneous solid samples. The fused glass technique has been applied to a wide range of reference materials from ultra-basic rocks through basalts and andesites to granites, as well as syenite, mica schist, and black shale. For all of the elements commonly used to generate multi-element discrimination diagrams the data obtained define straight line calibrations. This method is therefore capable of analyzing the complete range of silicate compositions normally encountered with a single calibration (i.e., there is no apparent matrix effect). 47 refs., 4 figs., 5 tabs.

  14. High resolution analysis of uranium and thorium concentration as well as U-series isotope distributions in a Neanderthal tooth from Payre (Ardèche, France) using laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Grün, Rainer; Aubert, Maxime; Joannes-Boyau, Renaud; Moncel, Marie-Hélène

    2008-11-01

    We have mapped U ( 238U) and Th ( 232Th) elemental concentrations as well as U-series isotope distributions in a Neanderthal tooth from the Middle Palaeolithic site of Payre using laser ablation ICP-MS. The U-concentrations in an enamel section varied between 1 and 1500 ppb. The U-concentration maps show that U-migration through the external enamel surface is minute, the bulk of the uranium having migrated internally via the dentine into the enamel. The uranium migration and uptake is critically dependent on the mineralogical structure of the enamel. Increased U-concentrations are observed along lineaments, some of which are associated with cracks, and others may be related to intra-prismatic zones or structural weaknesses reaching from the dentine into the enamel. The uranium concentrations in the dentine vary between about 25,000 and 45,000 ppb. Our systematic mapping of U-concentration and U-series isotopes provides insight into the time domain of U-accumulation. Most of the uranium was accumulated in an early stage of burial, with some much later overprints. None of the uranium concentration and U-series profiles across the root of the tooth complied with a single stage diffusion-adsorption (D-A) model that is used for quality control in U-series dating of bones and teeth. Nevertheless, in the domains that yielded the oldest apparent U-series age estimates, U-leaching could be excluded. This means that the oldest apparent U-series ages of around 200 ka represent a minimum age for this Neanderthal specimen. This is in good agreement with independent age assessments (200-230 ka) for the archaeological layer, in which it was found. The Th elemental concentrations in the dental tissues were generally low (between about 1 and 20 ppb), and show little relationship with the nature of the tissue.

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

    SciTech Connect

    Havrilla, George Joseph; Gonzalez, Jhanis

    2015-06-10

    The use of femtosecond laser ablation inductively coupled plasma mass spectrometry was used to demonstrate the feasibility of measuring the isotopic ratio of uranium directly in U-10Mo fuel foils. The measurements were done on both the flat surface and cross sections of bare and Zr clad U-10Mo fuel foil samples. The results for the depleted uranium content measurements were less than 10% of the accepted U235/238 ratio of 0.0020. Sampling was demonstrated for line scans and elemental mapping over large areas. In addition to the U isotopic ratio measurement, the Zr thickness could be measured as well as trace elemental composition if required. A number of interesting features were observed during the feasibility measurements which could provide the basis for further investigation using this methodology. The results demonstrate the feasibility of using fs-LA-ICP-MS for measuring the U isotopic ratio in U-10Mo fuel foils.

  16. Grain-scale iron isotopic distribution of pyrite from Precambrian shallow marine carbonate revealed by a femtosecond laser ablation multicollector ICP-MS technique: Possible proxy for the redox state of ancient seawater

    NASA Astrophysics Data System (ADS)

    Nishizawa, Manabu; Yamamoto, Hiroki; Ueno, Yuichiro; Tsuruoka, Subaru; Shibuya, Takazo; Sawaki, Yusuke; Yamamoto, Shinji; Kon, Yoshiaki; Kitajima, Kouki; Komiya, Tsuyoshi; Maruyama, Shigenori; Hirata, Takafumi

    2010-05-01

    The redox state of Precambrian shallow seas has been linked with material cycle and evolution of the photosynthesis-based ecosystem. Iron is a redox-sensitive element and exists as a soluble Fe(II) species or insoluble Fe(III) species on Earth's surface. Previous studies have shown that the iron isotopic ratio of marine sedimentary minerals is useful for understanding the ocean redox state, although the redox state of the Archean shallow sea is poorly known. This is partly because the conventional bulk isotope analytical technique has often been used, wherein the iron isotopic record may be dampened by the presence of isotopically different iron-bearing minerals within the same sample. Here we report a microscale iron isotopic ratio of individual pyrite grains in shallow marine stromatolitic carbonates over geological time using a newly developed, near-infrared femtosecond laser ablation multicollector ICP-MS technique (NIR-fs-LA-MC-ICP-MS). We have determined that the grain-scale iron isotopic distribution of pyrite from coeval samples shows a bimodal (2.7 and 2.3 Ga) or unimodal pattern (2.9, 2.6, and 0.7 Ga). In particular, pyrite from the 2.7 Ga Fortescue Group shows a unique bimodal distribution with highly positive (+1.0‰ defined as Type 1) and negative δ 56Fe values (-1.8‰ defined as Type 2). Type 1 and 2 pyrites occasionally occur within different siliceous layers in the same rock specimen. Layer-scale iron isotopic heterogeneity indicates that the iron isotopic ratios of the two types of pyrite are not homogenized by diagenesis after deposition. Some cubic pyrites have a core with a positive δ 56Fe value (1‰) and a rim with a crustal δ 56Fe value (0‰). The observed isotopic zoning suggests that the positive δ 56Fe value is a primary signature at the time of stromatolite formation, while secondary pyrite precipitated during diagenesis. The positive δ 56Fe value of Type 1 and the large iron isotopic difference between Type 1 and 2 (2.8

  17. Laser ablation plasmas for diagnostics of structured electronic and optical materials during or after laser processing

    NASA Astrophysics Data System (ADS)

    Russo, Richard E.; Bol'shakov, Alexander A.; Yoo, Jong H.; González, Jhanis J.

    2012-03-01

    Laser induced plasma can be used for rapid optical diagnostics of electronic, optical, electro-optical, electromechanical and other structures. Plasma monitoring and diagnostics can be realized during laser processing in real time by means of measuring optical emission that originates from the pulsed laser-material interaction. In post-process applications, e.g., quality assurance and quality control, surface raster scanning and depth profiling can be realized with high spatial resolution (~10 nm in depth and ~3 μm lateral). Commercial instruments based on laser induced breakdown spectrometry (LIBS) are available for these purposes. Since only a laser beam comes in direct contact with the sample, such diagnostics are sterile and non-disruptive, and can be performed at a distance, e.g. through a window. The technique enables rapid micro-localized chemical analysis without a need for sample preparation, dissolution or evacuation of samples, thus it is particularly beneficial in fabrication of thin films and structures, such as electronic, photovoltaic and electro-optical devices or circuits of devices. Spectrum acquisition from a single laser shot provides detection limits for metal traces of ~10 μg/g, which can be further improved by accumulating signal from multiple laser pulses. LIBS detection limit for Br in polyethylene is 90 μg/g using 50-shot spectral accumulation (halogen detection is a requirement for semiconductor package materials). Three to four orders of magnitude lower detection limits can be obtained with a femtosecond laser ablation - inductively coupled plasma mass spectrometer (LA-ICP-MS), which is also provided on commercial basis. Laser repetition rate is currently up to 20 Hz in LIBS instruments and up to 100 kHz in LA-ICP-MS.

  18. Solid sampling with 193-nm excimer laser ablation

    NASA Astrophysics Data System (ADS)

    Delmdahl, Ralph

    2007-02-01

    Reproducible and sensitive elemental analysis of solid samples is a crucial task in areas of geology (e.g. microanalysis of fluid inclusions), material sciences, industrial quality control as well as in environmental, forensic and biological studies. To date the most versatile detection method is mass-spectroscopic multi-element analysis. In order to obtain reproducible results, this requires transferring the solid sample into the gas-phase while preserving the sample's stoichiometric composition. Laser ablation in combination with Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) is a proven powerful technique to meet the requirements for reliable solid sample analysis. The sample is laser ablated in an air-tight cell and the aerosol is carried by an inert gas to a micro-wave induced plasma where its constituents are atomized and ionized prior to mass analysis. The 193 nm excimer laser ablation, in particular, provides athermal sample ablation with very precise lateral ablation and controlled depth profiling. The high photon energy and beam homogeneity of the 193 nm excimer laser system avoids elemental fractionation and permits clean ablation of even transmissive solid materials such as carbonates, fluorites and pure quartz.

  19. Comparative imaging of P, S, Fe, Cu, Zn and C in thin sections of rat brain tumor as well as control tissues by laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Zoriy, Myroslav V.; Dehnhardt, Markus; Matusch, Andreas; Becker, J. Sabine

    2008-03-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for quantitative imaging of selected elements (P, S, Fe, Cu, Zn and C) in thin sections of rat brain samples (thickness 20 μm). The sample surface was scanned (raster area ~ 2 cm 2) with a focused laser beam (wavelength 266 nm, diameter of laser crater 50 μm, and irradiance 1 × 10 9 W cm - 2 ). The laser ablation system was coupled to a double-focusing sector field. The possibility was evaluated of using carbon (via measurement of 13C +) as an internal standard element for imaging element distribution as part of this method. The LA-ICP-MS images obtained for P, S, Fe Cu and Zn were quantified using synthetically prepared matrix-matched laboratory standards. Depending on the sample analyzed, concentrations of Cu and Zn in the control tissue were found to be in the range of 8-10 μg g - 1 and 10-12 μg g - 1 , while in the tumor tissue these concentrations were in the range of 12-15 μg g - 1 and 15-17 μg g - 1 , respectively. The measurements of P, S and Fe distribution revealed the depletion of these elements in tumor tissue. In all the samples, the shape of the tumor could be clearly distinguished from the surrounding healthy tissue by the depletion in carbon. Additional experiments were performed in order to study the influence of the water content of the analyzed tissue on the intensity signal of the analyte. The results of these measurements show the linear correlation ( R2 = 0.9604) between the intensity of analyte and amount of water in the sample. The growth of a brain tumor was thus studied for the first time by imaging mass spectrometry.

  20. Characterization of toners and inkjets by laser ablation spectrochemical methods and Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy

    NASA Astrophysics Data System (ADS)

    Trejos, Tatiana; Corzo, Ruthmara; Subedi, Kiran; Almirall, José

    2014-02-01

    Detection and sourcing of counterfeit currency, examination of counterfeit security documents and determination of authenticity of medical records are examples of common forensic document investigations. In these cases, the physical and chemical composition of the ink entries can provide important information for the assessment of the authenticity of the document or for making inferences about common source. Previous results reported by our group have demonstrated that elemental analysis, using either Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) or Laser Ablation Induced Breakdown Spectroscopy (LIBS), provides an effective, practical and robust technique for the discrimination of document substrates and writing inks with minimal damage to the document. In this study, laser-based methods and Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDS) methods were developed, optimized and validated for the forensic analysis of more complex inks such as toners and inkjets, to determine if their elemental composition can differentiate documents printed from different sources and to associate documents that originated from the same printing source. Comparison of the performance of each of these methods is presented, including the analytical figures of merit, discrimination capability and error rates. Different calibration strategies resulting in semi-quantitative and qualitative analysis, comparison methods (match criteria) and data analysis and interpretation tools were also developed. A total of 27 black laser toners originating from different manufacturing sources and/or batches were examined to evaluate the discrimination capability of each method. The results suggest that SEM-EDS offers relatively poor discrimination capability for this set (~ 70.7% discrimination of all the possible comparison pairs or a 29.3% type II error rate). Nonetheless, SEM-EDS can still be used as a complementary method of analysis since it has

  1. Gold in the Brunswick No. 12 volcanogenic massive sulfide deposit, Bathurst Mining Camp, Canada: Evidence from bulk ore analysis and laser ablation ICP-MS data on sulfide phases

    NASA Astrophysics Data System (ADS)

    McClenaghan, Sean H.; Lentz, David R.; Martin, Jillian; Diegor, Wilfredo G.

    2009-07-01

    The 329-Mt Brunswick No. 12 volcanogenic massive sulfide deposit (total resource of 163 Mt at 10.4% Zn, 4.2% Pb, 0.34% Cu, and 115 g/t Ag) is hosted within a Middle Ordovician bimodal volcanic and sedimentary sequence. Massive sulfides are for the most part syngenetic, and the bulk of the sulfide ore occurs as a Zn-Pb-rich banded sulfide facies that forms an intimate relationship with a laterally extensive Algoma-type iron formation and defines the Brunswick Horizon. Zone refining of stratiform sulfides is considered to have resulted in the development of a large replacement-style Cu-rich basal sulfide facies, which is generally confined between the banded sulfide facies and an underlying stringer sulfide zone. Complex polyphase deformation and associated lower- to upper-greenschist facies regional metamorphism is responsible for the present geometry of the deposit. Textural modification has resulted in a general increase in grain size through the development of pyrite and arsenopyrite porphyroblasts, which tend to overprint primary mineral assemblages. Despite the heterogeneous ductile deformation, primary features have locally been preserved, such as fine-grained colloform pyrite and base and precious metal zonation within the Main Zone. Base metal and trace element abundances in massive sulfides from the Brunswick No. 12 deposit indicate two distinct geochemical associations. The basal sulfide facies, characterized by a proximal high-temperature hydrothermal signature (Cu-Co-Bi-Se), contains generally low Au contents averaging 0.39 ppm ( n = 34). Conversely, Au is enriched in the banded sulfide facies, averaging 1.1 ppm Au ( n = 21), and is associated with an exhalative suite of elements (Zn-Pb-As-Sb-Ag-Sn). Finely laminated sulfide lenses hosted by iron formation at the north end of the Main Zone are further enriched in Au, averaging 1.7 ppm ( n = 41) and ranging up to 8.2 ppm. Laser ablation inductively coupled plasma-mass spectrometry (ICP-MS) analyses of

  2. Distribution of iron in size resolved aerosols generated by femtosecond laser ablation: Influence of cell geometry and implications for in situ isotopic measurements using LA-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    d'Abzac, F.; Czaja, A. D.; Beard, B. L.; Schauer, J. J.; Johnson, C.

    2012-12-01

    Laser Ablation (LA) Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a common and reliable method for the in situ chemical analysis in geosciences. In contrast, use of LA for analyzing naturally occurring mass dependent isotope fractionation in geological samples is not widely used because of the difficulties of differentiating laser induced isotope fractionation from naturally occurring mass dependent isotope fractionation. A critical aspect for accurate in situ stable isotope analysis is the chemical and isotopic composition, size, and morphology of aerosols generated by LA. We report on the iron mass distribution over the particle size distribution (PSD) of aerosols produced by femtosecond LA of magnetite and pyrite. A Photon Machines "Analyte" fs-G2 was used that provides τ~150fs pulses in the near UV (λ=263nm) with an adjustable repetition rate 1Ablations were performed under Helium (~0.5L.min-1 outgoing flow) and two different cells were used: one cylindrical with a ~10s wash out time, the other (Photon Machines HelEx), with a wash out of less than 1s. For all experiments, aerosols were collected on Teflon filters using a MOUDI cascade impactor, according to their aerodynamic diameter, within a range of da<0.056μm to da>18μm (Marple, Rubow et al., 1991). Filters loads were dissolved in HCl (magnetite) or HNO3 (pyrite) and iron concentration was determined spectroscopically using the ferrozine method or by isotope dilution mass spectrometery. The PSD for a given cell is similar for both pyrite and magnetite and is independent of fluence (1-3J.cm-2). However, significant differences appear from one cell to the other. The cylindrical cell gives a unimodal distribution with a peak centered on da=0.18μm and spread from da=0.056μm to 0.56μm (83% of the total Fe mass). Using the Helex cell the PSD is bi modal with ~1/3 of the particles having a da<0.056μm in addition to the peak at da=0.18μm. Importantly we note that for a given mineral

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Guillong, M.; Günther, D.

    2001-07-01

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

  5. Coupling centrifuge modeling and laser ablation inductively coupled plasma mass spectrometry to determine contaminant retardation in clays.

    PubMed

    Timms, Wendy; Hendry, M Jim; Muise, Jason; Kerrich, Robert

    2009-02-15

    Quantifying the retardation (Rd) of reactive solutes as they migrate through low-permeability clay-rich media is difficult, thus motivating this study to assess the viability of combining centrifuge modeling and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) techniques. An influent solution containing Cl-, trace metals, and lanthanide species flowed at 1.0 mL x h(-1) through an undisturbed clay-rich core sample (33 mm diameter x 50 mm long) mounted in a UFA Beckman centrifuge operating at 3000 rpm (N factor = 876 g). During the 87 day experiment the hydraulic conductivity of the core was 3.4 x 10(-10) m x s(-1). Effluent breakthrough data indicate the Rd of Tl to be 10; incomplete breakthrough (non-steady-state) data for 145Nd and 171Yb suggest Rd values of >75 and >85, respectively. At the completion of the transport experiment, longitudinal sections of the core solid were analyzed for 145Nd and 171Yb using a Cetac laser ablation system coupled with an ICP-MS. The longitudinal core sections yielded Rd values of >10000 for 145Nd and 171Yb. This study demonstrates coupling these techniques can provide Rd values for a wide range of reactive solutes with relatively rapid testing of small-scale, low hydraulic conductivity core samples.

  6. The solubility of platinum and gold in NaCl brines at 1.5 kbar, 600 to 800°C: A laser ablation ICP-MS pilot study of synthetic fluid inclusions

    NASA Astrophysics Data System (ADS)

    Hanley, Jacob J.; Pettke, Thomas; Mungall, James E.; Spooner, Edward T. C.

    2005-05-01

    The concentration and distribution of Pt and Au in a fluid-melt system has been investigated by reacting the metals with S-free, single-phase aqueous brines (20, 50, 70 wt% eq. NaCl) ± peraluminous melt at a confining pressure of 1.5 kbar and temperatures of 600 to 800 °C, trapping the fluid in synthetic fluid inclusions (quartz-hosted) and vesicles (silicate melt-hosted), and quantifying the metal content of the trapped fluid and glass by laser ablation ICP-MS. HCl concentration was buffered using the assemblage albite-andalusite-quartz and f was buffered using the assemblage Ni-NiO. Over the range of experimental conditions, measured concentrations of Pt and Au in the brines ( CPtfluid, CAufluid) are on on the order of 1-10 3 ppm. Concentrations of Pt and Au in the melt ( CPtmelt, CAumelt) are ˜35-100 ppb and ˜400-1200 ppb, respectively. Nernst partition coefficients ( DPtfluid/melt, DAufluid/melt) are on the order of 10 2-10 3 and vary as a function of Cmetalfluid (non-Henry's Law behavior). Trapped fluids show a significant range of metal concentrations within populations of inclusions from single experiments (˜ 1 log unit variability for Au; ˜2-3 log unit variability for Pt). Variability in metal concentration within single inclusion groups is attributed to premature brine entrapment (prior to metal-fluid-melt equilibrium being reached); this allows us to make only minimum estimates of metal solubility using metal concentrations from primary inclusions. The data show two trends: (i) maximum and average values of CAufluid and CPtfluid in inclusions decrease ˜2 orders of magnitude as fluid salinity ( m∑Clfluid) increases from ˜4 to 40 molal (20 to 70 wt % eq. NaCl) at a constant temperature; (ii) maximum and average values of CAufluid increase approximately 1 order of magnitude for every 100°C increase temperature at a fixed m∑Clfluid. The observed behavior may be described by the general expression: log⁡(mmetalfluid,T,1.5kbar

  7. Isotopic ratio measurements with ICP-MS

    SciTech Connect

    Russ, G.P. III; Bazan, J.M.

    1986-06-03

    An inductively-coupled-plasma source mass spectrometer (ICP-MS) has been used to measure the isotopic composition of U, Pb, Os, and B standards. Particular emphasis has been placed on uranium because of its nuclear and environmental interest and because of the availability of a well-characterized set of standards with a wide range of isotopic compositions. The precision and accuracy obtainable in isotope ratio measurements by ICP-MS depend on many factors including background, interferences, dead time, mass fractionation (bias), abundance sensitivity, and counting statistics. Which, if any, of these factors controls accuracy and precision depends on the type of sample being analyzed and the characteristics of the mass spectrometer. These issues are discussed in detail.

  8. Quantitative solid sample analysis by ArF excimer laser ablation

    NASA Astrophysics Data System (ADS)

    Delmdahl, Ralph; von Oldershausen, Georg

    2005-06-01

    Reproducible and sensitive elemental analysis of solid samples is a crucial task in areas of geology (e.g. microanalysis of fluid inclusions), material sciences, industrial quality control as well as in environmental, forensic and biological studies. To date the most versatile detection method is mass-spectroscopic multi-element analysis. In order to obtain reproducible results, this requires transferring the solid sample into the gas-phase while preserving the sample's stoichiometric composition. Laser Ablation in combination with inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a proven powerful technique to meet the requirements for reliable solid sample analysis. The sample is laser ablated in an air-tight cell and the aerosol is carried by an inert gas to a micro-wave induced plasma where its constituents are atomized and ionized prior to mass analysis. The 193 nm excimer laser ablation, in particular, provides athermal sample ablation with very precise lateral ablation and controlled depth profiling. The high photon energy and beam homogeneity of the 193 nm excimer laser system avoids elemental fractionation and permits clean ablation of even transmissive solid materials such as carbonates, fluorites and pure quartz.

  9. Comparison of Time-of-flight and Multicollector ICP Mass Spectrometers for Measuring Actinides in Small Samples using single shot Laser Ablations

    SciTech Connect

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

    2005-11-01

    The objective of these experiments is to evaluate the performance of two types of ICP-MS device for measurement of actinide isotopes by laser ablation (LA) ICP-MS. The key advantage of ICP-MS compared to monitoring of radioactive decay is that the element need not decay during the measurement time. Hence ICP-MS is much faster for long-lived radionuclides. The LA process yields a transient signal. When spatially resolved analysis is required for small samples, the laser ablation sample pulse lasts only {approx}10 seconds. It is difficult to measure signals at several isotopes with analyzers that are scanned for such a short sample transient. In this work, a time-of-flight (TOF) ICP-MS device, the GBC Optimass 8000 (Figure 1) is one instrument used. Strictly speaking, ions at different m/z values are not measured simultaneously in TOF. However, they are measured in very rapid sequence with little or no compromise between the number of m/z values monitored and the performance. Ions can be measured throughout the m/z range in single sample transients by TOF. The other ICP-MS instrument used is a magnetic sector multicollector MS, the NU Plasma 1700 (Figure 2). Up to 8 adjacent m/z values can be monitored at one setting of the magnetic field and accelerating voltage. Three of these m/z values can be measured with an electron multiplier. This device is usually used for high precision isotope ratio measurements with the Faraday cup detectors. The electron multipliers have much higher sensitivity. In our experience with the scanning magnetic sector instrument in Ames, these devices have the highest sensitivity and lowest background of any ICP-MS device. The ability to monitor several ions simultaneously, or nearly so, should make these devices valuable for the intended application: measurement of actinide isotopes at low concentrations in very small samples for nonproliferation purposes. The primary sample analyzed was an urban dust pellet reference material, NIST 1648

  10. A magnesium hydroxide preconcentration/matrix reduction method for the analysis of rare earth elements in water samples using laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Hsieh, Hui-Fang; Chen, Yi-Hsiang; Wang, Chu-Fang

    2011-08-15

    This paper describes a simple method for simultaneous preconcentration and matrix reduction during the analysis of rare earth elements (REEs) in water samples through laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). From a systematic investigation of the co-precipitation of REEs using magnesium hydroxide, we optimized the effects of several parameters - the pH, the amount of magnesium, the shaking time, the efficiency of Ba removal, and the sample matrix - to ensure quantitative recoveries. We employed repetitive laser ablation to remove the dried-droplet samples from the filter medium and introduce them into the ICP-MS system for determinations of REEs. The enrichment factors ranged from 8 to 88. The detection limit, at an enrichment factor of 32, ranged from 0.03 to 0.20 pg mL(-1). The relative standard deviations for the determination of REEs at a concentration of 1 ng mL(-1) when processing 40 mL sample solution were 2.0-4.8%. We applied this method to the satisfactory determination of REEs in lake water and synthetic seawater samples.

  11. Trace elemental content of biological materials. A comparison of NAA and ICP-MS analysis.

    PubMed

    Ward, N I; Abou-Shakra, F R; Durrant, S F

    1990-01-01

    The advantages and disadvantages of neutron activation analysis (NAA) and inductively coupled plasma-source mass spectrometry (ICP-MS) for the analysis of biological materials is reviewed. Comparison is made between NAA (instrumental) and ICP-MS (conventional pneumatic solution nebulization and laser ablation) analysis of the biological reference material National Bureau of Standards (NBS) SRM 1577 Bovine Liver. Relatively good agreement is achieved between the results for the 18 elements analyzed by both techniques and those either certified or reported in the literature. Elemental concentrations for Li, Mg, Al, Ca, Cr, Mn, Fe, Cu, Zn, Br, Rb, and Cs are also reported for IAEA Mixed Human Diet (H9), NBS SRM 909 Human Serum, and NBS SRM 1577a Bovine Liver, analyzed by solution nebulization ICP-MS.

  12. A LA-ICP-MS study of minerals in the Rocche Rosse magmatic enclaves: Evidence of a mafic input triggering the latest silicic eruption of Lipari Island (Aeolian Arc, Italy)

    NASA Astrophysics Data System (ADS)

    Davì, Marcella; De Rosa, Rosanna; Barca, Donatella

    2009-05-01

    The volcanic products of Lipari Island (Aeolian Arc, Italy) younger than 10 ka are mostly aphyric rhyolitic pumices and obsidians emitted during unusual strombolian-type eruptions, which ended with the emplacement of lava flows. The last volcanic activity on the island dates back to 1230 ± 40 AD, with the extrusion of Rocche Rosse (RR) obsidian lava flow. Recently, mafic enclaves of latitic to trachytic composition have been identified and an evolution process between these enclaves and the rhyolitic magma has been documented in detail [Davì, M., 2007. The Rocche Rosse rhyolitic lava flow (Lipari, Aeolian Islands): magmatological and volcanological aspects. Plinius, supplement to the European Journal of Mineralogy 33, 1-8]. In this work textural and trace-element investigation of mineral phases of the RR enclaves, such as crystals of clinopyroxene, olivine, plagioclase, alkali-feldspar and biotite, was carried out to delineate the most recent feeding system of the island, since such a reconstruction could be significant in terms of hazard forecasting. The results indicate that most of the mineral phases are reversely or oscillatory zoned with respect to both major and trace elements, suggesting an early crystallization under low fO 2 conditions from melts of intermediate composition, followed by a later growth from a more mafic (presumably shoshonitic-basaltic) magma than that from which their cores crystallized. Crystals of magnesium-rich pyroxene and forsteritic-rich olivine are indicative of the presence of this shoshonitic basaltic magma. Based on microanalytical data, it is suggested here that the feeding system of recent Lipari volcanic activity was characterized by a shoshonitic-basaltic magma originating from a deep reservoir, which may have evolved and stopped in the crust, generating zoned magma chambers at different depths, in which latitic and rhyolitic magmas reside. The sudden arrival of a new input of mafic melt may have interacted with these resident fractionated magmas and triggered the eruption. A plumbing system of this type has been shown to be active in the southern sector of the Aeolian Islands since the last 42 ka [Gioncada, A., Mazzuoli, R., Milton, A., 2005. Magma mixing at Lipari (Aeolian Islands, Italy): Insights from textural and compositional features of phenocrysts. J. Volcanol. Geotherm. Res. 145, 97-118; Peccerillo, A., Frezzotti, M.L., De Astis, G., Ventura, G., 2006. Modeling the magma plumbing system of Vulcano (Aeolian Islands, Italy) by integrated fluid-inclusion geobarometry, petrology and geophysics. Geology 34, 17-20]. It is concluded that the hazard assessment of Lipari Island should take into account the arrival of deep and never erupted mafic melts as eruption triggers of more evolved shallower magma bodies.

  13. Zircon U-Pb Age Distributions in Cogenetic Crystal-Rich Dacitic and Crystal-Poor Rhyolitic Members of Zoned Ignimbrites in the Southern Rocky Mountains by Chemical Abrasion Inductively-Coupled-Plasma Mass Spectrometry (CA-LA-ICP-MS).

    NASA Astrophysics Data System (ADS)

    Sliwinski, J.; Zimmerer, M. J.; Guillong, M.; Bachmann, O.; Lipman, P. W.

    2015-12-01

    The San Juan locus of the Southern Rocky Mountain Volcanic Field (SRMVF) in SW Colorado represents an erosional remnant of a mid-Tertiary (~37-23 Ma) ignimbrite flare up that produced some of the most voluminous ignimbrites on Earth. A key feature of many SRMVF ignimbrites is compositional zonation, with many volcanic units comprising both dacitic and rhyolitic horizons. Geochemical, field and petrographic evidence suggests that dacites and rhyolites are cogenetic. Here, we report U-Pb zircon ages by chemical abrasion inductively-coupled-plasma mass spectrometry (CA-LA-ICPMS) for rhyolitic and dacitic components in four units: the Bonanza, Rat Creek, Carpenter Ridge and Nelson Mountain Tuffs. All units show zircon age spectra that are either within analytical uncertainty of Ar/Ar ages or are appreciably older, indicating prolonged magma residence times (~500 ka) prior to eruption. Anomalously young Pb-loss zones in zircon have been largely removed by chemical abrasion. Older, inherited zircons and zircon cores (60-2000 Ma) are rare in all samples, suggesting limited assimilation of upper crustal Precambrian country rock or complete resorption during recharge events and magma chamber growth.

  14. The oldest sediments of Greece revealed by detrital zircon LA-ICP-MS U-Pb dating: Cambro-Ordovician sandstones from northern Gondwana in the External Hellenides - implications on the evolution of the eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Kydonakis, Konstantinos; Kostopoulos, Dimitrios; Poujol, Marc; Brun, Jean-Pierre; Papanikolaou, Dimitrios; Paquette, Jean-Louis

    2013-04-01

    Detrital zircon U-Pb ages of a quartzite from the Feneos locality of Peloponnesus, S. Greece, were determined by LA-ICPMS. The rock classifies as a mature quartz arenite and belongs to an original shale-sandstone succession now metamorphosed into a phyllite-quartzite unit. The latter chiefly represents the External Blueschist Belt of the Hellenides widely known as the Arna or Phyllite - Quartzite (PQ) Unit. Zircon age clusters at 0.5-0.75, 0.85, 0.95-1.1, 1.75-2 and 2.4-3 Ga point at the Saharan Metacraton and the Transgondwanan Supermountain as contributing sources; the youngest concordant grain is 522 Ma old. Based on great similarities in lithology, zircon age-distribution patterns and depositional setting between the Feneos quartzite and intact Cambro-Ordovician sandstone-shale sequences of Libya (Murzuq and Kufrah basins) we propose that the protolith of the former was deposited in an epeiric sea north of Libya during the Cambro-Ordovician. Feneos, as part of the Cimmerian block, had become detached from the NE Gondwanan margin during Late Carboniferous - Early Permian times and drifted northward. In central Crete, similar-looking sequences (Galinos beds) were originally deposited in an accretionary/fore-arc complex outboard of the south Laurussian active margin (Pelagonia) between ~297-230 Ma. The southern Pelagonian margin eventually collided (mild docking) with the northward drifting Cimmerian block signaling the closure of Palaeotethys by early Late Triassic. The Gondwanan affinity of the Feneos quartzite strongly contrasts the European one of the Galinos beds; the suture of Palaeotethys can thus be traced in S. Greece within the pre-Triassic sedimentary sequences of Peloponnesus and Crete. In the eastern Mediterranean realm, rocks with similar age clusters crop out in Greece (Peloponnesus, this study; eastern Crete, Sfaka locality; north-central Macedonia, Vertiskos terrane), NW Turkey (central Sakarya terrane), Libya (Murzuq and Kufrah basins), Israel (Elat locality) and Jordan (El-Quweira locality). Their zircon age spectra plotted with respect to sediment depositional age indicate a collisional margin setting for all. Evaluating the depositional setting of the arguably similar sedimentary sequences above we demonstrate their common provenance from the Gondwana Super-fan System which draped the northern Gondwanan periphery from ~525 to 460 Ma (Lower Cambrian - Middle Ordovician). Using as anchoring points the non-metamorphosed Early Palaeozoic outcrops of Libya and the Middle East that remained intact at their original deposition sites we have traced, in space and time, the path of the remainder time- and facies-equivalent rocks presently cropping out in the Hellenic and Turkish mountain belts. The fate of the northern Gondwanan margin was multiple rifting and travelling of the fragments thereof throughout the Palaeozoic before their final incorporation into younger orogenic belts.

  15. Aqueous Organometal Speciation by GC-ICP-MS and HPLC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Hannigan, R.

    2005-12-01

    Organometals, specifically organomercury, organotin and organolead, may only account for a small fraction of the total metal load in aquatic systems. Despite their lower relative abundance, organometal species may have a larger impact on the environment. Although biogeochemical studies of mercury, tin, and to a lesser degree lead, have been done, little is known about the transport and transformation of these organometals in the water column and, more specifically, at the sediment-water interface. Our knowledge is limited, in part, by the lack of instrumental techniques that provide simultaneous highly precise data about the metal species and binding ligand. We have developed a series of hyphenated techniques that allow for precise quantification of the elemental and organic forms of these metals. Most importantly these methods remove sample pre-treatment from the methods though headspace trap desorption, split injection and sequential chromatography with split detection providing detailed information about the metals and organics in stream water samples. Our data show that using headspace trap GC-ICP-MS it is possible to by-pass chromatographic separation of the species and detect elemental, dimethyl and methyl mercury in a single sample from a single injection. Additional research shows that GC-ICP-MS and HPLC-ICP-MS speciation of organotins provide differential speciation data with GC-ICP-MS detecting, at very low concentrations, butylins and HPLC-ICP-MS detecting, at very low concentrations, ethyltins. Integration of these techniques into a single system will eventually lead to a system which provides simultaneous detection of metals and organic binding ligands in a single sample.

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

    NASA Astrophysics Data System (ADS)

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

    1994-02-01

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

  17. Comparison of sp-ICP-MS and MDG-ICP-MS for the determination of particle number concentration.

    PubMed

    Gschwind, Sabrina; Aja Montes, Maria de Lourdes; Günther, Detlef

    2015-05-01

    In 2011, the European Commission introduced new regulations on how nanomaterials are defined. Since then, researchers have emphasized that more complete characterization of nanoparticles (NPs) includes not just mass and size determinations, but also the determination of the particle number concentrations. In this study, two different sample introduction approaches for the analysis of NP suspensions with inductively coupled plasma mass spectrometry (ICP-MS) were investigated: pneumatic nebulization (sp-ICP-MS) and microdroplet generation (MDG-ICP-MS). These approaches were compared for the determination of particle number concentrations (PNCs) of gold and silver NP suspensions diluted in either ultra-pure water or citrate solution. For accurate sp-ICP-MS analysis, it is crucial to know the transport efficiency of nebulized sample into the plasma. Here, transport efficiencies, measured by the waste collection method, were 11-14 % for Ag suspensions and 9-11 % for Au. In contrast, the droplet transport efficiency of MDG-ICP-MS was 100 %. Analysis by sp-ICP-MS yielded a lower particle number concentration than expected (only 20-40 % of the expected value), whereas MDG-ICP-MS had NP recoveries up to 80 %. This study indicates that NP reference materials are of major importance for particle number determination and detailed results on particle number concentrations for different suspensions with respect to storage time are discussed.

  18. Elemental impurity analysis of mercuric iodide by ICP/MS

    SciTech Connect

    Cross, E.S.; Mroz, E.; Olivares, J.A.

    1993-06-01

    A method has been developed to analyze mercuric iodide (HgI{sub 2}) for elemental contamination using Inductively Coupled Plasma/Mass Spectroscopy (ICP/MS). This paper will discuss the ICP/MS method, the effectiveness of purification schemes for removing impurities from HgI{sub 2}, as well as preliminary correlations between HgI{sub 2} detector performance and elemental contamination levels.

  19. Elemental impurity analysis of mercuric iodide by ICP/MS

    SciTech Connect

    Cross, E.S. . Santa Barbara Operations); Mroz, E.; Olivares, J.A. )

    1993-01-01

    A method has been developed to analyze mercuric iodide (HgI[sub 2]) for elemental contamination using Inductively Coupled Plasma/Mass Spectroscopy (ICP/MS). This paper will discuss the ICP/MS method, the effectiveness of purification schemes for removing impurities from HgI[sub 2], as well as preliminary correlations between HgI[sub 2] detector performance and elemental contamination levels.

  20. Micro-spatial variations of heavy metals in the teeth of walrus as determined by laser ablation ICP-MS: the potential for reconstructing a history of metal exposure.

    PubMed

    Evans, R D; Richner, P; Outridge, P M

    1995-01-01

    This study explored the possibility of using laser ablation inductively-coupled plasma-mass spectroscopy to measure trace metals and other elements within the annual growth layers of the teeth of walrus harvested from the Canadian Arctic. Using sample ablation "footprints" of 125 microns diameter on transects across the exposed cross-sections of teeth, this technique detected Pb, Cu, Zn and Sr, but not Cd, in tooth cementum. The micro-spatial patterns of elements were consistent among different transects on the same tooth, and revealed subtle differences between animals of different ages. The youngest walrus in the sample (4 yr) contained higher concentrations of Pb and Cu than older animals in the growth layer deposited during the first year of life, while the oldest animal (33 yr) exhibited higher Pb and Zn than younger animals in the outer layer corresponding to the year 1988. The differences between animals and across annual layers may reflect both life history and metal exposure phenomena, including high amounts of metals transferred from mothers to pups in maternal milk. The ability to detect metals in a repeatable fashion within annual growth layers suggests that metal exposure histories accurate to within a year might be re-constructed for the life-times of long-lived animals, and that a series of such individual studies would allow exposure histories covering centuries to be quickly assembled. These data may suggest the most likely explanation for the currently high levels of some metals observed in certain Arctic marine mammals, i.e., natural phenomenon or anthropogenic contamination.

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

    PubMed

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

    2016-02-01

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

  2. Analysis and Speciation of Lanthanoides by ICP-MS

    NASA Astrophysics Data System (ADS)

    Telgmann, Lena; Lindner, Uwe; Lingott, Jana; Jakubowski, Norbert

    2016-11-01

    Inductively coupled plasma mass spectrometry (ICP-MS) is based on formation of positively charged atomic ions in a high-frequency inductively coupled Argon plasma at atmospheric pressure. The ions are extracted and transferred from the plasma source into a mass analyzer operated at high vacuum via an interface equipped with a sampling and a skimmer cone. The ions are separated in the mass analyzer according to their charge to mass ratio. The ions are converted at a conversion dynode and are detected by use of a secondary electron multiplier or a Faraday cup. From an analytical point of view, ICP-MS is a well-established method for multi-elemental analysis in particular for elements at trace- and ultra-trace levels. Furthermore, methods based on ICP-MS offer simple quantification concepts, for which usually (liquid) standards are applied, low matrix effects compared to other conventional analytical techniques, and relative limits of detection (LODs) in the low pg g-1 range and absolute LODs down to the attomol range. For these applications, ICP-MS excels by a high sensitivity which is independent of the molecular structure and a wide linear dynamic range. It has found acceptance in various application areas and during the last decade ICP-MS is also more and more applied for detection of rare earth elements particularly in the life sciences. Due to the fact that all molecules introduced into the high temperature of the plasma in the ion source were completely dissociated and broken down into atoms, which are subsequently ionized, all elemental species information is completely lost. However, if the different species are separated before they enter the plasma by using adequate fractionation or separation techniques, then ICP-MS can be used as a very sensitive element-specific detector. We will discuss this feature of ICP-MS in this chapter in more detail at hand of the speciation of gadolinium-containing contrast agents.

  3. [Determination of blue ballpoint pen ink by laser ablation inductively coupled plasma mass spectrometry].

    PubMed

    Ma, Dong; Shen, Min; Luo, Yi-wen; Bo, Jun; Xu, Che; Zhuo, Xian-yi

    2010-10-01

    To establish an identification method for the forensic analysis of blue ballpoint ink by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), 95 kinds of blue ballpoint pen from different manufacturers were detected. These blue ballpoint pens were classified into 34 groups according to their metal element components, among which, 26 groups can be directly distinguished according to the types of metal element components contained in the ballpoint pen, the other groups can be distinguished by different element response ratios. Meanwhile the examination result on the papers showed that the papers have no impact on the ink handwriting analysis. Experimental results showed that the method's reproducibility is good and precision is less than 10%. This method has better identification ability than traditional identification technology for questioned document. Eighty eight kinds of blue ballpoint pen out of the total 95 selected kinds can be distinguished with this method. The established method is simple, rapid, with good precision, and almost has no damage to the sample. It is particularly suitable for the demand of identification of blue ballpoint pen in forensic science.

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

    PubMed

    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. A table of polyatomic interferences in ICP-MS

    USGS Publications Warehouse

    May, Thomas W.; Wiedmeyer, Ray H.

    1998-01-01

    Spectroscopic interferences are probably the largest class of interferences in ICP-MS and are caused by atomic or molecular ions that have the same mass-to-charge as analytes of interest. Current ICP-MS instrumental software corrects for all known atomic “isobaric” interferences, or those caused by overlapping isotopes of different elements, but does not correct for most polyatomic interferences. Such interferences are caused by polyatomic ions that are formed from precursors having numerous sources, such as the sample matrix, reagents used for preparation, plasma gases, and entrained atmospheric gases.

  6. Isotopic analyses by ICP-MS in clinical samples.

    PubMed

    Rodushkin, Ilia; Engström, Emma; Baxter, Douglas C

    2013-03-01

    This critical review focuses on inductively coupled plasma mass spectrometry (ICP-MS) based applications for isotope abundance ratio measurements in various clinical samples relevant to monitoring occupational or environmental exposure, human provenancing and reconstruction of migration pathways as well as metabolic research. It starts with a brief overview of recent advances in ICP-MS instrumentation, followed by selected examples that cover the fields of accurate analyte quantification using isotope dilution, tracer studies in nutrition and toxicology, and areas relying upon natural or man-made variations in isotope abundance ratios (Pb, Sr, actinides and stable heavy elements). Finally, some suggestions on future developments in the field are provided.

  7. Non-traditional isotopes in analytical ecogeochemistry assessed by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Prohaska, Thomas; Irrgeher, Johanna; Horsky, Monika; Hanousek, Ondřej; Zitek, Andreas

    2014-05-01

    Analytical ecogeochemistry deals with the development and application of tools of analytical chemistry to study dynamic biological and ecological processes within ecosystems and across ecosystem boundaries in time. It can be best described as a linkage between modern analytical chemistry and a holistic understanding of ecosystems ('The total human ecosystem') within the frame of transdisciplinary research. One focus of analytical ecogeochemistry is the advanced analysis of elements and isotopes in abiotic and biotic matrices and the application of the results to basic questions in different research fields like ecology, environmental science, climatology, anthropology, forensics, archaeometry and provenancing. With continuous instrumental developments, new isotopic systems have been recognized for their potential to study natural processes and well established systems could be analyzed with improved techniques, especially using multi collector inductively coupled plasma mass spectrometry (MC-ICP-MS). For example, in case of S, isotope ratio measurements at high mass resolution could be achieved at much lower S concentrations with ICP-MS as compared to IRMS, still keeping suitable uncertainty. Almost 50 different isotope systems have been investigated by ICP-MS, so far, with - besides Sr, Pb and U - Ca, Mg, Cd, Li, Hg, Si, Ge and B being the most prominent and considerably pushing the limits of plasma based mass spectrometry also by applying high mass resolution. The use of laser ablation in combination with MC-ICP-MS offers the possibility to achieve isotopic information on high spatial (µm-range) and temporal scale (in case of incrementally growing structures). The information gained with these analytical techniques can be linked between different hierarchical scales in ecosystems, offering means to better understand ecosystem processes. The presentation will highlight the use of different isotopic systems in ecosystem studies accomplished by ICP-MS. Selected

  8. Advances in ID-TIMS and LA-MC-ICP-MS U-Pb mass spectrometry with applications to geochronology and environmental U analysis

    NASA Astrophysics Data System (ADS)

    Parrish, R. R.; Noble, S. R.; Condon, D. J.; Horstwood, M. S.; Bowring, S.; Schoene, B.; Crowley, Q.

    2006-12-01

    Recent advances highlighted are the analysis of tiny quantities of U and Pb isotopes, ID-TIMS U-Pb dating using EARTHTIME double spike tracers and improved detectors, and the performance of integrated LA-MC- ICP-MS systems for U-Pb dating. Detector improvements: The use of 1012 ohm resistors with faraday detectors has shown that their noise levels conform closely to prediction and overlap ion intensities previously in the realm of ion counting detectors, enabling multiple faraday ion detection for <20 pg of radiogenic Pb. A trade-off in slower response time, however, hinders rapid peak-switching data acquisition and favours use in static multicollection mode. Sub-ng high precision U analysis of complex matrices: The accurate measurement of U isotopes, including ^{236}U at the <1e^{-5} level, in sub-ng quantities of uranium, represents a very significant challenge to the detection of human internal uranium contamination many years after exposure. We have used MC-ICP-MS instruments with mixed SEM-faraday detectors along with improvements in chemical separation and purification to measure uranium isotopes in urine with detection limits of a few fg. In a large study >95% of samples intentionally blind-doped with very small amounts (~3 fg to 40 pg) of either depleted uranium or pure ^{236}U were accurately quantified from a sample cohort of more than 300 urine samples. ID-TIMS: Recent developments spearheaded by the EARTHTIME project (www.earth-time.org) has driven a community effort to improve inter-laboratory U-Pb comparability (and accuracy) via the development of mixed U-Pb tracer solutions for community use. In addition a ^{202}Pb-^{205}Pb-^{233}U-^{235}U double spike has been mixed as part of this project aimed at achieving increased precision via real time Pb mass bias determination. LA-MC-ICP-MS: The Pb/U and 207Pb/206Pb precision by LA-(MC)-ICP-MS can be comparable to SIMS U-Pb dating of zircon. A weakness of LA-ICP-MS U-Pb analysis has been the large

  9. Elemental impurity analysis of mercuric iodide by ICP/MS

    SciTech Connect

    Cross, E.S.; Mroz, E.; Olivares, J.A.

    1994-06-01

    A method has been developed to analyze mercuric iodide (HgI{sub 2}) for elemental contamination using Inductively Coupled Plasma/Mass Spectroscopy (ICP/MS). This paper discusses the ICP/MS method, the effectiveness of purification schemes for removing impurities from HgI{sub 2}, as well as preliminary correlations between HgI{sub 2} detector performance and elemental contamination levels. The purified HgI{sub 2} is grown into a single crystal by physical vapor transport. The crystal are cut into slices and they are fabricated into room temperature radiation detectors and photocells. Crystals that produce good resolution gamma detector do not necessarily make good resolution photocells or x-ray detectors. Many factors other than elemental impurities may contribute to these differences in performance.

  10. Common-Lead Corrected U-Pb Age Dating of Perovskite by LA-SF-ICP-MS

    NASA Astrophysics Data System (ADS)

    Frei, D.

    2014-12-01

    Perovskite is a very useful mineral for dating the age of emplacement of kimberlites and associated rocks. Conventionally, U-Pb dating of perovskite is achieved using isotope dilution (ID-TIMS) or ion-probe (SHRIMP) techniques, which are time- and cost-intensive. The potential of the rapid and inexpensive laser ablation ICP-MS technique for U-Pb dating of perovskite has been demonstrated recently. We investigated the benefits of single collector magnetic sectorfield ICP-MS (SF-ICP-MS) instruments for U-Pb dating of perovskite by laser ablation. To this end perovskites from two kimberlites from Garnet Lake, W Greenland, and Pyramidefjeld, SW Greenland, have been separated. Multigrain aliquots of both perovskite separates were U-Pb dated by ID-TIMS, yielding emplacement ages of 568 ±11 Ma for the Garnet Lake kimberlite and 151 ±2 Ma for the Pyramidefjeld kimberlite. Subsequently both samples have been dated in-situ by laser ablation employing a ThermoFinnigan Element2 SF-ICP-MS coupled to a NewWave UP 213 laser system. A common lead correction was applied based on the measured 204Pb intensity (after correction for the measured 204(Pb+Hg) gas blank). Perovskite from the Ice River Complex, British Columbia, was used as a secondary standard for quality control purposes. Multiple in-situ measurements of the Ice River perovskite in two different analytical sessions yielded concordia ages of 359 ±3 Ma and 357 ±3 Ma, in excellent agreement with the age of 356 Ma determined by ID-TIMS (Heaman, pers. comm.). Nineteen in-situ analyses of perovskite grains extracted from the Garnet Lake kimberlite yielded a concordia age of 566 ±5 Ma, also in excellent agreement with the age obtained by ID-TIMS. Because of the very low Pb contents in perovskites from the Pyramidefjeld (around 1 ppm) and the associated large uncertainties of the common lead correction, no concordia age could be obtained. However, the in-situ laser ablation analysis yielded a common lead corrected weighted

  11. Analysis of some Romanian fruit juices by ICP-MS

    NASA Astrophysics Data System (ADS)

    Dehelean, A.; Magdas, D. A.

    2013-11-01

    The present study was carried out to evaluate the heavy metal content of 21 Romanian single strength fruit (plum, apple, sour cherry) juices. The samples were collected from five Romanian areas namely: Alba, Maramures, Cluj, Salaj and Moldova. The results indicated macro (Na, Mg, Ca, P) and micro (Fe, Zn, Ni, Cr, Cd, Pb, etc) elements in the selected samples. The determination was performed by ICP-MS. Our results for fruit juice were compared with allowable limits for drinking water in the United Kingdom (NS30).

  12. Sector field mass spectrometers in ICP-MS

    NASA Astrophysics Data System (ADS)

    Jakubowski, Norbert; Moens, Luc; Vanhaecke, Frank

    1998-11-01

    A new generation of sector field mass spectrometers, with improved analytical figures of merit at even lower prices, is commercially available, giving a strong impetus to the development of inductively coupled plasma mass spectrometry (ICP-MS) sector field instrument applications in the analytical community. It is the aim of this paper to give an overview of these instruments, to introduce some basic concepts, to discuss their peculiarities and performance, and to present some selected examples of analytical applications to demonstrate the `state of the art'.

  13. Fingerprinting of ground water by ICP-MS. Final report

    SciTech Connect

    Stetzenbach, K.; Johannesson, K.

    1996-04-30

    Geochemical investigations of groundwater sources and mixing have relied heavily on the major solutes (Na{sup +}, K{sup +}, Ca{sup 2+}, Mg{sup 2+}, Cl{sup -}, SO{sub 4}{sup 2-}, HCO{sub 3}{sup -}, CO{sub 3}{sup 2-}, {plus_minus}F{sup -}, Br{sup -} , PO{sub 4}{sup 3-}), stable isotopes of hydrogen and oxygen ({delta}D and {delta}{sup 18}O), and, occasionally, radionuclides such as tritium ({sup 3}H) and carbon-14 ({sup 14}C). Problems with geochemical interpretations of such analyses arise from the low number of major solutes (typically between 7 and 8 are reported) which results in insufficient information for definitive interpretations. Moreover, isotopic analyses can be very costly. We present an alternative approach using numerous trace elements that occur naturally in all ground waters and that can now be measured rapidly and routinely using the inductively coupled plasma-mass spectrometer (ICP-MS) at the Harry Reid Center for Environmental Studies (HRC) at a fraction of the cost of isotopic analysis. The tremendous number of solutes that can be measured by ICP-MS necessitates the examination of each data set by multivariate statistical techniques that help to reduce the data and illuminate correlations between trace elements and, therefore, ground waters of similar and/or different origins.

  14. Reduction of polyatomic interferences in ICP-MS by collision/reaction cell (CRC-ICP-MS) techniques

    SciTech Connect

    Eiden, Greg C; Barinaga, Charles J; Koppenaal, David W

    2012-05-01

    Polyatomic and other spectral interferences in plasma source mass spectrometry (PSMS) can be dramatically reduced using collision and reaction cells (CRC). These devices have been used for decades in fundamental studies of ion-molecule chemistry, but have only recently been applied to PSMS. Benefits of this approach as applied in inductively coupled plasma MS (ICP-MS) include interference reduction, isobar separation, and thermalization/focusing of ions. Novel ion-molecule chemistry schemes are now routinely designed and empirically evaluated with relative ease. These “chemical resolution” techniques can avert interferences requiring mass spectral resolutions of >600,000 (m/m). Purely physical ion beam processes, including collisional dampening and collisional dissociation, are also employed to provide improved sensitivity, resolution, and spectral simplicity. CRC techniques are now firmly entrenched in current-day ICP-MS technology, enabling unprecedented flexibility and freedom from many spectral interferences. A significant body of applications has now been reported in the literature. CRC techniques are found to be most useful for specialized or difficult analytical needs and situations, and are employed in both single- and multi-element determination modes.

  15. Trace element determination in vitamin E using ICP-MS.

    PubMed

    Ponce De León, Claudia A; Montes Bayón, Maria; Caruso, Joseph A

    2002-09-01

    Vitamin E supplements are either isolated from plants sources or prepared synthetically. Isolation from plants includes eight different tocopherol structures. Vitamin E synthesis includes seven different stereoisomers, which involves the use of several catalysts that may lead to trace element contamination in the vitamin. The use of ICP-MS is an ideal technique for detecting these trace elements. However, the oily nature of the samples requires the development of a sample preparation methodology. This study was done upon the request of synthetic vitamin E manufacturers to test the trace metal purity of their samples. In this work, the comparison of an acid microwave digestion and emulsion preparation is discussed. Cromium, nickel, tin and lead were found in the synthetic vitamin E analyzed and 200, 60, 9 and 45 ppb were the concentrations found respectively for these elements. Digesting the samples gives slightly lower detection limits compared to the emulsion preparation.

  16. Sensitive redox speciation of neptunium by CE-ICP-MS.

    PubMed

    Stöbener, Nils; Amayri, Samer; Gehl, Aaron; Kaplan, Ugras; Malecha, Kurtis; Reich, Tobias

    2012-11-01

    Capillary electrophoresis (CE) was used to separate the neptunium oxidation states Np(IV) and Np(V), which are the only oxidation states of Np that are stable under environmental conditions. The CE setup was coupled to an inductively coupled plasma mass spectrometer (Agilent 7500ce) using a Mira Mist CE nebulizer and a Scott-type spray chamber. The combination of the separation capacity of CE with the detection sensitivity of inductively coupled plasma mass spectrometry (ICP-MS) allows identification and quantification of Np(IV) and Np(V) at the trace levels expected in the far field of a nuclear waste repository. Limits of detection of 1 × 10(-9) and 5 × 10(-10) mol L(-1) for Np(IV) and Np(V), respectively, were achieved, with a linear range from 10(-9) to 10(-6) mol L(-1). The method was applied to study the redox speciation of the Np remaining in solution after interaction of 5 × 10(-7) mol L(-1) Np(V) with Opalinus Clay. Under mildly oxidizing conditions, a Np sorption of 31% was found, with all the Np remaining in solution being Np(V). A second sorption experiment performed in the presence of Fe(2+) led to complete sorption of the Np onto the clay. After desorption with HClO(4), a mixture of Np(IV) and Np(V) was found in solution by CE-ICP-MS, indicating that some of the sorbed Np had been reduced to Np(IV) by Fe(2+).

  17. Overview and comparison of ICP-MS methods for environmental analyses

    SciTech Connect

    Wolf, R.E.; Denoyer, E.; Grosser, Z.

    1996-11-01

    Inductively Coupled Plasma Mass Spectrometry (ICP-MS) offers the modern laboratory a number of advantages, including low detection limits and high sample throughput. The EPA has recognized the potential benefits of this technique for analytical capability and the ability to reduce the cost per test and has recently approved a series of new methods based on ICP-MS instrumentation.

  18. Selenite biotransformation during brewing. Evaluation by HPLC-ICP-MS.

    PubMed

    Sánchez-Martínez, Maria; da Silva, Erik Galvão P; Pérez-Corona, Teresa; Cámara, Carmen; Ferreira, Sergio L C; Madrid, Yolanda

    2012-01-15

    Yeast (Saccharomyces cerevisiae) and lactic bacteria have shown their ability to accumulate and transform inorganic selenium into organo Se compounds. The objective of this work was to evaluate selenium biotransformation during brewing by using S. cerevisiae and Saccharomyces uvarum for Ale and Lager fermentation, respectively. Se-enriched beer was produced by the addition of sodium selenite (0, 0.2, 1.0, 2.0, 10.0, 20.0 μg Se mL(-1), respectively) to the fermentation media composed of yeast, malt extract and water. The alcoholic fermentation process was not affected by the presence of selenium regardless of the type of Saccharomyces being used. The percentage of selenium incorporated into beer, added between 1.0 and 10 μg mL(-1) was 55-60% of the selenium initially present. Se-compounds in post-fermentation (beer and yeast) products were investigated by using an analytical methodology based on HPLC-ICP-MS. For this purpose, several sample treatments, including ultrasonic-assisted enzymatic hydrolysis, in conjunction with different separation mechanisms like dialysis and anion exchange HPLC chromatography were applied for unambiguously identifying Se-species that produce during brewing. Selenomethionine was the main selenium compound identified in beer and yeast, being this species in the only case of the former not associated to peptides or proteins.

  19. ICP MS selection of radiopure materials for the GERDA experiment

    SciTech Connect

    Di Vacri, M. L.; Nisi, S.; Cattadori, C.; Janicsko, J.; Lubashevskiy, A.; Smolnikov, A.; Walter, M.

    2015-08-17

    The GERDA (GERmanium Detector Array) experiment, located in the Gran Sasso Underground Laboratory (LNGS, Italy) aims to search for neutrinoless double beta (0νββ) decay of the {sup 76}Ge isotope. Both an ultra-low radioactivity background environment and active techniques to abate the residual background are required to reach the background index (of 10{sup −3} counts/keV kg y) at the Q{sub ββ}. In order to veto and suppress those events that partially deposit energy in Ge detectors, the readout of liquid argon (LAr) scintillation light (SL) has been implemented for the second GERDA experimental Phase. A double veto system has been designed and constructed using highly radiopure materials (scintillating fibers, wavelength shifters, polymeric foils, reflective foils). This work describes the study of lead, thorium and uranium ultra-trace content, performed at the LNGS Chemistry Laboratory by High Resolution Mass Spectrometry (HR ICP MS), for the selection of all materials involved in the construction of the veto system.

  20. Determination of 238u/235u, 236u/238u and uranium concentration in urine using sf-icp-ms and mc-icp-ms: an interlaboratory comparison.

    PubMed

    Parrish, Randall R; Thirlwall, Matthew F; Pickford, Chris; Horstwood, Matthew; Gerdes, Axel; Anderson, James; Coggon, David

    2006-02-01

    Accidental exposure to depleted or enriched uranium may occur in a variety of circumstances. There is a need to quantify such exposure, with the possibility that the testing may post-date exposure by months or years. Therefore, it is important to develop a very sensitive test to measure precisely the isotopic composition of uranium in urine at low levels of concentration. The results of an interlaboratory comparison using sector field (SF)-inductively coupled plasma-mass spectrometry (ICP-MS) and multiple collector (MC)-ICP-MS for the measurement of uranium concentration and U/U and U/U isotopic ratios of human urine samples are presented. Three urine samples were verified to contain uranium at 1-5 ng L and shown to have natural uranium isotopic composition. Portions of these urine batches were doped with depleted uranium (DU) containing small quantities of U, and the solutions were split into 100 mL and 400 mL aliquots that were subsequently measured blind by three laboratories. All methods investigated were able to measure accurately U/U with precisions of approximately 0.5% to approximately 4%, but only selected MC-ICP-MS methods were capable of consistently analyzing U/U to reasonable precision at the approximately 20 fg L level of U abundance. Isotope dilution using a U tracer demonstrates the ability to measure concentrations to better than +/-4% with the MC-ICP-MS method, though sample heterogeneity in urine samples was shown to be problematic in some cases. MC-ICP-MS outperformed SF-ICP-MS methods, as was expected. The MC-ICP-MS methodology described is capable of measuring to approximately 1% precision the U/U of any sample of human urine over the entire range of uranium abundance down to <1 ng L, and detecting very small amounts of DU contained therein.

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

    USGS Publications Warehouse

    Rusk, Brian; Koenig, Alan; Lowers, Heather

    2011-01-01

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

  2. Metal ion transport quantified by ICP-MS in intact cells.

    PubMed

    Figueroa, Julio A Landero; Stiner, Cory A; Radzyukevich, Tatiana L; Heiny, Judith A

    2016-02-03

    The use of ICP-MS to measure metal ion content in biological tissues offers a highly sensitive means to study metal-dependent physiological processes. Here we describe the application of ICP-MS to measure membrane transport of Rb and K ions by the Na,K-ATPase in mouse skeletal muscles and human red blood cells. The ICP-MS method provides greater precision and statistical power than possible with conventional tracer flux methods. The method is widely applicable to studies of other metal ion transporters and metal-dependent processes in a range of cell types and conditions.

  3. Metal ion transport quantified by ICP-MS in intact cells

    PubMed Central

    Figueroa, Julio A. Landero; Stiner, Cory A.; Radzyukevich, Tatiana L.; Heiny, Judith A.

    2016-01-01

    The use of ICP-MS to measure metal ion content in biological tissues offers a highly sensitive means to study metal-dependent physiological processes. Here we describe the application of ICP-MS to measure membrane transport of Rb and K ions by the Na,K-ATPase in mouse skeletal muscles and human red blood cells. The ICP-MS method provides greater precision and statistical power than possible with conventional tracer flux methods. The method is widely applicable to studies of other metal ion transporters and metal-dependent processes in a range of cell types and conditions. PMID:26838181

  4. A simple laser ablation ICPMS method for the determination of trace metals in a resin gel.

    PubMed

    Gao, Yue; Lehto, Niklas

    2012-04-15

    Trace metal analysis of DGT gels using laser ablation inductively coupled plasma (LA-ICP-MS) has traditionally been carried out by ablating single spots along a line to provide high resolution data on trace metal distributions on a resin gel. This work compares the performance of two different LA-ICPMS systems, one at Lancaster University, UK and another at VUB, Belgium, in terms of instrument sensitivity and limit of detection in the analysis of trace metals (Co, Ni, Cu, Zn, Cd, and Pb) bound by a DGT resin gel using SPR-IDA resin. No defocusing of the laser beam was necessary to prevent burning through the resin gel and the internal standardization became very simple by using (13)C, naturally present in the resin-gel, instead of impregnating a back-up layer with (115)In. Furthermore, this work also explores the option of analysing the spatial distribution of resin bound trace metals by means of ablating a continuous line between two points and considers the advantages of using this approach. The work found that the LODs assessed on blank samples for Cu and Pb are similar for both LA-ICPMS systems, while for Co, Ni and Zn they are lower for the one at VUB and for Cd for the other one at Lancaster. The work found that the laser ablation systems at the two laboratories allowed more precise control over laser power and spot size than previously reported. For the line scan, the optimum scan parameters were determined as: scan speed of 50 μm s(-1), output energy of 40% and repetition rate of 30 Hz. An acquisition time of 25 ms, resulted in a much lower resolution (10 μm) compared to the spot ablation (a crater size of 100 μm and also some space between craters) and a better sensitivity. The LODs using the line scan were found to be lower than those obtained by the spot ablation. However, for some of the metals the difference is rather small. This work suggests that the time and gas consumption achieved by using the line scan is about 30% lower than for the

  5. In-situ Strontium Isotopes Analysis on Single Conodont Apatite by LA-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Zhang, L.; Chen, Z. Q.; Ma, D.; Qiu, H.; Lv, Z.; Hu, Z.; Wang, F.

    2014-12-01

    Strontium isotope played an important role in stratigraphic chronology and sedimentary geochemistry research (McArthur et al., 2001). Conodonts is a kind of extinct species of marine animals and widely distributed in marine sediments all over the world. Rich in radiogenic Sr contents and difficulty to be affected during diagenesis alteration makes conodonts a good choice in seawater Sr isotope composition studies (John et al., 2008). Conodont samples were collected from 24th to 39th layer across Permian-Triassic boundary at Meishan D section (GSSP), Zhejiang Province, South China (Yin et al., 2001). Conodonts was originated from fresh limestone and only conodont elements with CAI<2 were chosen for in-situ strontium isotope analysis using laser-ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Conodont samples are from totally 25 layers in seven conodont zones making it possible for a high resolution 87Sr/ 86Sr curve reconstruction during the Permian-Triassic transition. 87Sr/ 86Sr ratio kept a relatively high value (0.70752) in the middle part of the Clarkina yini zone and a lower value (0.70634) in the upperpart of Clarkina taylorae zone. Of which, 87Sr/ 86Sr ratio emerged a rapid decrease within the Clarkina taylorae zone. After a subsequent increase, 87Sr/ 86Sr ratio dropped to 0.70777 in the Isarcicella staeschei zone. These results helps providing reference data for the biological mass extinction events during the Permian-Triassic transition. Our study also makes is possible for high resolution 87Sr/ 86Sr ratio testing on the single conodont apatite and riched the in-situ studies on the conodont apatite, which of great significance for the future conodont Sr isotope research (Zhao et al., 2009; Zhao et al., 2013). Keywords: Conodonts, Strontium isotope, LA-MC-ICP-MS, Permian-Triassic transition, Meishan D section [1] John et al., 2008 3P[2] McArthur et al., 2001 J. of Geology [3] Yin et al., 2001 Episodes [4] Zhao et al

  6. Multielemental speciation analysis by advanced hyphenated technique - HPLC/ICP-MS: A review.

    PubMed

    Marcinkowska, Monika; Barałkiewicz, Danuta

    2016-12-01

    Speciation analysis has become an invaluable tool in human health risk assessment, environmental monitoring or food quality control. Another step is to develop reliable multielemental speciation methodologies, to reduce costs, waste and time needed for the analysis. Separation and detection of species of several elements in a single analytical run can be accomplished by high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Our review assembles articles concerning multielemental speciation determination of: As, Se, Cr, Sb, I, Br, Pb, Hg, V, Mo, Te, Tl, Cd and W in environmental, biological, food and clinical samples analyzed with HPLC/ICP-MS. It addresses the procedures in terms of following issues: sample collection and pretreatment, selection of optimal conditions for elements species separation by HPLC and determination using ICP-MS as well as metrological approach. The presented work is the first review article concerning multielemental speciation analysis by advanced hyphenated technique HPLC/ICP-MS.

  7. Improved stratigraphic dating at a low accumulation Alpine ice core through laser ablation trace element profiling at sub-mm depth resolution

    NASA Astrophysics Data System (ADS)

    Bohleber, Pascal; Spaulding, Nicole; Mayewski, Paul; Sneed, Sharon; Handley, Mike; Erhardt, Tobias; Wagenbach, Dietmar

    2015-04-01

    The small scale Colle Gnifetti glacier saddle (4450 m asl, Monte Rosa region) is the only ice core drilling site in the European Alps with a net accumulation low enough to offer multi-millennia climate records. However, a robust interpretation of such long term records (i.e. mineral dust, stable water isotopes) at the Colle Gnifetti (CG) multi core array is strongly challenged by depositional noise associated with a highly irregular annual layer stratigraphy. In combination with a relatively large vertical strain rate and rapid layer thinning, annual layer counting gets increasingly ambiguous as of approximately 100 years. In addition, this prevents clear attribution of likely volcanic horizons to historical eruption dates. To improve stratigraphic dating under such intricate conditions, we deployed laser ablation (LA) ICP-MS at sub-mm sample resolution. We present here the first LA impurity profiles from a new Colle Gnifetti ice core drilled 73 m to bedrock in 2013 at a site where the net snow accumulation is around 20 cm w.e. per year. We contrast the LA signal variability (including Ca, Fe, Na) to continuous flow analyses (CFA) records at cm-resolution (Ca, Na, melt water conductivity, micro- particle) recorded over the whole core length. Of special concern are the lower 28 m to bedrock, which have been continuously profiled in LA Ca, thus offering the direct comparison of Ca-signals between CFA and LA. By this means, we first validate at upper depths LA based annual layer identification through agreement with CFA based counting efforts before demonstrating the LA based counting still works at depths where CFA derived annual layers become spurious since embedded in strong, multi-year cycles. Finally, LA ice core profiling of our CG core has potential for not only dating improvement but also reveals benefits in resolving highly thinned basal ice sections including accounting for micro-structural features such as grain boundaries.

  8. Single Particle ICP-MS: Advances toward routine analysis of nanomaterials.

    PubMed

    Montaño, Manuel D; Olesik, John W; Barber, Angela G; Challis, Katie; Ranville, James F

    2016-07-01

    From its early beginnings in characterizing aerosol particles to its recent applications for investigating natural waters and waste streams, single particle inductively coupled plasma-mass spectrometry (spICP-MS) has proven to be a powerful technique for the detection and characterization of aqueous dispersions of metal-containing nanomaterials. Combining the high-throughput of an ensemble technique with the specificity of a single particle counting technique and the elemental specificity of ICP-MS, spICP-MS is capable of rapidly providing researchers with information pertaining to size, size distribution, particle number concentration, and major elemental composition with minimal sample perturbation. Recently, advances in data acquisition, signal processing, and the implementation of alternative mass analyzers (e.g., time-of-flight) has resulted in a wider breadth of particle analyses and made significant progress toward overcoming many of the challenges in the quantitative analysis of nanoparticles. This review provides an overview of spICP-MS development from a niche technique to application for routine analysis, a discussion of the key issues for quantitative analysis, and examples of its further advancement for analysis of increasingly complex environmental and biological samples. Graphical Abstract Single particle ICP-MS workflow for the analysis of suspended nanoparticles.

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

    PubMed

    Chahrour, Osama; Malone, John

    2016-12-12

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

  10. Detrital zircon LASS-ICP-MS petrochronologic depth profiling for determining source-to-sink relationships in the Central Alps.

    NASA Astrophysics Data System (ADS)

    Anfinson, O. A.; Stockli, D. F.; Stockli, L.; Malusa', M. G.

    2015-12-01

    Laser Ablation-Split Stream Depth Profiling (LASS-DP) ICP-MS petrochronology of detrital zircon (DZ) from Oligocene-Miocene strata in the Molasse and Northern Apennines showcases, in the light of the well-constrained depositional history of these successions, the advantages of this novel approach compared to traditional single and split-stream detrital zircon techniques in elucidating sediment provenance and source-to-sink relationships. While DZ U-Pb data from Oligocene-Miocene strata deposited in both the Molasse and Northern Apennines document shifts in the relative abundance of Cadomian, Caledonian, Variscan and Alpine aged detrital zircon, the source regions remain ambiguous due to non-diagnostic crystallization ages, leading to minimal zircon age variability. In contrast, DZ LASS-DP-ICP-MS petrochronology allows for the simultaneous recovery of multiple U-Pb ages and corresponding geochemical data, and thus dramatically increases our ability to resolve the petrogenetic history of individual DZ grains. The technique shows the immense power of determining the growth history of single DZ grains (rim to core relationships) and identifying/resolving the presence and age of thin magmatic/metamorphic overgrowths. Rupelian turbidites in the Apenninic foredeep exhibit a DZ population with consistent <5 mm Cretaceous metamorphic overgrowths that would likely not be resolved as a coherent population in polished sections. LASS-DP ICP-MS analysis of Caledonian and Variscan detrital zircon populations from the Molasse Basin show a distinct shift in rim-core age pairs in individual zircons that point to the erosion of different source during progressive Alpine unroofing. The geochemical data confirm a crustally derived magmatic source for the majority of the detrital zircon grains within the basin. While this technique, in comparison to traditional polished mounts, might underrepresent older core ages, this slight bias is clearly offset by the better definition and

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

    SciTech Connect

    Lewis, L.A.

    1998-05-01

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

  12. Evolving Pb isotope signatures of London airborne particulate matter (PM 10)-constraints from on-filter and solution-mode MC-ICP-MS.

    PubMed

    Noble, Stephen R; Horstwood, Matthew S A; Davy, Pamela; Pashley, Vanessa; Spiro, Baruch; Smith, Steve

    2008-07-01

    Pb isotope compositions of biologically significant PM(10) atmospheric particulates from a busy roadside location in London UK were measured using solution- and laser ablation-mode MC-ICP-MS. The solution-mode data for PM(10) sampled between 1998-2001 document a dramatic shift to increasingly radiogenic compositions as leaded petrol was phased out. LA-MC-ICP-MS isotope analysis, piloted on a subset of the available samples, is shown to be a potential reconnaissance analytical technique. PM(10) particles trapped on quartz filters were liberated from the filter surface, without ablating the filter substrate, using a 266 nm UV laser and a dynamic, large diameter, low-fluence ablation protocol. The Pb isotope evolution noted in the London data set obtained by both analytical protocols is similar to that observed elsewhere in Western Europe following leaded petrol elimination. The data therefore provide important baseline isotope composition information useful for continued UK atmospheric monitoring through the early 21(st) century.

  13. Development of analytical procedures for determination of total chromium by quadrupole ICP-MS and high-resolution ICP-MS, and hexavalent chromium by HPLC-ICP-MS, in different materials used in the automotive industry.

    PubMed

    Séby, F; Gagean, M; Garraud, H; Castetbon, A; Donard, O F X

    2003-10-01

    A European directive was recently adopted limiting the use of hazardous substances such as Pb, Hg, Cd, and Cr(VI) in vehicle manufacturing. From July 2003 a maximum of 2 g Cr(VI) will be authorised per vehicle in corrosion-preventing coatings of key components. As no standardised procedures are available to check if produced vehicles are in agreement with this directive, the objective of this work was to develop analytical procedures for total chromium and Cr(VI) determination in these materials. The first step of this study was to optimise digestion procedures for total chromium determination in plastic and metallic materials by inductively coupled plasma mass spectrometry (ICP-MS). High resolution (HR) ICP-MS was used to examine the influence of polyatomic interferences on the detection of the (52)Cr(+) and (53)Cr(+) isotopes. If there was strong interference with m/ z 52 for plastic materials, it was possible to use quadrupole ICP-MS for m/ z 53 if digestions were performed with HNO(3)+H(2)O(2). This mixture was also necessary for digestion of chromium from metallic materials. Extraction procedures in alkaline medium (NH(4)(+)/NH(3) buffer solution at pH 8.9) assisted by sonication were developed for determining Cr(VI) in four different corrosion-preventing coatings by HPLC-ICP-MS. After optimisation and validation with the only solid reference material certified for its Cr(VI) content (BCR 545; welding dusts), the efficiency of this extraction procedure for screw coatings was compared with that described in the EN ISO 3613 standard generally used in routine laboratories. For coatings comprising zinc and aluminium passivated in depth with chromium oxides the extraction procedure developed herein enabled determination of higher Cr(VI) concentrations. This was also observed for the screw covered with a chromium passivant layer on zinc-nickel. For coating comprising a chromium passivant layer on alkaline zinc the standardized extraction procedure was more efficient

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

    SciTech Connect

    Ebert, Christopher Hysjulien

    2012-01-01

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

  15. Improving Alpha Spectrometry Energy Resolution by Ion Implantation with ICP-MS

    SciTech Connect

    Dion, Michael P.; Liezers, Martin; Farmer, Orville T.; Miller, Brian W.; Morley, Shannon M.; Barinaga, Charles J.; Eiden, Gregory C.

    2015-01-01

    We report results of a novel technique using an Inductively Coupled Plasma Mass Spectrometer (ICP-MS) as a method of source preparation for alpha spectrometry. This method produced thin, contaminant free 241Am samples which yielded extraordinary energy resolution which appear to be at the lower limit of the detection technology used in this research.

  16. Accurate and precise determination of isotopic ratios by MC-ICP-MS: a review.

    PubMed

    Yang, Lu

    2009-01-01

    For many decades the accurate and precise determination of isotope ratios has remained a very strong interest to many researchers due to its important applications in earth, environmental, biological, archeological, and medical sciences. Traditionally, thermal ionization mass spectrometry (TIMS) has been the technique of choice for achieving the highest accuracy and precision. However, recent developments in multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) have brought a new dimension to this field. In addition to its simple and robust sample introduction, high sample throughput, and high mass resolution, the flat-topped peaks generated by this technique provide for accurate and precise determination of isotope ratios with precision reaching 0.001%, comparable to that achieved with TIMS. These features, in combination with the ability of the ICP source to ionize nearly all elements in the periodic table, have resulted in an increased use of MC-ICP-MS for such measurements in various sample matrices. To determine accurate and precise isotope ratios with MC-ICP-MS, utmost care must be exercised during sample preparation, optimization of the instrument, and mass bias corrections. Unfortunately, there are inconsistencies and errors evident in many MC-ICP-MS publications, including errors in mass bias correction models. This review examines "state-of-the-art" methodologies presented in the literature for achievement of precise and accurate determinations of isotope ratios by MC-ICP-MS. Some general rules for such accurate and precise measurements are suggested, and calculations of combined uncertainty of the data using a few common mass bias correction models are outlined.

  17. Studying the distribution pattern of selenium in nut proteins with information obtained from SEC-UV-ICP-MS and CE-ICP-MS.

    PubMed

    Kannamkumarath, Sasi S; Wrobel, Katarzyna; Wuilloud, Rodolfo G

    2005-03-31

    In this work, size exclusion chromatography (SEC) with UV and inductively coupled plasma mass spectrometry (ICP-MS) detection was used to study the association of selenium to proteins present in Brazil nuts (Bertholletia excelsa) under five different extraction conditions. As expected, better solubilization of proteins was observed using 0.05molL(-1) sodium hydroxide and 1% sodium dodecylsulfate (SDS) in Tris/HCl buffer (0.05molL(-1), pH 8) as compared to 0.05molL(-1) HCl, 0.05molL(-1) Tris/HCl or hot water (60 degrees C). Due to non-destructive character of Tris-SDS treatment, this was applied for studying molecular weight (MW) distribution patterns of selenium-containing nut proteins. Three different SEC columns were used for obtaining complete MW distribution of selenium: Superdex 75, Superdex Peptide, and Superdex 200 were tested with 50mmolL(-1) Tris buffer (pH 8), 150mmolL(-1) ammonium bicarbonate buffer (pH 7.8), phosphate (pH 7.5), and CAPS (pH 10.0) mobile phases. Using Superdex 200 column, the elution of at least three MW fractions was observed with UV detection (200-10kDa) and ICP-MS chromatogram showed the co-elution of selenium with the two earlier fractions. The apparent MWs of these selenium-containing fractions were respectively about 107 and 50kDa, as evaluated from the column calibration. For further characterization of individual selenium species, the defatted nuts were hydrolyzed with proteinase K and analyzed by capillary electrophoresis (CE) with ICP-MS detection. The suitability of CE for the separation of selenite, selenate, selenocystine and selenomethionine in the presence of the nut sample matrix is demonstrated. Complete separation of the above mentioned selenium species was obtained within a migration time of 7min. In the analysis of nut extracts with CE-ICP-MS, selenium was found to be present mainly as selenomethionine.

  18. Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

    NASA Technical Reports Server (NTRS)

    Morgan, Leah E.; Lloyd, Nicholas S.; Ellam, Robert M.; Simon, Justin I.

    2012-01-01

    Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample

  19. High-precision isotopic characterization of USGS reference materials by TIMS and MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Weis, Dominique; Kieffer, Bruno; Maerschalk, Claude; Barling, Jane; de Jong, Jeroen; Williams, Gwen A.; Hanano, Diane; Pretorius, Wilma; Mattielli, Nadine; Scoates, James S.; Goolaerts, Arnaud; Friedman, Richard M.; Mahoney, J. Brian

    2006-08-01

    The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR-1, 2; BHVO-1, 2), andesite (AGV-1, 2), rhyolite (RGM-1, 2), syenite (STM-1, 2), granodiorite (GSP-2), and granite (G-2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR-1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC-ICP-MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR-ICP-MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC-ICP-MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC-ICP-MS, respectively). Our results also show that the first- and second-generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC-ICP-MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC-ICP-MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first- and second-generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions

  20. Quantitative determination of bromine and iodine in food samples using ICP-MS.

    PubMed

    Nguyen, Thi Kim Dzung; Ludwig, Rainer

    2014-01-01

    Trace concentrations of bromine and iodine in food samples and certified reference materials (CRMs) were determined by an inductively coupled plasma-mass spectrometry (ICP-MS) technique after low-power microwave digestion and extraction into an aqueous quaternary ammonium hydroxide solution. The recovery after sample preparation was quantitative. The internal standard for the measurement of the analyte on ICP-MS was optimized in this study. The detection limits were 0.19 and 0.68 ng g(-1) for I and Br, respectively, when a 10 ng g(-1) Te solution as an internal standard was used, applying the signal of (125)Te. The high recovery and reproducibility are sufficient for the quantitative analysis of these elements, and the analytical procedure is recommended for the analysis of Br and I in various kinds of bio-samples.

  1. Development of ICP-MS based nanometrology techniques for characterization of silver nanoparticles in environmental systems

    NASA Astrophysics Data System (ADS)

    Mitrano, Denise Marie

    The ubiquitous use of goods containing nanoparticles (NPs) will lead inevitably to environmental release and interaction with biota. Methods to detect, quantify, and characterize NPs in environmental matrices are highlighted as one of the areas of highest priority research in understanding potential environmental and health risks. Specifically, techniques are needed to determine the size and concentration of NPs in complex matrices. Particular analytical challenges include distinguishing NPs from other constituents of the matrix (i.e. natural particles, humic substances, and debris), method detection limits are often higher than exposure concentrations, and differentiating dissolved metal and NPs. This work focuses on the development and optimization of two methods that address a number of challenges for nanometrology: single particle (sp)ICP-MS and asymmetrical flow field flow fractionation (AF4)-ICP-MS. Advancements in the spICP-MS method included systematic studies on distinction between ionic and NP fractions, resolution of polydisperse NP samples, and defining the techniques' dynamic range (in terms of both particle size and concentration). Upon application of the technique, silver (Ag) NPs were discovered in raw wastewater treatment plant influent and effluent. Furthermore, methodical Ag NP stability studies determined the influence of particle capping agents and water chemistry parameters in a variety of synthetic, natural and processed waters. Method development for AF4-ICP-MS revolved around optimizing run conditions (i.e. operational flows, carrier fluid, membrane choice) to study detection limits, sample recovery, and resolution of polydisperse samples. Practical studies included sizing Ag NP in a sediment-dwelling, freshwater oligochaete (Lumbriculus variegatus) and the kinetics of accumulation of protein bound Ag+. In direct comparison, spICP-MS was found to be more versatile with less sample preparation and lower total analyte detection limit (ng/L vs

  2. Methods for the Detection and Characterization of Silica Colloids by Microsecond spICP-MS.

    PubMed

    Montaño, Manuel D; Majestic, Brian J; Jämting, Åsa K; Westerhoff, Paul; Ranville, James F

    2016-05-03

    The rapid development of nanotechnology has led to concerns over their environmental risk. Current analytical techniques are underdeveloped and lack the sensitivity and specificity to characterize these materials in complex environmental and biological matrices. To this end, single particle ICP-MS (spICP-MS) has been developed in the past decade, with the capability to detect and characterize nanomaterials at environmentally relevant concentrations in complex environmental and biological matrices. However, some nanomaterials are composed of elements inherently difficult to quantify by quadrupole ICP-MS due to abundant molecular interferences, such as dinitrogen ions interfering with the detection of silicon. Three approaches aimed at reducing the contribution of these background molecular interferences in the analysis of (28)Si are explored in an attempt to detect and characterize silica colloids. Helium collision cell gases and reactive ammonia gas are investigated for their conventional use in reducing the signal generated from the dinitrogen interference and background silicon ions leaching from glass components of the instrumentation. A new approach brought on by the advent of microsecond dwell times in single particle ICP-MS allows for the detection and characterization of silica colloids without the need for these cell gases, as at shorter dwell times the proportion of signal attributed to a nanoparticle event is greater relative to the constant dinitrogen signal. It is demonstrated that the accurate detection and characterization of these materials will be reliant on achieving a balance between reducing the contribution of the background interference, while still registering the maximum amount of signal generated by the particle event.

  3. Simultaneous Speciation of Arsenic, Selenium, and Chromium by HPLC-ICP-MS

    USGS Publications Warehouse

    Wolf, Ruth E.; Morman, Suzette A.; Morrison, Jean M.; Lamothe, Paul J.

    2008-01-01

    An adaptation of an analytical method developed for chromium speciation has been utilized for the simultaneous determination of As(III), As(V), Se(IV), Se(VI), Cr(III), and Cr(VI) species using high performance liquid chromatography (HPLC) separation with ICP-MS detection. Reduction of interferences for the determination of As, Se, and Cr by ICP-MS is a major consideration for this method. Toward this end, a Dynamic Reaction Cell (DRC) ICP-MS system was used to detect the species eluted from the chromatographic column. A variety of reaction cell gases and conditions may be utilized, and the advantages and limitations of the gases tested to date will be presented and discussed. The separation and detection of the As, Se, and Cr species of interest can be achieved using the same chromatographic conditions in less than 2 minutes by complexing the Cr(III) with EDTA prior to injection on the HPLC column. Practical aspects of simultaneous speciation analysis will be presented and discussed, including issues with HPLC sample vial contamination, standard and sample contamination, species stability, and considerations regarding sample collection and preservation methods. The results of testing to determine the method's robustness to common concomitant element and anion effects will also be discussed. Finally, results will be presented using the method for the analysis of a variety of environmental and geological samples including waters, soil leachates and simulated bio-fluid leachates.

  4. Assessment of CE-ICP/MS hyphenation for the study of uranyl/protein interactions.

    PubMed

    Huynh, Thi-Ngoc Suong; Bourgeois, Damien; Basset, Christian; Vidaud, Claude; Hagège, Agnès

    2015-06-01

    Identification of uranyl transport proteins is key to develop efficient detoxification approaches. Therefore, analytical approaches have to be developed to cope with the complexity of biological media and allow the analysis of metal speciation. CE-ICP/MS was used to combine the less-intrusive character and high separation efficiency of CE with the sensitive detection of ICP/MS. The method was based on the incubation of samples with uranyl prior to the separation. Electrophoretic buffers were compared to select a 10 mM Tris to 15 mM NaCl buffer, which enabled analyses at pH 7.4 and limited dissociation. This method was applied to the analysis of a serum. Two main fractions were observed. By comparison with synthetic mixtures of proteins, the first one was attributed to fetuin and in a lesser extent to HSA, and the second one to uranyl unbound to proteins. The analysis showed that fetuin was likely to be the main target of uranyl. CE-ICP/MS was also used to investigate the behavior of the fetuin-uranyl complex, in the presence of carbonate, an abundant complexing agent of uranyl in blood. This method enabled association constants determination, suggesting the occurrence of both FETUA(UO2(2+)) and FETUA(UO2(2+))(CO3(2-)) complexes, depending on the carbonate concentration.

  5. Evaluation of Ultra-Low Background Materials for Uranium and Thorium Using ICP-MS

    SciTech Connect

    Hoppe, Eric W.; Overman, Nicole R.; LaFerriere, Brian D.

    2013-08-08

    An increasing number of physics experiments require low background materials for their construction. The presence of Uranium and Thorium and their progeny in these materials present a variety of unwanted background sources for these experiments. The sensitivity of the experiments continues to drive the necessary levels of detection ever lower as well. This requirement for greater sensitivity has rendered direct radioassay impractical in many cases requiring large quantities of material, frequently many kilograms, and prolonged counting times, often months. Other assay techniques have been employed such as Neutron Activation Analysis but this requires access to expensive facilities and instrumentation and can be further complicated and delayed by the formation of unwanted radionuclides. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a useful tool and recent advancements have increased the sensitivity particularly in the elemental high mass range of U and Th. Unlike direct radioassay, ICP-MS is a destructive technique since it requires the sample to be in liquid form which is aspirated into a high temperature plasma. But it benefits in that it usually requires a very small sample, typically about a gram. Here we will discuss how a variety of low background materials such as copper, polymers, and fused silica are made amenable to ICP-MS assay and how the arduous task of maintaining low backgrounds of U and Th is achieved.

  6. Evaluation of ultra-low background materials for uranium and thorium using ICP-MS

    SciTech Connect

    Hoppe, E. W.; Overman, N. R.; LaFerriere, B. D.

    2013-08-08

    An increasing number of physics experiments require low background materials for their construction. The presence of Uranium and Thorium and their progeny in these materials present a variety of unwanted background sources for these experiments. The sensitivity of the experiments continues to drive the necessary levels of detection ever lower as well. This requirement for greater sensitivity has rendered direct radioassay impractical in many cases requiring large quantities of material, frequently many kilograms, and prolonged counting times, often months. Other assay techniques have been employed such as Neutron Activation Analysis but this requires access to expensive facilities and instrumentation and can be further complicated and delayed by the formation of unwanted radionuclides. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a useful tool and recent advancements have increased the sensitivity particularly in the elemental high mass range of U and Th. Unlike direct radioassay, ICP-MS is a destructive technique since it requires the sample to be in liquid form which is aspirated into a high temperature plasma. But it benefits in that it usually requires a very small sample, typically about a gram. This paper discusses how a variety of low background materials such as copper, polymers, and fused silica are made amenable to ICP-MS assay and how the arduous task of maintaining low backgrounds of U and Th is achieved.

  7. Fingerprinting of ground water by ICP-MS; Progress report, July 1, 1991--December 31, 1991

    SciTech Connect

    Stetzenbach, K.

    1991-12-31

    The purpose of this project is to investigate the use of minor constituents of ground water and vadose zone water such as the rare earths and some lighter elements, to delineate ground water flow paths and recharge zones in the Yucca Mountain area. The major piece of equipment required to perform this task is an inductively coupled plasma-mass spectrometer (ICP-MS). This instrument has been purchased and should be delivered in February 1992. During this reporting period, three ICP-MS systems were evaluated the Perkin-Elmer Elan 5000 was chosen. As part of the evaluation process, samples of J-13 water and tuff were prepared and analyzed by each of the competing companies. This gave us the opportunity to make initial observations as to the number of compounds and their concentrations present in the J-13 samples. Table 1 lists the results of the analysis of J-13 water. Once the ICP-MS is operational, we will be collecting and analyzing waters from existing wells, springs, and seeps to determine which of these minor chemical constituents will be most helpful in establishing chemical signatures for the ground waters beneath Yucca Mountain.

  8. Fast Scanning Single Collector ICP-MS for Low Level Isotope Ratio Measurements

    NASA Astrophysics Data System (ADS)

    Newman, K.; Georg, B.

    2010-12-01

    Multiple collector (MC)-ICP-MS is recognized as a workhorse in the field of isotope ratio measurements. With its unrivalled precision, high sample throughput and multi-element coverage, MC-ICPMS has opened up new areas of study in earth, environmental and biological sciences. However, SC-ICP-MS is fit for purpose for many applications where sample amount is limited and fractionations are relatively large. To compensate for the inherent ion beam instability associated with the ICP ion source, fast scanning magnetic sector instruments are used. Here, we describe and discuss the use of the Nu Attom SC-ICP-MS for low level isotope ratio measurements. The Nu Attom is a double focusing magnetic sector mass spectrometer with unique fast scanning capabilities. Deflectors located at the entrance and exit of the flight tube are used to alter the effective magnet radius by changing the ion trajectory. This enables a fast electrostatic scan over a mass range of approximately 40%. In contrast to other fast scanning magnetic sector instruments, there is no change in the ion energy which may introduce additional mass bias effects. The Nu Attom also has fully adjustable source and collector slits. This facilitates measurements in medium mass resolution (R=1500-2500), whilst maintaining a flat topped peak necessary for precise isotope ratio measurements. The potential applications of the Nu Attom in isotope ratio measurements will be explored.

  9. Improving the accuracy of hand-held X-ray fluorescence spectrometers as a tool for monitoring brominated flame retardants in waste polymers.

    PubMed

    Guzzonato, A; Puype, F; Harrad, S J

    2016-09-01

    An optimised method for Br quantification as a metric of brominated flame retardant (BFR) concentrations present in Waste Electrical and Electronic Equipment (WEEE) polymers is proposed as an alternative to the sophisticated, yet time consuming GC-MS methods currently preferred. A hand-held X-ray fluorescence (XRF) spectrometer was validated with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Customized standard materials of specific BFRs in a styrenic polymer were used to perform an external calibration for hand-held XRF ranging from 0.08 to 12 wt% of Br, and cross-checking with LA-ICP-MS having similar LODs (0.0004 wt% for LA-ICP-MS and 0.0011 wt% for XRF). The "thickness calibration" developed here for hand-held XRF and the resulting correction, was applied to 28 real samples and showed excellent (R(2) = 0.9926) accordance with measurements obtained via LA-ICP-MS. This confirms the validity of hand-held XRF as an accurate technique for the determination of Br in WEEE plastics. This is the first use of solid standards to develop a thickness-corrected quantitative XRF measurement of Br in polymers using LA-ICP-MS for method evaluation. Thermal desorption gas chromatography mass spectrometry (TD-GC-MS) was used to confirm the presence of specific BFRs in WEEE polymer samples. We propose that expressing limit values for BFRs in waste materials in terms of Br rather than BFR concentration (based on a conservative assumption about the BFR present), presents a practical solution to the need for an accurate, yet rapid and inexpensive technique capable of monitoring compliance with limit values in situ.

  10. Nanoparticle size detection limits by single particle ICP-MS for 40 elements.

    PubMed

    Lee, Sungyun; Bi, Xiangyu; Reed, Robert B; Ranville, James F; Herckes, Pierre; Westerhoff, Paul

    2014-09-02

    The quantification and characterization of natural, engineered, and incidental nano- to micro-size particles are beneficial to assessing a nanomaterial's performance in manufacturing, their fate and transport in the environment, and their potential risk to human health. Single particle inductively coupled plasma mass spectrometry (spICP-MS) can sensitively quantify the amount and size distribution of metallic nanoparticles suspended in aqueous matrices. To accurately obtain the nanoparticle size distribution, it is critical to have knowledge of the size detection limit (denoted as Dmin) using spICP-MS for a wide range of elements (other than a few available assessed ones) that have been or will be synthesized into engineered nanoparticles. Herein is described a method to estimate the size detection limit using spICP-MS and then apply it to nanoparticles composed of 40 different elements. The calculated Dmin values correspond well for a few of the elements with their detectable sizes that are available in the literature. Assuming each nanoparticle sample is composed of one element, Dmin values vary substantially among the 40 elements: Ta, U, Ir, Rh, Th, Ce, and Hf showed the lowest Dmin values, ≤10 nm; Bi, W, In, Pb, Pt, Ag, Au, Tl, Pd, Y, Ru, Cd, and Sb had Dmin in the range of 11-20 nm; Dmin values of Co, Sr, Sn, Zr, Ba, Te, Mo, Ni, V, Cu, Cr, Mg, Zn, Fe, Al, Li, and Ti were located at 21-80 nm; and Se, Ca, and Si showed high Dmin values, greater than 200 nm. A range of parameters that influence the Dmin, such as instrument sensitivity, nanoparticle density, and background noise, is demonstrated. It is observed that, when the background noise is low, the instrument sensitivity and nanoparticle density dominate the Dmin significantly. Approaches for reducing the Dmin, e.g., collision cell technology (CCT) and analyte isotope selection, are also discussed. To validate the Dmin estimation approach, size distributions for three engineered nanoparticle samples were

  11. High precision 11B/10B analysis with a simplified MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Tanimizu, M.; Nagaishi, K.

    2012-04-01

    Boron isotope ratio is a powerful tracer in the fields of geochemistry, biochemistry, and environmental chemistry. One important application of 11B/10B isotope ratio in geochemistry is as an indicator for paleo pH of seawater recorded in marine carbonates in deep-sea sediments. Boron isotope ratios are determined by TIMS or MC-ICP-MS with precisions of better than 0.1 % RSD, but a large inter-lab discrepancy of 0.6 % is still observed for actual carbonate samples (Foster, 2008). Here, we tried to determine B isotope ratio by MC-ICP-MS with a simple and common analytical techniques using a quartz sample introduction system with a PFA nebulizer, and compared to recently developed precise B isotope ratio analysis techniques by TIMS in positive ion detection mode determined as Cs2BO2+ ions with sample amount of <100 ng (Ishikawa and Nagaishi, 2011) and by MC-ICP-MS (Foster, 2008, Louvat et al., 2011). 11B/10B isotope ratios of a 50 ppb B solution dissolved in a HNO3, mannitol, HF-mixed solution were determined against an isotopic reference NIST-SRM 951 with a standard sample bracketing technique in the wet plasma condition. Resultant analytical reproducibility (twice standard deviation) was +/-0.02 % with a consumption of 50 ng B, and the washout time was comparable to that of NH3 gas addition to the introduction system (Foster, 2008). 11B/10B isotope ratios of actual carbonate sample and seawater were determined after simple chemical purification with a common cation exchange resin instead of a boron selective resin. Their relative differences from the standard were consistent with those determined by the positive TIMS within analytical uncertainty. Current potential of MC-ICP-MS for precise B isotopic analysis will be discussed. Foster, G., 2008. Seawater pH, pCO2 and [CO32-] variations in the Caribbean Sea over the last 130kyr: A boron isotope and B/Ca study of planktic foraminifera, Earth Planet. Sci. Lett., 271, 254-266. Ishikawa, T. and Nagaishi, K., 2011. High

  12. Determination of trace elements on polysilicates by ID-ICP-MS with ultrasonic nebulization/membrane desolvation

    SciTech Connect

    Bonchin-Cleland, S.; Olivares, J.A.; Miller, G.G.; Gallegos, L.; Dawson, H.J.

    1996-06-01

    This work investigates the performance of an ID-ICP-MS (isotope dilution-inductively coupled plasma mass spectrometry) system with USN/MD (ultrasonic nebulization/membrane desolvation) sample introduction for the determination of trace metal impurities in polysilicon.

  13. Small-Volume U-Pb Zircon Geochronology by Laser Ablation-Multicollector-ICP-MS

    DTIC Science & Technology

    2008-11-03

    30-second acquisition routine that measures backgrounds followed by sample peaks in one-second integration periods . Background intensities are...essential to repeat these linearity experiments periodically to check linearity and recalibrate the correction models, if necessary. 2.3. Data...extraction efficiency, 3) low signals that require longer counting integration periods of 1 s, and 4) the short 8–10 s duration of the sample signal

  14. In Situ Analysis of Orthopyroxene in Diogenites Using Laser Ablation ICP-MS

    NASA Technical Reports Server (NTRS)

    Elk, Mattias; Quinn, J. E.; Mittlefehldt, D. W.

    2012-01-01

    Howardites, eucrites and diogenites (HED) form a suit of igneous achondrite meteorites that are thought to have formed on a single asteroidal body. While there have been many different models proposed for the formation of the HED parent asteroid they can be generalized into two end member models. One is the magma ocean model (e.g. [1]) in which the entire HED parent body was continuously fractionated from a planet wide magma ocean with diogenites representing the lower crust and eucrites being upper crustal rocks. The second model hypothesizes that diogenites and eucrites were formed as a series of intrusions and/or extrusions of partial melts of a primitive proto-Vesta [2]. We use in situ trace element analysis together with major and minor element analysis to try and distinguish between these different hypotheses for the evolution of the HED parent body.

  15. Post hoc interlaboratory comparison of single particle ICP-MS size measurements of NIST gold nanoparticle reference materials.

    PubMed

    Montoro Bustos, Antonio R; Petersen, Elijah J; Possolo, Antonio; Winchester, Michael R

    2015-09-01

    Single particle inductively coupled plasma-mass spectrometry (spICP-MS) is an emerging technique that enables simultaneous measurement of nanoparticle size and number quantification of metal-containing nanoparticles at realistic environmental exposure concentrations. Such measurements are needed to understand the potential environmental and human health risks of nanoparticles. Before spICP-MS can be considered a mature methodology, additional work is needed to standardize this technique including an assessment of the reliability and variability of size distribution measurements and the transferability of the technique among laboratories. This paper presents the first post hoc interlaboratory comparison study of the spICP-MS technique. Measurement results provided by six expert laboratories for two National Institute of Standards and Technology (NIST) gold nanoparticle reference materials (RM 8012 and RM 8013) were employed. The general agreement in particle size between spICP-MS measurements and measurements by six reference techniques demonstrates the reliability of spICP-MS and validates its sizing capability. However, the precision of the spICP-MS measurement was better for the larger 60 nm gold nanoparticles and evaluation of spICP-MS precision indicates substantial variability among laboratories, with lower variability between operators within laboratories. Global particle number concentration and Au mass concentration recovery were quantitative for RM 8013 but significantly lower and with a greater variability for RM 8012. Statistical analysis did not suggest an optimal dwell time, because this parameter did not significantly affect either the measured mean particle size or the ability to count nanoparticles. Finally, the spICP-MS data were often best fit with several single non-Gaussian distributions or mixtures of Gaussian distributions, rather than the more frequently used normal or log-normal distributions.

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

    PubMed

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

    2013-01-01

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

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

    PubMed

    Morton, Jackie; Leese, Elizabeth

    2011-02-01

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

  18. A comparison of double-focusing sector field ICP-MS, ICP-OES and octopole collision cell ICP-MS for the high-accuracy determination of calcium in human serum.

    PubMed

    Simpson, Lorna A; Hearn, Ruth; Merson, Sheila; Catterick, Tim

    2005-02-28

    Human serum is routinely measured for total calcium content in clinical studies. A definitive high-accuracy and low-uncertainty method is required for reference measurements to underpin medical diagnoses. This study presents a novel octopole collision cell ICP-MS, high-accuracy, methodology and comparison of that technique with double-focusing sector field ICP-MS and an ICP-OES method. Double-matched isotope dilution mass spectrometry (IDMS) was employed for ICP-MS techniques and an exact matching bracketing technique using scandium as an internal standard was used for ICP-OES analysis. Medium resolution mode was utilised for double-focusing sector field ICP-MS analysis to resolve the dominant interferences on the (44)Ca/(42)Ca isotope pair. Hydrogen reaction gas was employed to chemically resolve a number of polyatomic interferences predominantly through charge transfer reactions in the octopole collision cell. Comparison data presented for NIST CRM 909b human serum analysis from all three techniques demonstrates highest accuracy (99.6%) and lowest uncertainty (1.1%) for octopole collision cell ICP-MS. Data from ICP-OES using a non-IDMS technique produces comparably accurate data and low-uncertainties. The much higher total expanded uncertainties for double-focusing sector field ICP-MS compared with octopole collision cell data are explained by lower precision on the measurement of the (44)Ca/(42)Ca isotope ratio. Data for octopole collision cell ICP-MS submitted for an international blind trial comparison (CCQM K-14) demonstrated excellent agreement with the mean of all participants with a low expanded uncertainty.

  19. Determination of δ88/86Sr Using Matrix Correction by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Zhu, B.; Yang, T.; Bian, X. P.; Zhu, Z. Y.

    2014-12-01

    Stable Sr isotopic compositions (δ88/86Sr) in marine carbonates potentially provide key information on paleoseawater temperature (Rüggeberg et al. 2008). Traditional methods for δ88/86Sr determination by 87Sr-84Sr double-spike TIMS or MC-ICP-MS require chemical purification of Sr before spectrometric measurements because of matrix effects. Recent studies suggested that the matrix-matching method, in which matrix-matched standard solutions were used to bracket untreated water samples, gave precise and accurate results for sulfur isotopic ratios by MC-ICP-MS (Lin et al., 2014). The obvious advantage of this method is that there is no need for chemical purification, thus eliminating the possibility of isotope fractionation during the ion chromatography and expediting sample throughput. In this study, we applied the matrix-matching method to δ88/86Sr determination by MC-ICP-MS. NIST 987 Sr solution and a purified seawater sample (collected from the South China Sea) were selected for this study. Given that major matrices in carbonate come form Ca2+, NIST 987 and SW solutions containing 40 ppm Ca2+ were prepared by adding high-purity Ca solution. All solutions used contained 200 ppb Sr and the 88Sr/86Sr ratios were measured using a Neptune MC-ICP-MS. The purified SW was first determined using SSB method, in which pure NIST 987 was used as standard to bracket SW and yielded δ88/86Sr value of 0.366 ± 0.008‰ (2SE, n = 10). The δ88/86Sr values of Ca-bearing SW were then measured by using pure NIST 987 solution as the working standard to investigate matrix effects. The determined δ88/86Sr value (0.039 ± 0.021‰; 2SE, n = 10) deviated obviously from the reference value. Finally, the matrix-matched NIST 987 was applied as the working standard to bracket the Ca-bearing SW, and the measured δ88/86Sr value is 0.351 ± 0.009‰ (2SE, n = 10), consistent with the reference value within uncertainties. The consistent δ88/86Sr values and comparable external precision

  20. Fingerprinting of groundwater by ICP-MS. Quarterly progress report, October 1, 1995--December 31, 1995

    SciTech Connect

    Stetzenbach, K.

    1996-02-01

    This document is a progress report for the Fingerprinting of Ground Water by ICP-MS project during the time period from October 1, 1995 to December 31, 1995. The groundwater fingerprinting study has been expanded by including samples from more wells on the Nevada Test Site and from the region east and north of Yucca Mountain as well as from several more springs in the area. Geochemical analyses of these new samples were performed in order to more thoroughly evaluate the regional groundwater chemistry and flow regime. The results of the geochemical analyses are described in this report.

  1. Simultaneous iron, zinc, sulfur and phosphorus speciation analysis of barley grain tissues using SEC-ICP-MS and IP-ICP-MS.

    PubMed

    Persson, Daniel P; Hansen, Thomas H; Laursen, Kristian H; Schjoerring, Jan K; Husted, Søren

    2009-09-01

    The increasing prevalence of iron (Fe) and zinc (Zn) deficiencies in human populations worldwide has stressed the need for more information about the distribution and chemical speciation of these elements in cereal products. In order to investigate these aspects, barley grains were fractionated into awns, embryo, bran and endosperm and analysed for Fe and Zn. Simultaneously, phosphorus (P) and sulfur (S) were determined since these elements are major constituents of phytic acid and proteins, respectively, compounds which are potentially involved in Fe and Zn binding. A novel analytical method was developed in which oxygen was added to the octopole reaction cell of the ICP-MS. This approach greatly improved the sensitivity of sulfur, measured as (48)SO(+). Simultaneously, Fe was measured as (72)FeO(+), P as (47)PO(+), and Zn as (66)Zn(+), enabling sensitive and simultaneous analysis of these four elements. The highest concentrations of Zn, Fe, S and P were found in the bran and embryo fractions. Further analysis of the embryo using SEC-ICP-MS revealed that the speciation of Fe and Zn differed. The majority of Fe co-eluted with P as a species with the apparent mass of 12.3 kDa, whereas the majority of Zn co-eluted with S as a 3 kDa species, devoid of any co-eluting P. Subsequent ion pairing chromatography of the Fe/P peak showed that phytic acid (myo-inositol-1,2,3,4,5,6-hexakisphosphate: IP(6)) was the main Fe binding ligand, with the stoichiometry Fe(4)(IP(6))(18). When incubating the embryo tissue with phytase, the enzyme responsible for degradation of phytic acid, the extraction efficiency of both Fe and P was doubled, whereas that of Zn and S was unaffected. Protein degradation on the other hand, using protease XIV, boosted the extraction of Zn and S, but not that of Fe and P. It is concluded that Fe and Zn have a different speciation in cereal grain tissues; Zn appears to be mainly bound to peptides, while Fe is mainly associated with phytic acid.

  2. Hf Isotopic Geochemistry of Zircon by Multiple Collector-Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS): A New Chemical Procedure

    NASA Astrophysics Data System (ADS)

    Goolaerts, A.; Mattielli, N.; Weis, D.; Scoates, J. S.

    2001-12-01

    Zircon is the major reservoir of Hf in most crustal rocks and is characterized by low Lu/Hf. In situ analysis of zircon by laser ablation MC-ICP-MS is currently gaining favor in the geochemical community due to the precise spatial control of analysis required for zircons with complex internal morphology. However, the disadvantages of the laser ablation technique include lower precision than MC-ICP-MS, increased isobaric interferences, important memory effects, and poor control of Lu-Hf fractionation. We present a new chemical and analytical method for determining the Hf isotopic composition of zircon specifically designed for a new-generation MC-ICP-MS instrument (Nu Plasma). After dissolution, our chemical procedure involves chromatographic separation in two stages with an overall yield of ~80%: Hf-Zr are isolated from the REE using AG50W X8 resin and Lu-Yb are isolated from the lighter REE using HDEHP resin. Routine isotopic analysis of 176Hf/177Hf on the standard JMC-475 gives an internal precision of 19 ppm and an external precision of 40 ppm with a sensitivity of 20 volts/ppm for an uptake of 80 μ l/min. The average 176Hf/177Hf value for JMC-475 is 0.282162 +/- 3 (2se), which falls within error of the accepted value of 0.282163 +/- 9. The isotopic composition of Lu was carried out using a mixed Lu-Yb standard solution (AAS, Alfa Aesar) of 50 ppb with an average value for 175Lu/176Lu of 37.72 +/- 2 (2sd). Preliminary results from low-U (<100 ppm) zircon in monzonitic intrusions of the 1.43 Ga Laramie anorthosite complex, Wyoming, USA, demonstrate the extreme sensitivity of Hf isotopes in magmatic zircon to crustal contamination. Initial ɛ Hf values vary from -1 to +4 and are positively correlated with the whole rock Zr concentrations (299-2143 ppm) and negatively correlated with initial 87Sr/86Sr (0.70749-0.71295) for a constant value of initial ɛ Nd (-2.5) in the whole rocks. These correlations clearly reflect the effects of contamination by Archean crustal

  3. Potential Health Benefits and Metabolomics of Camel Milk by GC-MS and ICP-MS.

    PubMed

    Ahamad, Syed Rizwan; Raish, Mohammad; Ahmad, Ajaz; Shakeel, Faiyaz

    2017-02-01

    None of the research reports reveals the metabolomics and elemental studies on camel milk. Recent studies showed that camel milk possesses anticancer and anti-inflammatory activity. Metabolomics and elemental studies were carried out in camel milk which showed us the pathways and composition that are responsible for the key biological role of camel milk. Camel milk was dissolved in methanol and chloroform fraction and then vortexed and centrifuged. Both the fractions were derivatized by N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA) and TMCS after nitrogen purging and analyzed by GC-MS. Camel milk was also analyzed by ICP-MS after microwave digestion. We found that higher alkanes and fatty acids are present in the chloroform fraction and amino acids, sugars and fatty acid derivatives are present in aqueous fractions. All the heavy metals like As, Pb, Cd, Co, Cu, and Ni were in the safe limits in terms of maximum daily intake of these elements. Na, K, Mg, and Ca were also present in the safe limits in terms of maximum daily intake of these elements. These results suggested that the camel milk drinking is safe and there is no health hazard. The present data of GC-MS and ICP-MS correlate the activities related to camel milk.

  4. [Determination of 27 elements in Maca nationality's medicine by microwave digestion ICP-MS].

    PubMed

    Yu, Gui-fang; Zhong, Hai-jie; Hu, Jun-hua; Wang, Jing; Huang, Wen-zhe; Wang, Zhen-zhong; Xiao, Wei

    2015-12-01

    An analysis method has been established to test 27 elements (Li, Be, B, Mg, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Sr, Mo, Cd, Sn, Sb, Ba, La, Hg, Pb, Bi) in Maca nationality's medicine with microwave digestion-ICP-MS. Sample solutions were analyzed by ICP-MS after microwave digestion, and the contents of elements were calculated according to their calibration curves, and internal standard method was adopted to reduce matrix effect and other interference effects. The experimental results showed that the linear relations of all the elements were very good; the correlation coefficient (r) was 0.9994-1.0000 (Hg was 0.9982) ; the limits of detection were 0.003-2.662 microg x L(-1); the relative standard deviations for all elements of reproducibility were lower than 5% (except the individual elements); the recovery rate were 78.5%-123.7% with RSD lower than 5% ( except the individual elements). The analytical results of standard material showed acceptable agreement with the certified values. This method was applicable to determinate the contents of multi-elements in Maca which had a high sensitivity, good specificity and good repeatability, and provide basis for the quality control of Maca.

  5. A rapid ICP-MS screen for heavy metals in pharmaceutical compounds.

    PubMed

    Lewen, Nancy; Mathew, Shyla; Schenkenberger, Martha; Raglione, Thomas

    2004-06-29

    A robust general inductively coupled plasma-mass spectrometry (ICP-MS) based method was developed as an alternative to the wet chemical heavy metals test prescribed in the United States Pharmacopoeia (USP), British Pharmacopoeia (BP), Japanese Pharmacopoeia (JP) and European Pharmacopoeia (EP). The described method provides specific detection and quantitation for each of the elements expected to give rise to a positive response in the compendial methods: arsenic (As), selenium (Se), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), lead (Pb), bismuth (Bi), silver (Ag), palladium (Pd), platinum (Pt), mercury (Hg), molybdenum (Mo) and ruthenium (Ru). The subjectiveness of the visual based semi-quantitative comparison that is performed in the compendial methods is eliminated through the utilization of the ICP-MS. The described method has been in use for several years and its versatility has been demonstrated by successfully applying it to a wide variety of sample matrices. Analysis of the specific elemental data from the numerous sample matrices investigated indicates that there is no dependence of the various chemical functionalities contained in the sample matrices on the individual element recoveries. The average recovery for each element from the various sample matrices investigated ranged from 89 to 102%.

  6. Evaluation of the inorganic selenium biotransformation in selenium-enriched yogurt by HPLC-ICP-MS.

    PubMed

    Alzate, Adriana; Cañas, Benito; Pérez-Munguía, Sandra; Hernández-Mendoza, Hector; Pérez-Conde, Concepción; Gutiérrez, Ana Maria; Cámara, Carmen

    2007-11-28

    Selenium is an essential element in the human diet. Interestingly, there has been an increased consumption of dietary supplements containing this element in the form of either inorganic or organic compounds. The effect of using selenium as a dietary supplement in yogurt has been evaluated. For this purpose, different concentrations of inorganic Se (ranging from 0.2 to 5000 microg g(-1)) have been added to milk before the fermentation process. Biotransformation of inorganic Se into organic species has been carefully evaluated by ion-exchange, reversed-phase, or size-exclusion chromatography, coupled to inductively coupled plasma mass spectrometry (ICP-MS). Yogurt fermentation in the presence of up to 2 microg g(-1) of Se(IV) produces a complete incorporation of this element into proteins as has been demonstrated applying a dialysis procedure. Analysis by SEC-ICP-MS showed that most of them have a molecular mass in the range of 30-70 kDa. Species determination after enzymatic hydrolysis has allowed the identification of Se-cystine using two different chromatographic systems. The biotransformation process that takes place during yogurt fermentation is very attractive because yogurt can act as a source of selenium supplementation.

  7. A lead isotope distribution study in swine tissue using ICP-MS

    USGS Publications Warehouse

    May, T.W.; Wiedmeyer, Ray H.; Brown, L.D.; Casteel, S.W.

    1999-01-01

    In the United States lead is an ubiquitous environmental pollutant that is a serious human health hazard, especially for women of childbearing age, developing fetuses, and young children. Information concerning the uptake and distribution of lead to maternal and fetal tissues during pregnancy is poorly documented. A study was designed using domestic swine and lead isotope enrichment methodology to focus on maternal absorption and distribution of lead into bone and soft tissues, including the fetal compartment, under varying conditions of oral lead exposure and during altered physiological states (pregnant vs unbred). Total lead levels and Pb207/Pb206 ratios in bone (femur and vertebra), blood, and soft tissues (liver, kidney, brain) were determined by ICP-MS. Lead in fetal tissues derived from maternal bone could be differentiated from that derived from exogenous dosing. Unbred swine absorbed much less lead than pregnant females receiving the same dose. The accuracy and precision of ICP-MS at the instrumental level and for the entire method (sample collection, digestion, and analysis) were evaluated for both Pb207/Pb206 ratios and total lead. Several changes were suggested in method design to improve both instrumental and total method precision.

  8. Detection of Engineered Copper Nanoparticles in Soil Using Single Particle ICP-MS

    PubMed Central

    Navratilova, Jana; Praetorius, Antonia; Gondikas, Andreas; Fabienke, Willi; von der Kammer, Frank; Hofmann, Thilo

    2015-01-01

    Regulatory efforts rely on nanometrology for the development and implementation of laws regarding the incorporation of engineered nanomaterials (ENMs) into industrial and consumer products. Copper is currently one of the most common metals used in the constantly developing and expanding sector of nanotechnology. The use of copper nanoparticles in products, such as agricultural biocides, cosmetics and paints, is increasing. Copper based ENMs will eventually be released to the environment through the use and disposal of nano-enabled products, however, the detection of copper ENMs in environmental samples is a challenging task. Single particle inductively coupled plasma mass spectroscopy (spICP-MS) has been suggested as a powerful tool for routine nanometrology efforts. In this work, we apply a spICP-MS method for the detection of engineered copper nanomaterials in colloidal extracts from natural soil samples. Overall, copper nanoparticles were successfully detected in the soil colloidal extracts and the importance of dwell time, background removal, and sample dilution for method optimization and recovery maximization is highlighted. PMID:26690460

  9. Detection of Engineered Copper Nanoparticles in Soil Using Single Particle ICP-MS.

    PubMed

    Navratilova, Jana; Praetorius, Antonia; Gondikas, Andreas; Fabienke, Willi; von der Kammer, Frank; Hofmann, Thilo

    2015-12-10

    Regulatory efforts rely on nanometrology for the development and implementation of laws regarding the incorporation of engineered nanomaterials (ENMs) into industrial and consumer products. Copper is currently one of the most common metals used in the constantly developing and expanding sector of nanotechnology. The use of copper nanoparticles in products, such as agricultural biocides, cosmetics and paints, is increasing. Copper based ENMs will eventually be released to the environment through the use and disposal of nano-enabled products, however, the detection of copper ENMs in environmental samples is a challenging task. Single particle inductively coupled plasma mass spectroscopy (spICP-MS) has been suggested as a powerful tool for routine nanometrology efforts. In this work, we apply a spICP-MS method for the detection of engineered copper nanomaterials in colloidal extracts from natural soil samples. Overall, copper nanoparticles were successfully detected in the soil colloidal extracts and the importance of dwell time, background removal, and sample dilution for method optimization and recovery maximization is highlighted.

  10. Extraction techniques for arsenic species in rice flour and their speciation by HPLC-ICP-MS.

    PubMed

    Narukawa, Tomohiro; Suzuki, Toshihiro; Inagaki, Kazumi; Hioki, Akiharu

    2014-12-01

    The extraction of arsenic (As) species present in rice flour samples was investigated using different extracting solvents, and the concentration of each species was determined by HPLC-ICP-MS after heat-assisted extraction. The extraction efficiencies for total arsenic species and especially for arsenite [As(III)] and arsenate [As(V)] were investigated. As(III), As(V) and dimethylarsinic acid (DMAA) were found in the samples, and the concentration of DMAA did not vary with treatment conditions. However, the concentrations of extracted total arsenic and those of As(III) and As(V) depended on the extracting solvents. When an extracting solvent was highly acidic, the concentrations of extracted total arsenic were in good agreement with the total arsenic concentration determined by ICP-MS after microwave-assisted digestion, though a part of the As(V) was reduced to As(III) during the highly acidic extraction process. Extraction under neutral conditions increased the extracted As(V), but extracted total arsenic was decreased because a part of the As(III) could not be extracted. Optimum conditions for the extraction of As(III) and As(V) from rice flour samples are discussed to allow the accurate determinations of As(III), As(V) and DMAA in the rice flour samples. Heat block extraction techniques using 0.05 mol L(-1) HClO4 and silver-containing 0.15 mol L(-1) HNO3 were also developed.

  11. Reduction of Solvent Effect in Reverse Phase Gradient Elution LC-ICP-MS

    SciTech Connect

    Sullivan, Patrick Allen

    2005-12-17

    Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity of the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such separations, an alternative to isotope dilution for quantification would be is needed. To this end, a new method was developed using the Apex-Q desolvation system (ESI, Omaha, NE) to couple LC instrumentation with an ICP-MS device. The desolvation power of the system allowed greater concentrations of methanol to be introduced to the plasma prior to destabilization than with direct methanol injection into the plasma. Studies were performed, using simulated and actual linear methanol gradients, to find analyte-internal standard (AIS) pairs whose ratio remains consistent (deviations {+-} 10%) over methanol concentration ranges of 5

  12. Novel Applications of Lanthanoides as Analytical or Diagnostic Tools in the Life Sciences by ICP-MS-based Techniques

    NASA Astrophysics Data System (ADS)

    Müller, Larissa; Traub, Heike; Jakubowski, Norbert

    2016-11-01

    Inductively coupled plasma mass spectrometry (ICP-MS) is a well-established analytical method for multi-elemental analysis in particular for elements at trace and ultra-trace levels. It has found acceptance in various application areas during the last decade. ICP-MS is also more and more applied for detection in the life sciences. For these applications, ICP-MS excels by a high sensitivity, which is independent of the molecular structure of the analyte, a wide linear dynamic range and by excellent multi-element capabilities. Furthermore, methods based on ICP-MS offer simple quantification concepts, for which usually (liquid) standards are applied, low matrix effects compared to other conventional bioanalytical techniques, and relative limits of detection (LODs) in the low pg g-1 range and absolute LODs down to the attomol range. In this chapter, we focus on new applications where the multi-element capability of ICP-MS is used for detection of lanthanoides or rare earth elements, which are applied as elemental stains or tags of biomolecules and in particular of antibodies.

  13. Determination of phosphorus in small amounts of protein samples by ICP-MS.

    PubMed

    Becker, J Sabine; Boulyga, Sergei F; Pickhardt, Carola; Becker, J; Buddrus, Stefan; Przybylski, Michael

    2003-02-01

    Inductively coupled plasma mass spectrometry (ICP-MS) is used for phosphorus determination in protein samples. A small amount of solid protein sample (down to 1 micro g) or digest (1-10 micro L) protein solution was denatured in nitric acid and hydrogen peroxide by closed-microvessel microwave digestion. Phosphorus determination was performed with an optimized analytical method using a double-focusing sector field inductively coupled plasma mass spectrometer (ICP-SFMS) and quadrupole-based ICP-MS (ICP-QMS). For quality control of phosphorus determination a certified reference material (CRM), single cell proteins (BCR 273) with a high phosphorus content of 26.8+/-0.4 mg g(-1), was analyzed. For studies on phosphorus determination in proteins while reducing the sample amount as low as possible the homogeneity of CRM BCR 273 was investigated. Relative standard deviation and measurement accuracy in ICP-QMS was within 2%, 3.5%, 11% and 12% when using CRM BCR 273 sample weights of 40 mg, 5 mg, 1 mg and 0.3 mg, respectively. The lowest possible sample weight for an accurate phosphorus analysis in protein samples by ICP-MS is discussed. The analytical method developed was applied for the analysis of homogeneous protein samples in very low amounts [1-100 micro g of solid protein sample, e.g. beta-casein or down to 1 micro L of protein or digest in solution (e.g., tau protein)]. A further reduction of the diluted protein solution volume was achieved by the application of flow injection in ICP-SFMS, which is discussed with reference to real protein digests after protein separation using 2D gel electrophoresis.The detection limits for phosphorus in biological samples were determined by ICP-SFMS down to the ng g(-1) level. The present work discusses the figure of merit for the determination of phosphorus in a small amount of protein sample with ICP-SFMS in comparison to ICP-QMS.

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

    PubMed

    Krzciuk, Karina

    2016-07-03

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

  15. The Determination of Metals in Sediment Pore Waters and in 1N HCl-Extracted Sediments by ICP-MS

    USGS Publications Warehouse

    May, T.W.; Wiedmeyer, Ray H.; Brumbaugh, W.G.; Schmitt, C.J.

    1997-01-01

    Concentrations of metals in sediment interstitial water (pore water) and those extractable from sediment with weak acids can provide important information about the bioavailability and toxicological effects of such contaminants. The highly variable nature of metal concentrations in these matrices requires instrumentation with the detection limit capability of graphite furnace atomic absorption and the wide dynamic linear range capability of ICP-OES. These criteria are satisfied with ICP-MS instrumentation. We investigated the performance of ICP-MS in the determination of certain metals from these matrices. The results for three metals were compared to those determined by graphite furnace atomic absorption spectroscopy. It was concluded that ICP-MS was an excellent instrumental approach for the determination of metals in these matrices.

  16. Direct lead isotope analysis in Hg-rich sulfides by LA-MC-ICP-MS with a gas exchange device and matrix-matched calibration.

    PubMed

    Zhang, Wen; Hu, Zhaochu; Günther, Detlef; Liu, Yongsheng; Ling, Wenli; Zong, Keqing; Chen, Haihong; Gao, Shan

    2016-12-15

    In situ Pb isotope data of sulfide samples measured by LA-MC-ICP-MS provide valuable geochemical information for studies of the origin and evolution of ore deposits. However, the severe isobaric interference of (204)Hg on (204)Pb and the lack of matrix-matched sulfide reference materials limit the precision of Pb isotopic analyses for Hg-rich sulfides. In this study, we observe that Hg forms vapor and can be completely removed from sample aerosol particles produced by laser ablation using a gas exchange device. Additionally, this device does not influence the signal intensities of Pb isotopes. The within-run precision, the external reproducibility and the analytical accuracy are significantly improved for the Hg-rich sulfide samples using this mercury-vapor-removing device. Matrix effects are observed when using silicate glass reference materials as the external standards to assess the relationship of mass fractionation factors between Tl and Pb in sulfide samples, resulting in a maximum deviation of ∼0.20% for (20x)Pb/(204)Pb. Matrix-matched reference materials are therefore required for the highly precise and accurate Pb isotope analyses of sulfide samples. We investigated two sulfide samples, MASS-1 (the Unites States Geological Survey reference materials) and Sph-HYLM (a natural sphalerite), as potential candidates. Repeated analyses of the two proposed sulfide reference materials by LA-MC-ICP-MS yield good external reproducibility of <0.04% (RSD, k = 2) for (20x)Pb/(206)Pb and <0.06% (RSD, k = 2) for (20x)Pb/(204)Pb with the exception of (20x)Pb/(204)Pb in MASS-1, which provided an external reproducibility of 0.24% (RSD, k = 2). Because the concentration of Pb in MASS-1 (76 μg g(-1)) is ∼5.2 times lower than that in Sph-HYLM (394 ± 264 μg g(-1)). The in situ analytical results of MASS-1 and Sph-HYLM are consistent with the values obtained by solution MC-ICP-MS, demonstrating the reliability and robustness of our analytical protocol.

  17. Evaluation of chelation preconcentration for the determination of actinide elements by flow injection ICP-MS

    SciTech Connect

    Evans, E.H.; Truscott, J.B.; Bromley, L.; Jones, P.; Turner, J.; Fairman, B.E.

    1998-12-31

    A chelation column preconcentration method has been developed for the determination of uranium and thorium in waters by ICP-MS. Detection limits of 24 pg and 60 pg respectively were obtained, but these were blank limited. Uranium and Thorium were determined in certified reference materials. Results for uranium were 121 {+-} 21 and 15 {+-} 3 ng/g in NIST 1566a and NIST 1575 compared with certified values of 132 {+-} 12 and 20 {+-} 4 ng/g respectively. Results for thorium were 29 {+-} 8 and 28 {+-} 5 ng/g in NIST 1566a and NIST 1575 compared with indicative and certified values of 40 and 37 {+-} 3 ng/g respectively. The on-line separation of actinide radionuclides was achieved by selective elution of U, Th, Pu, Np, and Am.

  18. Studies on the content of heavy metals in Aries River using ICP-MS

    SciTech Connect

    Voica, Cezara Kovacs, Melinda Feher, Ioana

    2013-11-13

    Among the industrial branches, the mining industry has always been an important source of environmental pollution, both aesthetically and chemically. Through this paper results of ICP-MS characterization of Aries River Basin are reported. Mining activities from this area has resulted in contamination of environment and its surrounding biota. This is clearly evidenced in analyzed water samples, especially from Baia de Aries site where increased amount of trace elements as Cr, Zn, As, Se, Cd, Pb and U were founded. Also in this site greater amount of rare earth elements was evidenced also. Through monitoring of Aries River from other non-mining area it was observed that the quantitative content of heavy metals was below the maximum permissible levels which made us to conclude that the water table wasn't seriously affected (which possibly might be attributed to the cessation of mining activities in this area from a few years ago)

  19. Elemental speciation in biomolecules by LC-ICP-MS with magnetic sector and collision cell instruments

    SciTech Connect

    Wang, Jin

    1999-11-08

    A methodology that can monitor and identify inorganic elements in biological and environmental systems was developed. Size exclusion chromatography (SEC) separates biomolecules, which are then nebulized by a microconcentric nebulizer. The resulting aerosol is desolved and introduced into either a high resolution ICP-MS device or a quadrupole device with a collision cell. Because of the high sensitivity and spectral resolution and high sample introduction efficiency, many unusual or difficult elements, such as Cr, Se, Cd and U, can be observed at ambient levels bound to proteins in human serum. These measurements are made in only a few minutes without preliminary isolation and preconcentration steps. Serum samples can be titrated with spikes of various elements to determine which proteins bind a given metal and oxidation state. Experiments concerning the effects of breaking disulfide linkages and denaturation on metal binding in proteins were also investigated. Elemental distribution in liver extract was also obtained.

  20. Oxygenation mechanism of ions in dynamic reaction cell ICP-MS.

    PubMed

    Narukawa, Tomohiro; Chiba, Koichi

    2013-01-01

    A dynamic reaction cell (DRC) is one of the most effective tools for eliminating spectral interferences caused by polyatomic molecules in inductively coupled plasma mass spectrometry (ICP-MS). Oxygen gas (O2), by producing oxygenated ions, is very effective in reducing some specific spectral interferences. In this study, the oxygenation of elemental ions (M(+)) in the DRC was investigated experimentally, and a new explanation for oxygenation based on the enthalpy changes in the oxygenating reactions is proposed. The enthalpy changes of each M(+) were calculated and the possibility of each reaction occurring was evaluated. The calculations were in good agreement with experimental observations. Theoretical and experimental results supported the hypothesis that the enthalpy changes (ΔH) of M(+)+ O2 → MO(+) + O and M(+) + O → MO(+) and the thermodynamic stability of M(+)-O are key factors controlling oxygenation of M(+) in the DRC.

  1. Determination of 241Pu in nuclear waste slurries: a comparative study using LSC and ICP-MS.

    PubMed

    Jäggi, M; Röllin, S; Alvarado, J A Corcho; Eikenberg, J

    2012-02-01

    (241)Pu was determined in slurry samples from a nuclear reactor decommissioning project at the Paul Scherrer Institute (Switzerland). To validate the results, the (241)Pu activities of five samples were determined by LSC (TriCarb and Quantulus) and ICP-MS, with each instrument at a different laboratory. In lack of certified reference materials for (241)Pu, the methods were further validated using the (241)Pu information values of two reference sediments (IAEA-300 and IAEA-384). Excellent agreement with the results was found between LSC and ICP-MS in the nuclear waste slurries and the reference sediments.

  2. [Analysis of different types of soil by FTIR and ICP-MS].

    PubMed

    Zhao, Shuai-qun; Liu, Gang; Ou, Quan-hong; Xu, Juan; Ren, Jing; Hao, Jian-ming

    2014-12-01

    Fourier transform infrared spectroscopy (FTIR) and inductively coupled plasma mass spectrometry (ICP-MS) were used to study six types of farmland soil from different areas. The FTIR results showed that the infrared spectra of soil were mainly composed of the absorption band of clay minerals, organic matter and inorganic salts, such as carbonate, phosphate, manganate and so on. The mineral atlas of six soil samples were all of montmorillonite type. The ICP-MS test results showed that the available elements content of different types and colours of soil samples were different There was significant lack status of available Ca between different types of farmland soil, the content of available Mg in Huludao soil was in the medium level, other areas were in the status of shortage. There was only significant lack status of available Mn and available Zn in Baiyin soil, the content of available Fe in Chenggong soil was in the status of shortage, the content of available Cu in all areas was particularly rich. The content of available P in Jining soil was rich, Luoyang and Huludao soil were in the medium level, the soil of Chenggong, Baiyin and Luliang were in the status of shortage. The content of available K in Luoyang, Chenggong and Jining soil was relatively rich, Luliang soil was in the medium level, the soil of Huludao and Baiyin were in the status of shortage. It is observed that the deeper the color of soil samples, the richer the amount of some available trace elements such as magnesium, copper, iron, manganese and zinc. According to the national classification standard of available elements content, we analyzed the nutrients of available elements content in the farmland soil of different areas, and implemented remedial measures for the lacking of available elements for all of the six areas.

  3. New approach of a transient ICP-MS measurement method for samples with high salinity.

    PubMed

    Hein, Christina; Sander, Jonas Michael; Kautenburger, Ralf

    2017-03-01

    In the near future it is necessary to establish a disposal for high level nuclear waste (HLW) in deep and stable geological formations. In Germany typical host rocks are salt or claystone. Suitable clay formations exist in the south and in the north of Germany. The geochemical conditions of these clay formations show a strong difference. In the northern ionic strengths of the pore water up to 5M are observed. The determination of parameters like Kd values during sorption experiments of metal ions like uranium or europium as homologues for trivalent actinides onto clay stones are very important for long term safety analysis. The measurement of the low concentrated, not sorbed analytes commonly takes place by inductively coupled plasma mass spectrometry (ICP-MS). A direct measurement of high saline samples like seawater with more than 1% total dissolved salt content is not possible. Alternatives like sample clean up, preconcentration or strong dilution have more disadvantages than advantages for example more preparation steps or additional and expensive components. With a small modification of the ICP-MS sample introduction system and a home-made reprogramming of the autosampler a transient analysing method was developed which is suitable for measuring metal ions like europium and uranium in high saline sample matrices up to 5M (NaCl). Comparisons at low ionic strength between the default and the transient measurement show the latter performs similarly well to the default measurement. Additionally no time consuming sample clean-up or expensive online dilution or matrix removal systems are necessary and the analysation shows a high sensitivity due to the data processing based on the peak area.

  4. Application of Elemental Fingerprinting to Evaluate the Dynamics of Larval Exchange

    DTIC Science & Technology

    2001-09-30

    more recently, by Laser Ablation (LA)-ICP MS. Three species have been targeted: Mytilus galloprovincialis (Bay mussel), M. californianus (California... galloprovincialis and M. californianus have not been considered separately. To confirm identifications, Mytilus soft parts are being identified to species by...based on site, species, and size. Overall, the ability to distinguish small (,000 ppb Ca) Mytilus individuals from among Mission Bay, San

  5. Comparison of GC-ICP-MS and HPLC-ICP-MS for species-specific isotope dilution analysis of tributyltin in sediment after accelerated solvent extraction.

    PubMed

    Wahlen, Raimund; Wolff-Briche, Céline

    2003-09-01

    This study describes a direct comparison of GC and HPLC hyphenated to ICP-MS determination of tributyltin (TBT) in sediment by species-specific isotope dilution analysis (SS-IDMS). The certified reference sediment PACS-2 (NRC, Canada) and a candidate reference sediment (P-18/HIPA-1) were extracted using an accelerated solvent extraction (ASE) procedure. For comparison of GC and LC methods an older bottle of PACS-2 was used, whilst a fresh bottle was taken for demonstration of the accuracy of the methods. The data obtained show good agreement between both methods for both the PACS-2 sediment (LC-ICP-IDMS 828+/-87 ng g(-1) TBT as Sn, GC-ICP-IDMS 848+/-39 ng g(-1) TBT as Sn) and the P-18/ HIPA-1 sediment (LC-ICP-IDMS 78.0+/-9.7 ng g(-1) TBT as Sn, GC-ICP-IDMS 79.2+/-3.8 ng g(-1) TBT as Sn). The analysis by GC-ICP-IDMS offers a greater signal-to-noise ratio and hence a superior detection limit of 0.03 pg TBT as Sn, in the sediment extracts compared to HPLC-ICP-IDMS (3 pg TBT as Sn). A comparison of the uncertainties associated with both methods indicates superior precision of the GC approach. This is related to the better reproducibility of the peak integration, which affects the isotope ratio measurements used for IDMS. The accuracy of the ASE method combined with HPLC-ICP-IDMS was demonstrated during the international interlaboratory comparison P-18 organised by the Comité Consultatif pour la Quantité de Matière (CCQM). The results obtained by GC-ICP-IDMS for a newly opened bottle of PACS-2 were 1087+/-77 ng g(-1) Sn for DBT and 876+/-51 ng g(-1) Sn for TBT (expanded uncertainties with a coverage factor of 2), which are in good agreement with the certified values of 1090+/-150 ng g(-1) Sn and 980+/-130 ng g(-1) Sn, respectively.

  6. Selenium speciation analysis of Misgurnus anguillicaudatus selenoprotein by HPLC-ICP-MS and HPLC-ESI-MS/MS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Analytical methods for selenium (Se) speciation were developed using high performance liquid chromatography (HPLC) coupled to either inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionization tandem mass spectrometry (ESI-MS/MS). Separations of selenomethionine (Se-Met) and sel...

  7. Antimony Isotope Variations in Natural Systems Determined by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Ludden, J.; Rouxel, O.; Fouquet, Y.

    2001-12-01

    Sb has two stable isotopes of mass 121 and 123 with average abundance of 57.362% and 42.638% respectively and to date no geochemical or cosmochemical investigations of the variations of these isotopes have been attempted. In fact, the development of Sb isotope measurements for biogeochemical studies is challenging as Sb isotopes have a low percentage mass differences (1.6%) precluding large mass fractionation and Sb is a trace element below 100 ng/g for most geological samples and below 100 ng/l for seawater. However, it is anticipated that the redox changes of Sb(V) and Sb(III) species as well as biological activity and Sb volatilization or transport in hydrothermal systems can produce significant isotope fractionation in natural systems. The isotopic analyses of Sb have been performed using a continuous flow hydride generation system coupled to a Micromass MC-ICP-MS and the instrumental mass fractionation is corrected using a standard-sample bracketing approach. Total Sb, as well as Sb(III) and Sb(V) aqueous species are chemically purified prior to HG-MC-ICP-MS analysis. Using this analytical scheme, the minimum Sb required per analysis is 10 ng and the estimated external precision of the 123Sb/121Sb isotope ratio is 0.4 ɛ -units (2σ ). The data are reported relative to our internal standards (MERCK elemental standard solution). The isotopic fractionation factors between the coexisting species Sb(III) and Sb(V) have been investigated both on-line and after chemical separation. For the kinetic reduction experiment of Sb(V), the reducing agent used was KI as classically used for Sb(V) reduction and we obtained an instantaneous fractionation factor of 8.6 ɛ -units. For off-line experiments, we separated Sb(III) from a partially oxidized Sb solution and obtained a fractionation factor ranging from 5 to 6 ɛ -units. Preliminary results on Sb isotopic composition of selected terrestrial materials including seawater, soils, sediments and hydrothermal sulfides have

  8. Measurement of elemental speciation by liquid chromatography -- inductively coupled plasma mass spectrometry (LC-ICP-MS) with the direct injection nebulizer (DIN)

    SciTech Connect

    Shum, Sam

    1993-05-01

    This thesis is divided into 4 parts: elemental speciation, speciation of mercury and lead compounds by microbore column LC-ICP-MS with direct injection nebulization, spatially resolved measurements of size and velocity distributions of aerosol droplets from a direct injection nebulizer, and elemental speciation by anion exchange and size exclusion chromatography with detection by ICP-MS with direct injection nebulization.

  9. Quantitating Iron in Serum Ferritin by Use of ICP-MS

    NASA Technical Reports Server (NTRS)

    Smith, Scott M.; Gillman, Patricia L.

    2003-01-01

    A laboratory method has been devised to enable measurement of the concentration of iron bound in ferritin from small samples of blood (serum). Derived partly from a prior method that depends on large samples of blood, this method involves the use of an inductively-coupled-plasma mass spectrometer (ICP-MS). Ferritin is a complex of iron with the protein apoferritin. Heretofore, measurements of the concentration of serum ferritin (as distinguished from direct measurements of the concentration of iron in serum ferritin) have been used to assess iron stores in humans. Low levels of serum ferritin could indicate the first stage of iron depletion. High levels of serum ferritin could indicate high levels of iron (for example, in connection with hereditary hemochromatosis an iron-overload illness that is characterized by progressive organ damage and can be fatal). However, the picture is complicated: A high level of serum ferritin could also indicate stress and/or inflammation instead of (or in addition to) iron overload, and low serum iron concentration could indicate inflammation rather than iron deficiency. Only when concentrations of both serum iron and serum ferritin increase and decrease together can the patient s iron status be assessed accurately. Hence, in enabling accurate measurement of the iron content of serum ferritin, the present method can improve the diagnosis of the patient s iron status. The prior method of measuring the concentration of iron involves the use of an atomic-absorption spectrophotometer with a graphite furnace. The present method incorporates a modified version of the sample- preparation process of the prior method. First, ferritin is isolated; more specifically, it is immobilized by immunoprecipitation with rabbit antihuman polyclonal antibody bound to agarose beads. The ferritin is then separated from other iron-containing proteins and free iron by a series of centrifugation and wash steps. Next, the ferritin is digested with nitric acid

  10. Ni speciation in tea infusions by monolithic chromatography--ICP-MS and Q-TOF-MS.

    PubMed

    Ščančar, Janez; Zuliani, Tea; Žigon, Dušan; Milačič, Radmila

    2013-02-01

    For humans, Ni is not considered to be an essential trace element. Its compounds, at levels present in foodstuffs and drinks, are generally considered to be safe for consumption, but for individuals who already suffer from contact allergy to Ni and may be subject to develop systemic reactions from its dietary ingestion, dietary exposure to Ni must be kept under control. Being the second most popular beverage, tea is a potential source of dietary Ni. Present knowledge on its speciation in tea infusions is poor. Therefore, complete speciation analysis, consisting of separation by liquid chromatography using a weak CIM DEAE-1 monolithic column, "on-line" detection by inductively coupled plasma mass spectrometry (ICP-MS) and "off-line" identification of ligands by hybrid quadrupole time-of-flight mass spectrometry (Q-TOF MS), was implemented for the first time to study Ni speciation in tea infusions. Total concentrations of Ni in dry leaves of white, green, oolong and black tea (Camellia sinensis) and flowers of herbal chamomile (Matricaria chamomilla) and hibiscus (Hibiscus sabdariffa) tea were determined after microwave digestion by ICP-MS. They lay between 1.21 and 14.4 mg kg(-1). Good agreement between the determined and the certified values of the Ni content in the standard reference material SRM 1573a tomato leaves confirmed the accuracy of the total Ni determination. During the infusion process, up to 85 % of Ni was extracted from tea leaves or flowers. Separation of Ni species was completed in 10 min by applying aqueous linear gradient elution with 0.6 mol L(-1) NH(4)NO(3). Ni was found to be present in the chromatographic fraction in which quinic acid was identified by Q-TOF in all the tea infusions analysed, which had pH values between 5.6 and 6.0. The only exception was the infusion of hibiscus tea with a pH of 2.7, where results of speciation analysis showed that Ni is present in its divalent ionic form.

  11. Quantitative bioimaging of p-boronophenylalanine in thin liver tissue sections as a tool for treatment planning in boron neutron capture therapy.

    PubMed

    Reifschneider, Olga; Schütz, Christian L; Brochhausen, Christoph; Hampel, Gabriele; Ross, Tobias; Sperling, Michael; Karst, Uwe

    2015-03-01

    An analytical method using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was developed and applied to assess enrichment of 10B-containing p-boronophenylalanine-fructose (BPA-f) and its pharmacokinetic distribution in human tissues after application for boron neutron capture therapy (BNCT). High spatial resolution (50 μm) and limits of detection in the low parts-per-billion range were achieved using a Nd:YAG laser of 213 nm wavelength. External calibration by means of 10B-enriched standards based on whole blood proved to yield precise quantification results. Using this calibration method, quantification of 10B in cancerous and healthy tissue was carried out. Additionally, the distribution of 11B was investigated, providing 10B enrichment in the investigated tissues. Quantitative imaging of 10B by means of LA-ICP-MS was demonstrated as a new option to characterise the efficacy of boron compounds for BNCT.

  12. Microbeam Characterization of Corning Archeological Reference Glasses: New Additions to the Smithsonian Microbeam Standard Collection

    PubMed Central

    Vicenzi, Edward P.; Eggins, Stephen; Logan, Amelia; Wysoczanski, Richard

    2002-01-01

    An initial study of the minor element, trace element, and impurities in Corning archeological references glasses have been performed using three microbeam techniques: electron probe microanalysis (EPMA), laser ablation ICP-mass spectrometry (LA ICP-MS), and secondary ion mass spectrometry (SIMS). The EPMA results suggest a significant level of heterogeneity for a number of metals. Conversely, higher precision and a larger sampling volume analysis by LA ICP-MS indicates a high degree of chemical uniformity within all glasses, typically <2 % relative (1 σ). SIMS data reveal that small but measurable quantities of volatile impurities are present in the glasses, including H at roughly the 0.0001 mass fraction level. These glasses show promise for use as secondary standards for minor and trace element analyses of insulating materials such as synthetic ceramics, minerals, and silicate glasses. PMID:27446764

  13. On the condition of UO2 nuclear fuel irradiated in a PWR to a burn-up in excess of 110 MWd/kgHM

    NASA Astrophysics Data System (ADS)

    Restani, R.; Horvath, M.; Goll, W.; Bertsch, J.; Gavillet, D.; Hermann, A.; Martin, M.; Walker, C. T.

    2016-12-01

    Post-irradiation examination results are presented for UO2 fuel from a PWR fuel rod that had been irradiated to an average burn-up of 105 MWd/kgHM and showed high fission gas release of 42%. The radial distribution of xenon and the partitioning of fission gas between bubbles and the fuel matrix was investigated using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and electron probe microanalysis. It is concluded that release from the fuel at intermediate radial positions was mainly responsible for the high fission gas release. In this region thermal release had occurred from the high burn-up structure (HBS) at some point after the sixth irradiation cycle. The LA-ICP-MS results indicate that gas release had also occurred from the HBS in the vicinity of the pellet periphery. It is shown that the gas pressure in the HBS pores is well below the pressure that the fuel can sustain.

  14. Microbeam Characterization of Corning Archeological Reference Glasses: New Additions to the Smithsonian Microbeam Standard Collection.

    PubMed

    Vicenzi, Edward P; Eggins, Stephen; Logan, Amelia; Wysoczanski, Richard

    2002-01-01

    An initial study of the minor element, trace element, and impurities in Corning archeological references glasses have been performed using three microbeam techniques: electron probe microanalysis (EPMA), laser ablation ICP-mass spectrometry (LA ICP-MS), and secondary ion mass spectrometry (SIMS). The EPMA results suggest a significant level of heterogeneity for a number of metals. Conversely, higher precision and a larger sampling volume analysis by LA ICP-MS indicates a high degree of chemical uniformity within all glasses, typically <2 % relative (1 σ). SIMS data reveal that small but measurable quantities of volatile impurities are present in the glasses, including H at roughly the 0.0001 mass fraction level. These glasses show promise for use as secondary standards for minor and trace element analyses of insulating materials such as synthetic ceramics, minerals, and silicate glasses.

  15. Changes in trace and minor constituents and associated micro-architecture of Montastrea faveolata during time of "stress"

    USGS Publications Warehouse

    Holmes, C.W.; Buster, N.A.; Sorauf, J.E.; Hudson, J.H.; Kester, C.

    2003-01-01

    As corals grow, they secrete a calcareous skeleton with the aid of photosynthetic activity of endosymbiotic dinoflagellates. The rate of this secretion varies annually which produces annual bands. Entrapped with the carbonate are trace substances that record the chemistry of the surrounding ocean. Detailing these changes in chemistry requires careful high-resolution sampling. New procedures involving laser ablation inductive couple plasma mass spectroscopy (LA-ICP/MS) provides a unique method that does not involve tedious sample preparation. The La-ICP/MS data for a series of Atlantic corals from Looe Key, U.S. Florida Keys shows an intriguing distribution trace and minor elements whose concentrations are related to reported bleaching events. SEM data from the layers exhibit a change in crystal habit concurrent with the changes in chemistry. These changes reflected the affect of the variable influence of the symbiotic algae on the development of the coral skeleton.

  16. [Application of ICP-MS to detection of mineral elements and heavy metals in Cassava's byproducts].

    PubMed

    Tao, Hai-Teng; Zhang, Chun-Jiang; Chen, Xiao-Ming; Lüi, Fei-Jie; Tai, Jian-Xiang; Li, Kai-Mian

    2009-07-01

    Cassava is a main cultivated tropical crop in China, its rich starch roots are often used to produce fuel ethanol in recent years, so it's a kind of hot biomass energy crops. But cassava's byproducts such as leaves, stems and peels are regarded as waste, and are not fully utilized. Cassava's byproducts contain many nutrients, and can be used to process high value food products. The contents of mineral elements and heavy metals in cassava's byproducts were studied by ICP-MS. The results showed that cassava's byproducts contained many elements necessary to human health, the sequence of macroelements was K>Ca>P> Mg>S>Mn>Zn>Na>Fe>B>Cu, particularly, the contents of Fe, Mn, Zn and B ranged from 10 to 800 microg x g(-1) (DW), while the contents of microelements including Mo, Co, Se and Ge ranged from 0.01 to 0.2 microg x g(-1) (DW), which are important to human health. Besides macroelements and microelements, the contents of heavy metals (As, Cr, Pb and Hg) were also important to identify the quality of farm products, and the results showed that cassava's byproducts contained little heavy metals except Pb (2.19 microg x g(-1) (DW) in stalk peels). All the data showed that cassava's byproducts accorded with the national hygiene standards.

  17. Determination of Toxic Metals in Little Cigar Tobacco with “Triple Quad” ICP-MS

    PubMed Central

    Pappas, R. Steven; Martone, Naudia; Gonzalez-Jimenez, Nathalie; Fresquez, Mark R.; Watson, Clifford H.

    2015-01-01

    Smoking remains the leading cause of preventable death in the United States. Much of the focus on harmful constituents (HPHCs) in tobacco products has been on cigarettes. Little cigars have gained popularity over the last decade as tobacco taxes made cigarettes more expensive in the U.S. Many little cigar brands are similar in size with cigarettes and may be smoked in a similar manner. Scant data are available on HPHC levels in little cigars, therefore we developed and applied a new analytical method to determine concentrations of ten toxic metals in little cigar tobacco. The method utilizes “triple quadrupole” ICP-MS. By optimizing octapole bias, energy discrimination, and cell gas flow settings, we were able to accurately quantify a range of elements including those for which the cell gas reactions were endothermic. All standard modes (Single Quad No Gas, MS/MS NH3/He, and MS/MS O2) were utilized for the quantitation of ten toxic metals in little cigar tobacco, including uranium, which was added as an analyte in the new method. Because of the elimination of interfering ions at “shifted analyte masses,” detection limits were lower compared to a previous method. Tobacco selenium concentrations were below the limit of detection in the previous method, but the new technology made it possible to report all selenium concentrations. PMID:25724197

  18. Speciation of inorganic tellurium from seawater by ICP-MS following magnetic SPE separation and preconcentration.

    PubMed

    Huang, Chaozhang; Hu, Bin

    2008-03-01

    A new method was developed for the speciation of inorganic tellurium species in seawater by inductively coupled plasma-MS (ICP-MS) following selective magnetic SPE (MSPE) separation. Within the pH range of 2-9, tellurite (Te(IV)) could be quantitatively adsorbed on gamma-mercaptopropyltrimethoxysilane (gamma-MPTMS) modified silica-coated magnetic nanoparticles (MNPs), while the tellurate (Te(VI)) was not retained and remained in solution. Without filtration or centrifugation, these tellurite-loaded MNPs could be separated easily from the aqueous solution by simply applying external magnetic field. The Te(IV) adsorbed on the MNPs could be recovered quantitatively using a solution containing 2 mol/L HCl and 0.03 mol/L K2Cr2O7. Te(VI) was reduced to Te(IV) by L-cysteine prior to the determination of total tellurium, and its assay was based on subtracting Te(IV) from total tellurium. The parameters affecting the separation were investigated systematically and the optimal separation conditions were established. Under the optimal conditions, the LOD obtained for Te(IV) was 0.079 ng/L, while the precision was 7.0% (C = 10 ng/L, n = 7). The proposed method was successfully applied to the speciation of inorganic tellurium in seawater.

  19. Uranium levels in Cypriot groundwater samples determined by ICP-MS and α-spectroscopy.

    PubMed

    Charalambous, Chrystalla; Aletrari, Maria; Piera, Panagiota; Nicolaidou-Kanari, Popi; Efstathiou, Maria; Pashalidis, Ioannis

    2013-02-01

    The uranium concentration and the isotopic ratio (238)U/(234)U have been determined in Cypriot groundwater samples by ICP-MS after ultrafiltration and acidification of the samples and α-spectroscopy after pre-concentration and separation of uranium by cation-exchange (Chelex 100 resin) and electro-deposition on stainless steel discs. The uranium concentration in the groundwater samples varies strongly between 0.1 and 40 μg l(-1). The highest uranium concentrations are found in groundwater samples associated with sedimentary rock formations and the obtained isotopic ratio (238)U/(234)U varies between 0.95 and 1.2 indicating basically the presence of natural uranium in the studied samples. The pH of the groundwater samples is neutral to weak alkaline (7 < pH < 8) and this is attributed to the carbonaceous content of the sedimentary rocks and the ophiolitic origin of the igneous rocks, which form the background geology in Cyprus. Generally, in groundwaters uranium concentration in solution increases with decreasing pH (7 < pH < 8) and this is attributed to the fact that at lower pH dissolution of soil minerals occurs, and uranium, which is adsorbed or forms solid solution with the geological matrix enters the aqueous phase. This is also corroborated by the strong correlation between the uranium concentration and the electrical conductivity (e.g. dissolved solids) measured in the groundwaters under investigation.

  20. Total Arsenic, Cadmium, and Lead Determination in Brazilian Rice Samples Using ICP-MS

    PubMed Central

    Buzzo, Márcia Liane; de Arauz, Luciana Juncioni; Carvalho, Maria de Fátima Henriques; Arakaki, Edna Emy Kumagai; Matsuzaki, Richard; Tiglea, Paulo

    2016-01-01

    This study is aimed at investigating a suitable method for rice sample preparation as well as validating and applying the method for monitoring the concentration of total arsenic, cadmium, and lead in rice by using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Various rice sample preparation procedures were evaluated. The analytical method was validated by measuring several parameters including limit of detection (LOD), limit of quantification (LOQ), linearity, relative bias, and repeatability. Regarding the sample preparation, recoveries of spiked samples were within the acceptable range from 89.3 to 98.2% for muffle furnace, 94.2 to 103.3% for heating block, 81.0 to 115.0% for hot plate, and 92.8 to 108.2% for microwave. Validation parameters showed that the method fits for its purpose, being the total arsenic, cadmium, and lead within the Brazilian Legislation limits. The method was applied for analyzing 37 rice samples (including polished, brown, and parboiled), consumed by the Brazilian population. The total arsenic, cadmium, and lead contents were lower than the established legislative values, except for total arsenic in one brown rice sample. This study indicated the need to establish monitoring programs for emphasizing the study on this type of cereal, aiming at promoting the Public Health. PMID:27766178

  1. Bromate pollutant in ozonated bottled Zamzam water from Saudi Arabia determined by LC/ICP-MS.

    PubMed

    Al-Ansi, Seham A; Othman, Ahmed A; Al-Tufail, Mohammed A

    2011-01-01

    Bromate (BrO(3) (-)) as a human carcinogenic pollutant in bottled drinking Zamzam water from Mecca, Saudi Arabia has been determined using liquid chromatography inductively coupled plasma mass spectrometry (LC/ICP-MS). For analysis, samples were injected directly without any further pretreatment, using only 50 μL injection volume. The method showed: 0.5 μg/L detection limit, 1.0 μg/L limit of quantification and 1.0-200.0 μg/L linearity range (r(2) = 0.9998). The relative standard deviation (%RSD) values for reproducibility (interday precision) obtained are at 11 % and 14 % for bromate and bromide at low concentration levels (5, 10 μg/L) and at 4 % for both at high concentration levels (50, 100 μg/L), respectively. The results concluded that the ozonated bottled Zamzam water samples are contaminated with bromate. The concentration is 20 times higher than U.S. Environmental Protection Agency (U.S. EPA) allowable limit (10 μg/L) for bromate in bottled drinking water. Bottled drinking water brands, disinfected with ozone showed relatively lower levels of bromate as compared with Zamzam water.

  2. Reversed Phase Column HPLC-ICP-MS Conditions for Arsenic Speciation Analysis of Rice Flour.

    PubMed

    Narukawa, Tomohiro; Matsumoto, Eri; Nishimura, Tsutomu; Hioki, Akiharu

    2015-01-01

    New measurement conditions for arsenic speciation analysis of rice flour were developed using HPLC-ICP-MS equipped with a reversed phase ODS column. Eight arsenic species, namely, arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA), arsenobetaine (AsB) and arsenocholine (AsC), were separated and determined under the proposed conditions. In particular, As(III) and MMAA and DMAA and AsB were completely separated using a newly proposed eluent containing ammonium dihydrogen phosphate. Importantly, the sensitivity changes, in particular those of As(V) and As(III) caused by coexisting elements and by complex matrix composition, which had been problematical in previously reported methods, were eliminated. The new eluent can be applied to C8, C18 and C30 ODS columns with the same effectiveness and with excellent repeatability. The proposed analytical method was successfully applied to extracts of rice flour certified reference materials.

  3. Determination of iodine and molybdenum in milk by quadrupole ICP-MS.

    PubMed

    Reid, Helen J; Bashammakh, Abdul A; Goodall, Phillip S; Landon, Mark R; O'Connor, Ciaran; Sharp, Barry L

    2008-03-15

    A reliable method for the determination of iodine and molybdenum in milk samples, using alkaline digestion with tetramethylammonium hydroxide and hydrogen peroxide, followed by quadrupole ICP-MS analysis, has been developed and tested using certified reference materials. The use of He+O2 (1.0 ml min(-1) and 0.6 ml min(-1)) in the collision-reaction cell of the mass spectrometer to remove (129)Xe+-- initially to enable the determination of low levels of 129I--also resulted in the quantitative conversion of Mo(+) to MoO2+ which enabled the molybdenum in the milk to be determined at similar mass to the iodine with the use of Sb as a common internal standard. In order to separate and pre-concentrate iodine at sub microg l(-1) concentrations, a novel method was developed using a cation-exchange column loaded with Pd2+ and Ca2+ ions to selectively retain iodide followed by elution with a small volume of ammonium thiosulfate. This method showed excellent results for aqueous iodide solutions, although the complex milk digest matrix made the method unsuitable for such samples. An investigation of the iodine species formed during oxidation and extraction of milk sample digests was carried out with a view to controlling the iodine chemistry.

  4. Determination of Toxic Metals in Little Cigar Tobacco with 'Triple Quad' ICP-MS.

    PubMed

    Pappas, R Steven; Martone, Naudia; Gonzalez-Jimenez, Nathalie; Fresquez, Mark R; Watson, Clifford H

    2015-06-01

    Smoking remains the leading cause of preventable death in the USA. Much of the focus on harmful and potentially harmful constituents (HPHCs) in tobacco products has been on cigarettes. Little cigars gained popularity over the last decade until tobacco taxes made cigarettes more expensive in the USA. Many little cigar brands are similar in size with cigarettes and may be smoked in a similar manner. Scant data are available on HPHC concentrations in little cigars, therefore we developed and applied a new analytical method to determine concentrations of 10 toxic metals in little cigar tobacco. The method utilizes 'triple quadrupole' ICP-MS. By optimizing octapole bias, energy discrimination and cell gas flow settings, we were able to accurately quantify a range of elements including those for which the cell gas reactions were endothermic. All standard modes (Single Quad No Gas, MS-MS NH3/He and MS-MS O2) were utilized for the quantitation of 10 toxic metals in little cigar tobacco, including uranium, which was added as an analyte in the new method. Because of the elimination of interfering ions at 'shifted analyte masses', detection limits were lower compared with a previous method. Tobacco selenium concentrations were below the limit of detection in the previous method, but the new technology made it possible to report all selenium concentrations.

  5. The Effect of Aqueous Alteration in Antarctic Carbonaceous Chondrites from Comparative ICP-MS Bulk Chemistry

    NASA Technical Reports Server (NTRS)

    Alonso-Azcarate, J.; Trigo-Rodriguez, J. M.; Moyano-Cambero, C. E.; Zolensky, M.

    2014-01-01

    Terrestrial ages of Antarctic carbonaceous chondrites (CC) indicate that these meteorites have been preserved in or on ice for, at least, tens of thousands of years. Due to the porous structure of these chondrites formed by the aggregation of silicate-rich chondrules, refractory inclusions, metal grains, and fine-grained matrix materials, the effect of pervasive terrestrial water is relevant. Our community defends that pristine CC matrices are representing samples of scarcely processed protoplanetary disk materials as they contain stellar grains, but they might also trace parent body processes. It is important to study the effects of terrestrial aqueous alteration in promoting bulk chemistry changes, and creating distinctive alteration minerals. Particularly because it is thought that aqueous alteration has particularly played a key role in some CC groups in modifying primordial bulk chemistry, and homogenizing the isotopic content of fine-grained matrix materials. Fortunately, the mineralogy produced by parent-body and terrestrial aqueous alteration processes is distinctive. With the goal to learn more about terrestrial alteration in Antarctica we are obtaining reflectance spectra of CCs, but also performing ICP-MS bulk chemistry of the different CC groups. A direct comparison with the mean bulk elemental composition of recovered falls might inform us on the effects of terrestrial alteration in finds. With such a goal, in the current work we have analyzed some members representative of CO and CM chondrite groups.

  6. [Application of ICP-MS to Identify the Botanic Source of Characteristic Honey in South Yunnan].

    PubMed

    Wei, Yue; Chen, Fang; Wang, Yong; Chen, Lan-zhen; Zhang, Xue-wen; Wang, Yan-hui; Wu, Li-ming; Zhou, Qun

    2016-01-01

    By adopting inductively coupled plasma mass spectrometry (ICP-MS) combined with chemometric analysis technology, 23 kinds of minerals in four kinds of characteristic honey derived from Yunnan province were analyzed. The result showed that 21 kinds of mineral elements, namely Na, Mg, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Sb, Ba, Tl and Pb, have significant differences among different varieties of honey. The results of principal component analysis (PCA) showed that the cumulative variance contribution rate of the first four main components reached 77.74%, seven kinds of elements (Mg, Ca, Mn, Co, Sr, Cd, Ba) from the first main component contained most of the honey information. Through the stepwise discriminant analysis, seven kinds of elements (Mg, K, Ca, Cr, Mn, Sr, Pb) were filtered. out and used to establish the discriminant function model, and the correct classification rates of the proposed model reached 90% and 86.7%, respectively, which showed elements contents could be effectively indicators to discriminate the four kinds characteristic honey in southern Yunnan Province. In view of all the honey samples were harvested from apiaries located at south Yunnan Province where have similar climate, soil and other environment conditions, the differences of the mineral elements contents for the honey samples mainly due to their corresponding nectariferous plant. Therefore, it is feasible to identify honey botanical source through the differences of mineral elements.

  7. Fingerprinting of ground water by ICP-MS. Progress report, October 1, 1994--December 31, 1994

    SciTech Connect

    Stetzenbach, K.

    1994-12-31

    This report contains the results of the chemical analysis of water from springs in Death Valley National Park, California. The springs were selected to represent a variety of aquifers at various flow rates. Nevares, Texas, and Travertine springs are believed to represent carbonate aquifers, whereas the other springs are believed to come from volcanic or valley fill aquifers. Each spring was sampled two to five times between June, 1992 and March, 1994. Samples were collected and analyzed by the Harry Reid Center for Environmental Studies (HRC) Environmental/Analytical Laboratory, at the University of Nevada, Las Vegas. The coordinates and dates of sampling are included. The chemical analyses performed on these spring waters included major cations and anions and trace elements. The analyses for the major anions were performed by atomic absorption (AA) spectrophotometry, the anions by ion chromatography (IC) and the trace elements by inductively coupled plasma-mass spectrometry (ICP-MS). The standard operating procedures (SOP) used for each method are included. It is believed that this is the first effort at such a comprehensive trace element analysis of ground waters. HRC has had to develop, test, and refine sampling and analysis procedures throughout the course of this study. A great deal of effort has gone into ensuring that even with the variations in methods and procedures, the data quality from any one sampling is comparable to the others.

  8. [Application of ICP-MS to detecting ten kinds of heavy metals in KCl fertilizer].

    PubMed

    Rui, Yu-kui; Shen, Jian-bo; Zhang, Fu-suo; Yan, Yun; Jing, Jing-ying; Meng, Qing-feng

    2008-10-01

    With the rapid development of society, more and more attention has been focused on environmental safety, especially on the pollutions of heavy metals, pesticides, persistent organic pollutants and deleterious microorganism. Heavy metals are difficult to metabolize in human body are quite harmful, so research on the pollution of heavy metals is increasingly important. There are many pollution sources of heavy metals, including waste residue, waste water and exhaust gas from industry and automobile, and garbage from human life. The contents of 10 kinds of heavy metals (Cr, Ni, Cu, As, Cd, Sn, Sb, Hg, Tl and Pb) in potassium fertilizer (KCl) from Russia were analyzed by ICP-MS. The results showed that potassium fertilizer (KCl) contained less heavy metals than organic-inorganic compound fertilizer; the content of heavy metals Cr, Ni, Cu, As, Cd, Sn, Sb, Hg, Tl and Pb is 0.00, 65.54, 238.85, 190.60, 0.98, 14.98, 2.97, 10.04, 1.28 and 97.42 ng x g(-1), respectively, which accords with the correlative standards. All the data showed that if potassium fertilizer (KCl) is manufactured through normal channel, the content of heavy metals should be little and safe.

  9. Depth Profiling (ICP-MS) Study of Trace Metal `Grains' in Solid Asphaltenes

    NASA Astrophysics Data System (ADS)

    Pillay, Avin E.; Bassioni, Ghada; Stephen, Sasi; Kühn, Fritz E.

    2011-08-01

    Knowledge of trace metal `grains' in asphaltenes could play a significant role in enhancing refining and processing of crudes and also in providing useful information on mechanistic and migratory features linked to asphaltenes. These metals originate directly from interaction of oils with source-rock, mineral matter, and formation water and their accumulation in asphaltene matrices could vary from oil well to oil well. Suitable asphaltene samples were subjected to high-performance ICP-MS laser depth profiling (213 nm) to depths of 50 μm at 5 μm intervals. The study was conducted in the absence of standardization and characteristic intensities originating from the metals of interest were measured. Ten metal profiles were investigated (Na, Mg, Al, Mn, Fe, Zn, Sr, Pb, V, and Ni). The experimental results showed non-uniform distribution of trace metals and identified areas where such metals agglomerate. The data suggested that certain chemical and physical conditions within the structure of asphaltenes are favorable for metal `grain' formation at specific points. The exact mechanism for this behavior is not clear at this stage, and has considerable scope for future studies, including mathematical modeling simulations of asphaltenes. We also found that solid asphaltenes could be a useful forerunner of scale formation.

  10. Development of analytical techniques for ultra trace amounts of nuclear materials in environmental samples using ICP-MS for safeguards

    PubMed

    Magara; Hanzawa; Esaka; Miyamoto; Yasuda; Watanabe; Usuda; Nishimura; Adachi

    2000-07-01

    The authors have begun to develop analytical techniques for ultra trace amounts of nuclear materials and to prepare a clean chemistry laboratory for environmental sample analyses. The analytical techniques include bulk and particle analyses. For the bulk analysis, concentrations and isotopic ratios of U and/or Pu are determined by inductively-coupled plasma mass spectrometry (ICP-MS) and thermal ionization mass spectrometry (TIMS). In the particle analysis, isotopic ratios of U and/or Pu in each particle will be measured by secondary ion mass spectrometry (SIMS). This paper reports on the outline for the development of analytical techniques and the current situation of the development of the bulk analysis using ICP-MS is described.

  11. Triple Quad-ICP-MS Measurement of Toxic Metals in Mainstream Cigarette Smoke from Spectrum Research Cigarettes.

    PubMed

    Pappas, R Steven; Gray, Naudia; Gonzalez-Jimenez, Nathalie; Fresquez, Mark; Watson, Clifford H

    2016-01-01

    We previously reported toxic metal concentrations in the mainstream smoke from 50 varieties of commercial cigarettes available in the USA using quadrupole inductively coupled plasma-mass spectrometry (ICP-MS). However, efforts to continue producing high quality data on select mainstream cigarette smoke constituents demand continued improvements in instrumentation and methodology and application of the methodology to cigarettes that differ in design or construction. Here we report a new application of 'triple quad'-ICP-MS instrumentation to analyze seven toxic metals in mainstream cigarette smoke from the Spectrum variable nicotine research cigarettes. The Spectrum cigarettes are available for research purposes in different configurations of low or conventional levels of nicotine, mentholated or nonmentholated, and tar delivery ranges described as 'low tar' or 'high tar'. Detailed characterizations of specific harmful or potentially harmful constituents delivered by these research cigarettes will help inform researchers using these cigarettes in exposure studies, cessation studies and studies related to nicotine addiction or compensation.

  12. Method validation for determination of heavy metals in wine and slightly alcoholic beverages by ICP-MS

    NASA Astrophysics Data System (ADS)

    Voica, Cezara; Dehelean, Adriana; Pamula, A.

    2009-08-01

    The Organisation International de la Vigne et du Vin (OIV) fixed an uppermost level for some heavy metals in wine. Consequently, the need to determine very low concentration of elements that may be present in wine in trace and ultra trace levels occurred. Inductively coupled plasma mass spectrometry ICP-MS is considered an excellent tool for detailed characterization of the elementary composition of many samples, including samples of drinks. In this study a method of quantitative analysis for the determination of toxic metals (Cr, As, Cd, Ni, Hg, Pb) in wines and slightly alcoholic beverages by ICP-MS was validated. Several parameters have been taken into account and evaluated for the validation of method, namely: linearity, the minimum detection limit, the limit of quantification, accuracy and uncertainty.

  13. Simultaneous quantification of iodine and high valent metals via ICP-MS under acidic conditions in complex matrices.

    PubMed

    Brix, Kristina; Hein, Christina; Sander, Jonas Michael; Kautenburger, Ralf

    2017-05-15

    The determination of iodine as a main fission product (especially the isotopes I-129 and I-131) of stored HLW in a disposal beside its distribution as a natural ingredient of many different products like milk, food and seawater is a matter of particular interest. The simultaneous ICP-MS determination of iodine as iodide together with other elements (especially higher valent metal ions) relevant for HLW is analytically very problematic. A reliable ICP-MS quantification of iodide must be performed at neutral or alkaline conditions in contrast to the analysis of metal ions which are determined in acidic pH ranges. Herein, we present a method to solve this problem by changing the iodine speciation resulting in an ICP-MS determination of iodide as iodate. The oxidation from iodide to iodate with sodium hypochlorite at room temperature is a fast and convenient method with flexible reaction time, from one hour up to three days, thus eliminating the disadvantages of quantifying iodine species via ICP-MS. In the analysed concentration range of iodine (0.1-100µgL(-1)) we obtain likely quantitative recovery rates for iodine between 91% and 102% as well as relatively low RSD values (0.3-4.0%). As an additional result, it is possible to measure different other element species in parallel together with the generated iodate, even high valent metals (europium and uranium beside caesium) at recovery rates in the same order of magnitude (93-104%). In addition, the oxidation process operates above pH 7 thus offering a wide pH range for sample preparation. Even analytes in complex matrices, like 5M saline (NaCl) solution or artificial cement pore water (ACW) can be quantified with this robust sample preparation method.

  14. Multianalytical determination of trace elements in atmospheric biomonitors by k0-INAA, ICP-MS and AAS

    NASA Astrophysics Data System (ADS)

    Freitas, M. C.; Pacheco, A. M. G.; Dionísio, I.; Sarmento, S.; Baptista, M. S.; Vasconcelos, M. T. S. D.; Cabral, J. P.

    2006-08-01

    Elemental contents of atmospheric biomonitors—epiphytic lichens and tree bark, exposed in continuous and discontinuous modes—have been assessed through k0-standardised instrumental neutron activation analysis ( k0-INAA) (two different institutions), inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS). Certified reference materials—ISE-921 (river clay), NIST-1547 (peach leaves), ICHTJ-INCT-TL-1 (tea leaves; TL-1 hereinafter) and IAEA-336 (lichen material), and nonparametric statistics—rank-order correlations (Spearman RS) and enhanced-sign tests (Wilcoxon T)—were used for analytical control and data comparison, respectively. In general, quality of procedures was deemed good, except for k0-INAA in determining Br, Cu and Na, all likely affected by high counting statistics, and/or contamination issues (the latter). Results for Cu, Ni, Pb and Sr (by both ICP-MS and AAS) revealed that, despite an outstanding correlation (asymptotic p=0.000), they could be viewed as statistically equal for Cu only: AAS tended to yield higher values for Pb and Ni, and lower ones for Sr. The comparison between ICP-MS and k0-INAA data from TUDelft, for Al, Ca, Cu, Mg, Mn, Na, Ti and V, showed an excellent correlation (as above) and random (relative) magnitude for Cu, Mg, Mn and Ti only: ICP-MS tended to yield higher values for Al, Na and V, and lower ones for Ca, whereas between k0-INAA data from TUDelft and ITN, for Br, Ca and Na, resulted in systematically higher [Br] and [Ca] variates from TUDelft, even if all corresponding data sets were found to correlate at stringent significance levels. In a few cases, though—Ca, Sr in lichens; Pb in bark—matrix effects did appear to interfere in the outcome of matched-pairs, signed-rank tests, since random hierarchy of variates could be asserted just when lichen and bark data sets were processed separately.

  15. Advantages of reaction cell ICP-MS on doubly charged interferences for arsenic and selenium analysis in foods

    PubMed Central

    Jackson, Brian; Liba, Amir; Nelson, Jenny

    2014-01-01

    Recent reports of As concentrations in certain food and drinks have garnered public concern and led to a lowering of the US guideline maximum concentration for inorganic As in apple juice and proposed limits for As in rice products. In contrast Se is an essential micro-nutrient that can be limiting when Se-poor soils yield Se-poor food crops. Rare earth element (REE) doubly charged interferences on As and Se can be significant even when initial ICP-MS tuning minimizes doubly charged formation. We analyzed NIST 1547 (peach leaves) and 1515 (apple leaves), which contain high levels of REEs, by quadrupole ICP-MS with (He) collision mode, H2 reaction mode or triple quadrupole ICP-MS (ICP-QQQ) in mass-shift mode (O2 and O2/H2). Analysis by collision cell ICP-MS significantly over-estimated As and Se concentration due to REE doubly charged formation; mathematical correction increased the accuracy of analysis but is prone to error when analyte concentration and sensitivity is low and interferent is high. For Se, H2 reaction mode was effective in suppressing Gd2+ leading to accurate determination of Se in both SRMs without the need for mathematical correction. ICP-QQQ using mass-shift mode for As+ from m/z 75 to AsO+ at m/z 91 and Se+ from m/z 78 to SeO+ at m/z 94 alleviated doubly charged effects and resulted in accurate determination of As and Se in both SRMs without the need for correction equations. Zr and Mo isobars at 91 and 94 were shown to be effectively rejected by the MS/MS capability of the ICP-QQQ. PMID:25609851

  16. Advantages of reaction cell ICP-MS on doubly charged interferences for arsenic and selenium analysis in foods.

    PubMed

    Jackson, Brian; Liba, Amir; Nelson, Jenny

    Recent reports of As concentrations in certain food and drinks have garnered public concern and led to a lowering of the US guideline maximum concentration for inorganic As in apple juice and proposed limits for As in rice products. In contrast Se is an essential micro-nutrient that can be limiting when Se-poor soils yield Se-poor food crops. Rare earth element (REE) doubly charged interferences on As and Se can be significant even when initial ICP-MS tuning minimizes doubly charged formation. We analyzed NIST 1547 (peach leaves) and 1515 (apple leaves), which contain high levels of REEs, by quadrupole ICP-MS with (He) collision mode, H2 reaction mode or triple quadrupole ICP-MS (ICP-QQQ) in mass-shift mode (O2 and O2/H2). Analysis by collision cell ICP-MS significantly over-estimated As and Se concentration due to REE doubly charged formation; mathematical correction increased the accuracy of analysis but is prone to error when analyte concentration and sensitivity is low and interferent is high. For Se, H2 reaction mode was effective in suppressing Gd(2+) leading to accurate determination of Se in both SRMs without the need for mathematical correction. ICP-QQQ using mass-shift mode for As(+) from m/z 75 to AsO(+) at m/z 91 and Se(+) from m/z 78 to SeO(+) at m/z 94 alleviated doubly charged effects and resulted in accurate determination of As and Se in both SRMs without the need for correction equations. Zr and Mo isobars at 91 and 94 were shown to be effectively rejected by the MS/MS capability of the ICP-QQQ.

  17. Resolving global versus local/regional Pu sources in the environment using sector ICP-MS

    USGS Publications Warehouse

    Ketterer, M.E.; Hafer, K.M.; Link, C.L.; Kolwaite, D.; Wilson, Jim; Mietelski, J.W.

    2004-01-01

    Sector inductively coupled plasma mass spectrometry is a versatile method for the determination of plutonium activities and isotopic compositions in samples containing this element at fallout levels. Typical detection limits for 239+240Pu are 0.1, 0.02 and 0.002 Bq kg -1Pu for samples sizes of 0.5 g, 3 g, and 50 g of soil, respectively. The application of sector ICP-MS-based Pu determinations is demonstrated in studies in sediment chronology, soil Pu inventory and depth distribution, and the provenance of global fallout versus local or regional Pu sources. A sediment core collected from Sloans Lake (Denver, Colorado, USA) exhibits very similar 137Cs and 239+240Pu activity profiles; 240Pu/239Pu atom ratios indicate possible small influences from the Nevada Test Site and/or the Rocky Flats Environmental Technology Site. An undisturbed soil profile from Lockett Meadow (Flagstaff, Arizona, USA) exhibits an exponential decrease in 239+240Pu activity versus depth; 240Pu/239Pu in the top 3 cm is slightly lower than the global fallout range of 0.180 ?? 0.014 due to possible regional influence of Nevada Test Site fallout. The 239??240Pu inventory at Lockett Meadow is 56 ?? 4 Bq m-2, consistent with Northern Hemisphere mid-latitude fallout. Archived NdF3 sources, prepared from Polish soils, demonstrate that substantial 239+240Pu from the 1986 Chernobyl disaster has been deposited in north eastern regions of Poland; compared to global fallout, Chernobyl Pu exhibits higher abundances of 240Pu and 241Pu. The ratios 240Pu/239pu and 241Pu/239Pu co-vary and range from 0.186-0.348 and 0.0029-0.0412, respectively, in forest soils (241Pu/239Pu = 0.2407??[240Pu/239Pu] - 0.0413; r2 = 0.9924). ?? The Royal Society of Chemistry 2004.

  18. Measurement of arsenic and gallium content of gallium arsenide semiconductor waste streams by ICP-MS.

    PubMed

    Torrance, Keith W; Keenan, Helen E; Hursthouse, Andrew S; Stirling, David

    2010-01-01

    The chemistry of semiconductor wafer processing liquid waste, contaminated by heavy metals, was investigated to determine arsenic content. Arsenic and gallium concentrations were determined for waste slurries collected from gallium arsenide (GaAs) wafer processing at three industrial sources and compared to slurries prepared under laboratory conditions. The arsenic and gallium content of waste slurries was analyzed using inductively coupled plasma mass-spectrometry (ICP-MS) and it is reported that the arsenic content of the waste streams was related to the wafer thinning process, with slurries from wafer polishing having the highest dissolved arsenic content at over 1,900 mgL(-1). Lapping slurries had much lower dissolved arsenic (< 90 mgL(-1)) content, but higher particulate contents. It is demonstrated that significant percentage of GaAs becomes soluble during wafer lapping. Grinding slurries had the lowest dissolved arsenic content at 15 mgL(-1). All three waste streams are classified as hazardous waste, based on their solids content and dissolved arsenic levels and treatment is required before discharge or disposal. It is calculated that as much as 93% of material is discarded through the entire GaAs device manufacturing process, with limited recycling. Although gallium can be economically recovered from waste slurries, there is little incentive to recover arsenic, which is mostly landfilled. Options for treating GaAs processing waste streams are reviewed and some recommendations made for handling the waste. Therefore, although the quantities of hazardous waste generated are miniscule in comparison to other industries, sustainable manufacturing practices are needed to minimize the environmental impact of GaAs semiconductor device fabrication.

  19. Speciation and uptake of arsenic accumulated by corn seedlings using XAS and DRC-ICP-MS

    PubMed Central

    Parsons, J.G.; Martinez-Martinez, A.; Peralta-Videa, J. R.; Gardea-Torresdey, J. L.

    2014-01-01

    ICP-MS was used to investigate the uptake of As(III) and As(V) from hydroponics growth media by corn seedlings. It was found that arsenic uptake by the plant roots for the arsenic(V) and arsenic(III) treatments were 95 and 112 ppm, respectively. However, in the shoots of the arsenic (V) treatments had 18 ppm whereas arsenic(III) treatments had 12 ppm. XANES studies showed that As for both treatments arsenic was present as a mixture of an As(III) sulfur complex and an As(V) oxygen complex. The XANES data was corroborated by the EXAFS studies showing the presence of both oxygen and sulfur ligands coordinated to the arsenic. Iron concentrations were found to increase by 4 fold in the As(V) contaminated growth media and 7 fold in the As(III) treatment compared to the control iron concentration of 500 ppm. Whereas, the total iron concentration in the shoots was found to decrease by approximately the same amount for both treatments from 360 ppm in the control to approximately 125 ppm in both arsenic treatments. Phosphorus concentrations were found to decrease in both the roots and shoots compared to the control plants. The total sulfur in the roots was found to increase in the arsenic(III) and arsenic(V) treatments to 560 ppm and 800 ppm, respectively, compared to the control plants 358 ppm. In addition, the total sulfur in shoots of the plants was found to remain relatively constant at approximately 1080 ppm. The potassium concentrations in the plants were found to increase in the roots and decrease in the shoots. PMID:17928032

  20. Determination of B/Ca of natural carbonates by HR-ICP-MS

    NASA Astrophysics Data System (ADS)

    Misra, Sambuddha; Greaves, Mervyn; Owen, Robert; Kerr, Joanna; Elmore, Aurora C.; Elderfield, Henry

    2014-04-01

    report a new method for HR-ICP-MS based accurate and precise B/Ca determination from low mass natural carbonates (≤5 µg CaCO3), utilizing a mixed acid matrix (0.1 M HNO3 and 0.3 M HF) and accurate matrix matching technique. Our procedural B/Ca blank of 2.0 ± 1.0 µmol/mol, internal precision ≤1.0%, average within run external precision ≤4.0% (2σ), and rapid sample analysis (60 samples/day) make the method well suited for routine measurements. Established methods of B/Ca determination require ≥65 µg CaCO3 to achieve a comparable external precision of 3.5% (2σ). We report a B/Ca detection limit of 2 µmol/mol compared to ≥10 µmol/mol for previous methods, a fivefold improvement. The method presented here can determine a wide range of B/Ca (9.0-250 µmol/mol) in mass limited samples with considerable tolerance for matrix matching efficiency (≤±30%). The long-term reproducibility of B/Ca measured on Cambridge in-house consistency standards containing <20, ˜85, and ˜200 µmol/mol of B/Ca are ±3.7% (2σ, n = 100), ±3.9% (2σ, n = 150), and ±3.2% (2 s, n =180), respectively. A host of other trace element to Ca ratios can also be determined at comparable external precision from samples containing ≤5 µg CaCO3. This method is suitable for trace element analysis of single foraminifera shells.

  1. Discrimination of the Cigarettes Geographical Origin by DRC-ICP-MS Measurements of Pb Isotope Compositions

    NASA Astrophysics Data System (ADS)

    Guo, W.; Hu, S.; Jin, L.

    2014-12-01

    Trace Pb are taken up with the same isotopic ratios as is present in the source soil, and the isotopic composition of Pb could used to reflect these sources and provide powerful indicators of the geographic origin of agriculture products derived from vegetative matter. We developed a simple and high throughput method, which based on DRC-ICP-MS for determination of Pb isotope ratios for discriminating the geographic origin of cigarettes. After acid digestion procedure, the cigarette digested solutions were directly analyzed by ICP-QMS with a DRC pressurized by the non-reactive gas Ne. In the DRC, Ne molecules collision with Pb ions and improves Pb isotope ratios precision 3-fold, which may be due to the collisional dampling smoothes out the ion beam fluctuations. Under the optimum DRC rejection parameter Q (RPq = 0.45), the main matrix components (K, Na, Ca, Mg, Al, Fe etc.) originating from cigarettes were filtered out. Mass discrimination of 208Pb/206Pb ratio in Ne DRC mode increased 0.3% compared to the standard mode, the mass bias due to the in-cell Ne gas collision can be accurately corrected by NIST 981 Pb isotope standard. This method was verified by a tobacco reference material CTV-OTL-2. Results of 208Pb/206Pb and 207Pb/206Pb were 2.0848 ± 0.0028 (2δ) and 0.8452 ± 0.0011 (2δ) for CTA-VTL-2, which were agreed with the literature values (208Pb/206Pb = 2.0884 ± 0.0090 and 207Pb/206Pb = 0.8442 ± 0.0032). The precision of Pb isotope ratios (208Pb/206Pb and 207Pb/206Pb) for the cigarette samples are ranged from 0.01 to 0.08% (N = 5). It has sufficient precision to discriminate 91 different brand cigarettes originated from four different geographic regions (Shown in Fig).

  2. Precise Analysis of Gallium Isotopic Composition by MC-ICP-MS.

    PubMed

    Yuan, Wei; Chen, Jiu Bin; Birck, Jean-Louis; Yin, Zuo Ying; Yuan, Sheng Liu; Cai, Hong Ming; Wang, Zhong Wei; Huang, Qiang; Wang, Zhu Hong

    2016-10-04

    Though an isotope approach could be beneficial for better understanding the biogeochemical cycle of gallium (Ga), an analogue of the monoisotopic element aluminum (Al), the geochemistry of Ga isotopes has not been widely elaborated. We developed a two-step method for purifying Ga from geological (biological) samples for precise measurement of Ga isotope ratio using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Ga was thoroughly separated from other matrix elements using two chromatographic columns loaded with AG 1-X4 and Ln-spec resin, respectively. The separation method was carefully calibrated using both synthetic and natural samples and validated by assessing the extraction yield (99.8 ± 0.8%, 2SD, n = 23) and the reproducibility (2SD uncertainty better than 0.05‰, n = 116) of the measured isotopic ratio (expressed as δ(71)Ga). The validation of the whole protocol, together with instrumental analysis, was confirmed by the investigation of the matrix effect, the result of a standard addition experiment, and the comparison of Ga isotope measurement on two mass spectrometers-Nu Plasma II and Neptune Plus. Although the measurements using the sample-standard bracketing (SSB) correction method on both instruments resulted in identical δ(71)Ga values for reference materials, the modified empirical external normalization (MEEN) method gave relatively better precision compared to SSB on Neptune. Our preliminary results showed large variation of δ(71)Ga (up to 1.83‰) for 10 standards, with higher values in industrially produced materials, implying potential application of Ga isotopes.

  3. Evaluation of the combined measurement uncertainty in isotope dilution by MC-ICP-MS.

    PubMed

    Fortunato, G; Wunderli, S

    2003-09-01

    The combination of metrological weighing, the measurement of isotope amount ratios by a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) and the use of high-purity reference materials are the cornerstones to achieve improved results for the amount content of lead in wine by the reversed isotope dilution technique. Isotope dilution mass spectrometry (IDMS) and reversed IDMS have the potential to be a so-called primary method, with which close comparability and well-stated combined measurement uncertainties can be obtained. This work describes the detailed uncertainty budget determination using the ISO-GUM approach. The traces of lead in wine were separated from the matrix by ion exchange chromatography after HNO(3)/H(2)O(2) microwave digestion. The thallium isotope amount ratio ( n((205)Tl)/ n((203)Tl)) was used to correct for mass discrimination using an exponential model approach. The corrected lead isotope amount ratio n((206)Pb)/ n((208)Pb) for the isotopic standard SRM 981 measured in our laboratory was compared with ratio values considered to be the least uncertain. The result has been compared in a so-called pilot study "lead in wine" organised by the CCQM (Comité Consultatif pour la Quantité de Matière, BIPM, Paris; the highest measurement authority for analytical chemical measurements). The result for the lead amount content k(Pb) and the corresponding expanded uncertainty U given by our laboratory was:k(Pb)=1.329 x 10-10mol g-1 (amount content of lead in wine)U[k(Pb)]=1.0 x 10-12mol g-1 (expanded uncertainty U=kxuc, k=2)The uncertainty of the main influence parameter of the combined measurement uncertainty was determined to be the isotope amount ratio R(206,B) of the blend between the enriched spike and the sample.

  4. Surface Cleaning Techniques: Ultra-Trace ICP-MS Sample Preparation and Assay of HDPE

    SciTech Connect

    Overman, Nicole R.; Hoppe, Eric W.; Addleman, Raymond S.

    2013-06-01

    The world’s most sensitive radiation detection and assay systems depend upon ultra-low background (ULB) materials to reduce unwanted radiological backgrounds. Herein, we evaluate methods to clean HDPE, a material of interest to ULB systems and the means to provide rapid assay of surface and bulk contamination. ULB level material and ultra-trace level detection of actinide elements is difficult to attain, due to the introduction of contamination from sample preparation equipment such as pipette tips, sample vials, forceps, etc. and airborne particulate. To date, literature available on the cleaning of such polymeric materials and equipment for ULB applications and ultra-trace analyses is limited. For these reasons, a study has been performed to identify an effective way to remove surface contamination from polymers in an effort to provide improved instrumental detection limits. Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) was utilized to assess the effectiveness of a variety of leachate solutions for removal of inorganic uranium and thorium surface contamination from polymers, specifically high density polyethylene (HDPE). HDPE leaching procedures were tested to optimize contaminant removal of thorium and uranium. Calibration curves for thorium and uranium ranged from 15 ppq (fg/mL) to 1 ppt (pg/mL). Detection limits were calculated at 6 ppq for uranium and 7 ppq for thorium. Results showed the most effective leaching reagent to be clean 6 M nitric acid for 72 hour exposures. Contamination levels for uranium and thorium found in the leachate solutions were significant for ultralow level radiation detection applications.

  5. [Determination of Trace Elements in Marine Cetaceans by ICP-MS and Health Risk Assessment].

    PubMed

    Ding, Yu-long; Ning, Xi; Gui, Duan; Mo, Hui; Li, Yu-sen; Wu, Yu-ping

    2015-09-01

    The liver, kidney and muscle samples from seven cetaceans were digested by microwave digestion, and trace elements amounts of V, Cd, Cu, Zn, As, Cr, Ni, Mn, Se, Hg and Pb were determined by inductively coupled plasma mass spectrometry (ICP-MS), and the health risk assessment for Zn, Cu, Cd, Hg, Se in the liver was conducted. The results of international lobster hepatopancreas standard (TORT-2) showed acceptable agreement with the certified values, and the relative standard deviation (RSD) of eleven kinds of trace elements were less than 3.54%, showing that the method is suitable for the determination of trace elements in cetaceans. The experimental results indicated that different tissues and organs of the dolphins had different trace elements, presenting the tissue specificity. There is a certain inter-species difference among different dolphins about the bioaccumulation ability of the trace elements. The distribution of trace elements in whales presented a certain regularity: the contents of most elements in liver, kidney were much higher than the contents of muscle tissues, Cu, Mn, Hg, Se, and Zn exhibit the higher concentrations in liver, while Cd was mainly accumulated in kidney. And according to the health risk assessment in liver, the exceeding standardrate of selenium and copper in seven kinds of whales was 100%, suggesting that these whales were suffering the contamination of trace elements. The experimental results is instructive to the study of trace elements in cetaceans, while this is the first report for the concentrations in organs of Striped dolphin, Bottlenose dolphin, Fraser's Dolphin and Risso's dolphin in China, it may provide us valuable data for the conservation of cetaceans.

  6. Speciation And Uptake of Arsenic Accumulated By Corn Seedlings Using XAS And DRC-ICP-MS

    SciTech Connect

    Parsons, J.G.; Martinez-Martinez, A.; Peralta-Videa, J.R.; Gardea-Torresdey, J.L.

    2009-05-21

    ICP-MS was used to investigate the uptake of As(III) and As(V) from hydroponics growth media by corn seedlings. It was found that arsenic uptake by the plant roots for the arsenic(V) and arsenic(III) treatments were 95 and 112 ppm, respectively. However, in the shoots of the arsenic (V) treatments had 18 ppm whereas arsenic(III) treatments had 12 ppm. XANES studies showed that As for both treatments arsenic was present as a mixture of an As(III) sulfur complex and an As(V) oxygen complex. The XANES data was corroborated by the EXAFS studies showing the presence of both oxygen and sulfur ligands coordinated to the arsenic. Iron concentrations were found to increase by 4 fold in the As(V) contaminated growth media and 7 fold in the As(III) treatment compared to the control iron concentration of 500 ppm. Whereas, the total iron concentration in the shoots was found to decrease by approximately the same amount for both treatments from 360 ppm in the control to approximately 125 ppm in both arsenic treatments. Phosphorus concentrations were found to decrease in both the roots and shoots compared to the control plants. The total sulfur in the roots was found to increase in the arsenic(III) and arsenic(V) treatments to 560 ppm and 800 ppm, respectively, compared to the control plants 358 ppm. In addition, the total sulfur in shoots of the plants was found to remain relatively constant at approximately 1080 ppm. The potassium concentrations in the plants were found to increase in the roots and decrease in the shoots.

  7. Online determination of copper in aluminum alloy by microchip solvent extraction using isotope dilution ICP-MS method.

    PubMed

    Kagawa, Tsuyoshi; Ohno, Masashi; Seki, Tatsuya; Chikama, Katsumi

    2009-09-15

    Isotope dilution mass spectroscopy (IDMS)/ICP-MS combined with microchip solvent extraction was successfully applied for the online determination of copper in an aluminum alloy. The microchip solvent extraction was developed for the separation of Cu from major element, and optimal pH range was wider than that of the batchwise extraction method. The dimensions of the microchip were 30 mm x 70 mm and that of micro-channel on the microchip was 180 microm wide and 40 microm deep. The copper complex with 8-hydroxyquinoline was extracted into o-xylene at pH 5.5 and back extracted with 0.1 mol l(-1) nitric acid at flow rate of 20 microl min(-1). The total extraction efficiency (water/organic solvent/nitric acid) was around 40%. IDMS/ICP-MS was coupled with solvent extraction for precise determination of Cu. The extraction and back-extraction on the microchip took about 1s and the total measurement time for the IDMS/ICP-MS was about 40s/sample. The blank value of this method was 0.1 ng g(-1). The proposed method was used for the determination of Cu in Al standard materials (JSAC 0121-C, The Japan Society for Analytical Chemistry and 7074 Al alloy, Nippon Light Metal Co. Ltd.). The obtained analytical results are in good agreement with the certified values.

  8. Metabolomic and elemental analysis of camel and bovine urine by GC-MS and ICP-MS.

    PubMed

    Ahamad, Syed Rizwan; Alhaider, Abdul Qader; Raish, Mohammad; Shakeel, Faiyaz

    2017-01-01

    Recent studies from the author's laboratory indicated that camel urine possesses antiplatelet activity and anti-cancer activity which is not present in bovine urine. The objective of this study is to compare the volatile and elemental components of bovine and camel urine using GC-MS and ICP-MS analysis. We are interested to know the component that performs these biological activities. The freeze dried urine was dissolved in dichloromethane and then derivatization process followed by using BSTFA for GC-MS analysis. Thirty different compounds were analyzed by the derivatization process in full scan mode. For ICP-MS analysis twenty eight important elements were analyzed in both bovine and camel urine. The results of GC-MS and ICP-MS analysis showed marked difference in the urinary metabolites. GC-MS evaluation of camel urine finds a lot of products of metabolism like benzene propanoic acid derivatives, fatty acid derivatives, amino acid derivatives, sugars, prostaglandins and canavanine. Several research reports reveal the metabolomics studies on camel urine but none of them completely reported the pharmacology related metabolomics. The present data of GC-MS suggest and support the previous studies and activities related to camel urine.

  9. Determination of 90Sr in contaminated environmental samples by tuneable bandpass dynamic reaction cell ICP-MS.

    PubMed

    Taylor, V F; Evans, R D; Cornett, R J

    2007-01-01

    A rapid method for the extraction and determination of 90Sr in natural water, plant and sediment samples was developed using extraction chromatography and dynamic reaction cell ICP-MS, with O2 as a reaction gas. While isobaric interference from the stable isotope 90Zr was efficiently removed by this method, interferences produced from in-cell reactions with Fe+ and Ni+ required suppression by tuneable bandpass, and in sediments, additional chromatographic separation. Method detection limits were 0.1 pg g-1 (0.5 Bq g-1), 0.04 pg g-1(0.2 Bq g-1), and 3 pg L-1 (5 Bq L-1) for sediments, plant and water samples, respectively, and 90Sr concentrations determined by ICP-MS were in good agreement with activities determined by Cerenkov counting and with certified reference values. While mass spectrometric determination does not rival detection limits achievable by radiometric counting, radiometric determination of 90Sr, a pure beta-emitter, is hindered by long analysis times (several weeks); the comparatively fast analysis achieved via ICP-MS enables same-day preparation and analysis of samples, making this an important technique for the environmental monitoring of areas contaminated by radioactivity.

  10. Measurement of labile Cu in soil using stable isotope dilution and isotope ratio analysis by ICP-MS.

    PubMed

    Nolan, Annette L; Ma, Yibing; Lombi, Enzo; McLaughlin, Mike J

    2004-11-01

    Isotope dilution is a useful technique to measure the labile metal pool, which is the amount of metal in soil in rapid equilibrium (<7 days) with the soil solution. This is normally performed by equilibrating soil with a metal isotope, and sampling the labile metal pool by using an extraction (E value), or by growing plants (L value). For Cu, this procedure is problematic for E values, and impossible for L values, due to the short half-life of the 64Cu radioisotope (12.4 h), which makes access and handling very difficult. We therefore developed a technique using enriched 65Cu stable isotope and measurement of 63Cu/65Cu ratios by quadrupole inductively coupled plasma mass spectrometry (ICP-MS) to measure labile pools of Cu in soils using E value techniques. Mass spectral interferences in detection of 63Cu/65Cu ratios in soil extracts were found to be minimal. Isotope ratios determined by quadrupole ICP-MS compared well to those determined by high-resolution (magnetic sector) ICP-MS. E values determined using the stable isotope technique compared well to those determined using the radioisotope for both uncontaminated and Cu-contaminated soils.

  11. Kinetic energy discrimination in collision/reaction cell ICP-MS: Theoretical review of principles and limitations

    NASA Astrophysics Data System (ADS)

    Yamada, Noriyuki

    2015-08-01

    Kinetic energy discrimination (KED) is one of the means to control cell-formed interferences in collision/reaction cell ICP-MS, and also a technique to reduce polyatomic ion interferences derived from the plasma or vacuum interface in collision cell ICP-MS. The operation of KED is accurately described to explain how spectral interferences from polyatomic ions are reduced by this technique. The cell is operated under non-thermal conditions to implement KED, where the hard sphere collision model is aptly employed to portray the transmission of ions colliding with the cell gas that they don't chemically react with. It is theoretically explained that the analyte atomic ions surmount the energy barrier placed downstream of the cell and the interfering polyatomic ions do not due to their lower kinetic energy than the atomic ions, resulting in polyatomic interference reduction. The intrinsic limitations of this technique are shown to lie in the statistical nature of collision processes, which causes the broadening of ion kinetic energy distribution that hinders efficient KED. The reaction cell operation with KED, where plasma-derived interferences are reduced by the reactive cell gas while cell-formed interferences are suppressed by the energy barrier, is also described in a quantitative manner. This review paper provides an in-depth understanding of KED in cell-based ICP-MS for analysts to make better use of it.

  12. Determination of Plutonium Isotope Ratios at Very Low Levels by ICP-MS using On-Line Electrochemically Modulated Separations

    SciTech Connect

    Liezers, Martin; Lehn, Scott A; Olsen, Khris B; Farmer, Orville T; Duckworth, Douglas C

    2009-10-01

    Electrochemically modulated separations (EMS) are shown to be a rapid and selective means of extracting and concentrating Pu from complex solutions prior to isotopic analysis by inductively coupled plasma mass spectrometry (ICP-MS). This separation is performed in a flow injection mode, on-line with the ICP-MS. A three-electrode, flow-by electrochemical cell is used to accumulate Pu at an anodized glassy carbon electrode by redox conversion of Pu(III) to Pu (IV&VI). The entire process takes place in 2% v/v (0.46M) HNO3. No redox chemicals or acid concentration changes are required. Plutonium accumulation and release is redox dependent and controlled by the applied cell potential. Thus large transient volumetric concentration enhancements can be achieved. Based on more negative U(IV) potentials relative to Pu(IV), separation of Pu from uranium is efficient, thereby eliminating uranium hydride interferences. EMS-ICP-MS isotope ratio measurement performance will be presented for femtogram to attogram level plutonium concentrations.

  13. Validation of Electrochemically Modulated Separations Performed On-Line with MC-ICP-MS for Uranium and Plutonium Isotopic Analyses

    SciTech Connect

    Liezers, Martin; Olsen, Khris B.; Mitroshkov, Alexandre V.; Duckworth, Douglas C.

    2010-08-11

    The most time consuming process in uranium or plutonium isotopic analyses is performing the requisite chromatographic separation of the actinides. Filament preparation for thermal ionization (TIMS) adds further delays, but is generally accepted due to the unmatched performance in trace isotopic analyses. Advances in Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) are beginning to rival the performance of TIMS. Methods, such as Electrochemically Modulated Separations (EMS) can efficiently pre-concentrate U or Pu quite selectively from small solution volumes in a matrix of 0.5 M nitric acid. When performed in-line with ICP-MS, the rapid analyte release from the electrode is fast, and large transient analyte signal enhancements of >100 fold can be achieved as compared to more conventional continuous nebulization of the original starting solution. This makes the approach ideal for very low level isotope ratio measurements. In this paper, some aspects of EMS performance are described. These include low level Pu isotope ratio behavior versus concentration by MC-ICP-MS and uranium rejection characteristics that are also important for reliable low level Pu isotope ratio determinations.

  14. Single particle ICP-MS characterization of titanium dioxide, silver, and gold nanoparticles during drinking water treatment.

    PubMed

    Donovan, Ariel R; Adams, Craig D; Ma, Yinfa; Stephan, Chady; Eichholz, Todd; Shi, Honglan

    2016-02-01

    One of the most direct means for human exposure to nanoparticles (NPs) released into the environment is drinking water. Therefore, it is critical to understand the occurrence and fate of NPs in drinking water systems. The objectives of this study were to develop rapid and reliable analytical methods and apply them to investigate the fate and transportation of NPs during drinking water treatments. Rapid single particle ICP-MS (SP-ICP-MS) methods were developed to characterize and quantify titanium-containing, titanium dioxide, silver, and gold NP concentration, size, size distribution, and dissolved metal element concentration in surface water and treated drinking water. The effectiveness of conventional drinking water treatments (including lime softening, alum coagulation, filtration, and disinfection) to remove NPs from surface water was evaluated using six-gang stirrer jar test simulations. The selected NPs were nearly completely (97 ± 3%) removed after lime softening and alum coagulation/activated carbon adsorption treatments. Additionally, source and drinking waters from three large drinking water treatment facilities utilizing similar treatments with the simulation test were collected and analyzed by the SP-ICP-MS methods. Ti-containing particles and dissolved Ti were present in the river water samples, but Ag and Au were not present. Treatments used at each drinking water treatment facility effectively removed over 93% of the Ti-containing particles and dissolved Ti from the source water.

  15. Non-Traditional Spectroscopy for Analysis of Semiconductor and Photovoltaic Thin Film Materials

    NASA Astrophysics Data System (ADS)

    Li, Fuhe; Anderson, Scott

    2009-09-01

    Characterization of semiconductor thin films has long been determined by a number of traditional surface analysis techniques; Auger, ESCA/XPS, SEM-EDS and SIMS to name only a few. Depth profiles, contamination in the thin film or quantitative stoichiometry are specific application examples that predicate the technique best suited for the analysis need. The evolution of photovoltaic (PV) thin film compositions with new chemistries and growing importance of atomic layer deposition (ALD) for semiconductor and nanoscale applications provide a sustaining need for thin film analyses along with an avenue for new analytical tools. In this paper we will discuss the applications of two non-traditional material analysis techniques for the semiconductor and PV applications, glow discharge optical emission spectroscopy (RF GD-OES) and laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS). Depth profiles are available via both techniques with the ability to analyze monolayers (single nm) as well as analysis in the bulk (μm thickness). Depth resolution capabilities allow analysis without surface equilibrium issues seen with other techniques. In addition, the charging effect that can cause issues with electron and ion beam techniques is avoided with RF GD-OES and LA ICP-MS, and thus analysis of both conductive and non-conductive materials is very straight-forward. Contaminant analysis in thin films is very straight-forward and elements across the periodic table are analyzed in a simultaneous mode with both techniques. Detection limits to part-per-billion levels can be achieved and quantitation at low concentrations up to 99% achieved with LA ICP-MS. Lastly, t will be discussed that for some thin film applications, LA ICP-MS and RF GD-OES provide advantages over more traditional techniques, and these aspects as well as complementary features will be discussed.

  16. On the certification of cadmium at trace and ultratrace levels in standard reference materials using ID ICP-MS.

    PubMed

    Murphy, K E; Long, S E; Vocke, R D

    2007-04-01

    Analytical methods used for the isotope dilution inductively coupled plasma mass spectrometric (ID-ICP-MS) measurement of Cd at microg kg(-1) and sub-microg kg(-1) levels are described and applied to the certification of new dietary supplement, blood, and serum Standard Reference Materials (SRMs). The materials are: SRM 3240 Ephedra sinica Stapf Aerial Parts, SRM 3241 Ephedra sinica Stapf Native Extract, SRM 3243 Ephedra-Containing Solid Oral Dosage Form, SRM 3244 Ephedra-Containing Protein Powder, SRM 966 Toxic Metals in Bovine Blood, Level 1 (L1) and Level 2 (L2), and SRM 1598a Animal Serum. The concentration of Cd in the materials ranges from 120 microg kg(-1) down to 0.03 microg kg(-1). At these levels, the factors that most influence the accuracy of the ICP-MS data are the procedure blank and spectral and nonspectral interferences. Nonspectral interference, caused by the high concentration of dissolved solids in the matrices investigated, resulted in signal suppression. Matrix separation was used to enhance signal intensity and to reduce spectral interference for the accurate determination of Cd in SRM 1598a and SRM 3244. Chromatographic separation procedures using Chelex for SRM 1598a and anion exchange for SRM 3244 were optimized to achieve the desired separation characteristics without substantially increasing the procedure blank. Sensitivity for the determination of Cd in serum was additionally enhanced through the use of desolvation nebulization. We determined that separations were not required for the accurate ICP-MS determination of Cd in SRM 3240, SRM 3241, SRM 3243, and SRM 966 L2 under optimized analysis conditions. These samples were diluted to a minimum volume and introduced to the ICP-MS via low flow (40-100 microL/min) microconcentric nebulizers. SRM 966 L1 was also analyzed directly, but results were highly variable. The ID-ICP-MS sample preparation and ratio measurement protocols described here resulted in total expanded uncertainties of less

  17. Percolation Diffusion into Self-Assembled Mesoporous Silica Microfibres

    PubMed Central

    Canning, John; Huyang, George; Ma, Miles; Beavis, Alison; Bishop, David; Cook, Kevin; McDonagh, Andrew; Shi, Dongqi; Peng, Gang-Ding; Crossley, Maxwell J.

    2014-01-01

    Percolation diffusion into long (11.5 cm) self-assembled, ordered mesoporous microfibres is studied using optical transmission and laser ablation inductive coupled mass spectrometry (LA-ICP-MS). Optical transmission based diffusion studies reveal rapid penetration (<5 s, D > 80 μm2∙s−1) of Rhodamine B with very little percolation of larger molecules such as zinc tetraphenylporphyrin (ZnTPP) observed under similar loading conditions. The failure of ZnTPP to enter the microfibre was confirmed, in higher resolution, using LA-ICP-MS. In the latter case, LA-ICP-MS was used to determine the diffusion of zinc acetate dihydrate, D~3 × 10−4 nm2∙s−1. The large differences between the molecules are accounted for by proposing ordered solvent and structure assisted accelerated diffusion of the Rhodamine B based on its hydrophilicity relative to the zinc compounds. The broader implications and applications for filtration, molecular sieves and a range of devices and uses are described. PMID:28348290

  18. [Application of ICP-MS in evaluating element contamination in soils].

    PubMed

    Wu, Ying-juan; Chen, Yong-heng; Yang, Chun-xia; Chang, Xiang-yang

    2008-12-01

    The Yunfu pyrite was the second biggest pyrite bed in the world. Plants using industrial ore of the Yunfu pyrite are distributed in many sections across the country. In the present paper, elements V, Cr, Co, Cu, Zn, Mo, Cd, Sb, Rb and Cs in soil profiles in slag disposing area of a sulfuric acid plant using industrial ore of theYunfu pyrite were studied. A method for simultaneously determination of metals and some reference elements in soils by ICP-MS was developed. The correlations between the metals and their reference elements were fast found. Enrichment factors were applied for evaluating the degree of soil contamination, and the problem about choosing contamination elements background values was pointed out. The results indicated that element V showed apparent and serious pollution, The Co showed middle degree pollution, and there has been a trend of apparent pollution. The Cr, Mo and Cd showed pollution between light degree and middle degree. The Zn and Sb showed light degree pollution, and there was a latent trend of middle degree pollution. The Cu showed light degree pollution. The high enrichment points of the V and the Cr were observed in the upper part (4.0-10.5 cm) and deep part of soil profiles (44.0-75.5 cm). Those of Co and Mo were found in the surface of soil profiles (0-5.0 cm), middle-upper part (9.5-10.5 cm) and middle part (29.5-46.0 cm), while those of Cd and Cu occurred just in the middle of soil profiles (29.5-46.0 cm). The formation of highly enrichment points of contamination elements in the soil profiles was the result of leaching and accumulating effect of the metals released from slag and the residual metals of highly weathered red soils. Most of pollution of V in the soil was contributed by the V in soil bed. Part of the V pollution in the soil was supplied by leaching and accumulating effect of the V which came from catalyst with lost activity in sulfuric acid production volatilizing into slag.

  19. [Application of ICP-MS to Detect Rare Earth Elements in Three Economic Macroalgaes in China].

    PubMed

    Zhao, Yan-fang; Shang, De-rong; Zhai, Yu-xiu; Ning, Jin-song; Ding, Hai-yan; Sheng, Xiao-feng

    2015-11-01

    In order to investigate the content and distribution of rare earth elements (REE) in main economic macroalgaes in our country, fifteen rare earth elements in three economic macroalgaes (including 30 samples of kelp, 30 samples of laver and 15 samples of Enteromorpha) were detected using ICP-MS method. Results showed that the total content of REE in different species of macroalgaes was different. The highest total content of REE was in Enteromorpha (16,012.0 ng · g⁻¹), while in kelp and laver, the total REE was similar for two macroalgaes (3887.4 and 4318.1 ng · g⁻¹ respectively). The content of fifteen rare earth elements in kelp ranged from 7.9 to 1496.4 ng · g⁻¹; in laver, it ranged from 8.2 to 1836.6 ng · g⁻¹. For Enteromorpha, the concentration of 15 rare earth elements were between 19.2 and 6014.5 ng · g⁻¹. In addition, the content and distribution of different rare earth elements in different macroalgaes was also different. For kelp, the highest content of REE was Ce (1 496.4 ng · g⁻¹), and the second was La (689.1 ng · g⁻¹). For laver, the highest was Y (1836.6 ng · g⁻¹), and the second was Ce (682.2 ng · g⁻¹). For Enteromorpha, the highest was Ce (6014.5 ng · g⁻¹), and the second was La (2902.9 ng · g⁻¹). Present results also showed that three macroalgaes accumulated the light rare earth elements much more than the high rare earth elements. The light rare earth elements occupied 90.9%, 87.3% and 91.1% for kelp, laver and Enteromorpha respectively. The result that the Enteromorpha had high content of rare earth elements could provide important support for opening new research directions for the utilization of Enteromorpha.

  20. Danube catchment water chemistry monitoring - elemental pattern determination from source to mouth using ICP-MS

    NASA Astrophysics Data System (ADS)

    Tchaikovsky, Anastassiya; Zitek, Andreas; Irrgeher, Johanna; Prohaska, Thomas

    2014-05-01

    Monitoring the elemental composition of river water is an important tool to determine the chemical status of a river. However, currently many studies are limited to the analysis of heavy metals included in the EU Water Framework Directive Priority Substances List (Cd, Hg, Ni, Pb). Yet, the assessment of further elements (e.g. Ca, Mg, Si) can give additional relevant information for understanding catchment processes such as soil erosion, weathering, hydrological changes or glacial melting. In addition, site specific "elemental pattern" can be used as tracer for ecological studies, like habitat and migration studies of fish or birds. Elemental information is of particular interest complementary to isotopic data where only little variability in the isotopic signatures can be observed. In this work, we investigated water samples collected from 68 sampling sites along the longitudinal course of the river Danube including the major tributaries during the Joint Danube Survey 3 (JDS3) in 2013. Water samples were obtained as triplicates in the middle of the river and analyzed using Inductively Coupled - Plasma Mass Spectrometry (ICP-MS). Method validation was performed using riverine water (NRC SLRS-5) certified reference material as well as in-house prepared quality control standards. Due to the diverse geology and changing natural and anthropogenic factors along the longitudinal course of the Danube, pronounced elemental variations among the water samples were documented. For instance, especially some major elements (Ca, K, Mg, Na) together with some minor elements (Si, Sr) are known to reflect in particular regional geological morphologies. In addition, the variation in Si/Ca ratios can be used as an indicator for weathering conditions, especially in the mountainous areas along the Danube. Elevated concentrations of Cd, Cu, Fe, Ni, and Pb downstream of some large cities and industrial areas are signs of significant anthropogenic impact. In combination, the chemical

  1. An overview of recent applications of inductively coupled plasma-mass spectrometry (ICP-MS) in determination of inorganic impurities in drugs and pharmaceuticals.

    PubMed

    Nageswara Rao, R; Talluri, M V N Kumar

    2007-01-04

    The recent applications of inductively coupled plasma-mass spectrometry (ICP-MS) in determination of trace level inorganic impurities in drugs and pharmaceuticals have been reviewed. ICP-MS coupled with LC, GC and CE was used for speciation of heavy metals in pharmaceutical products. The review covers the period from 1995 to 2005 during which the technique was applied not only for determination of metallic impurities but also the assay of various trace elements in pharmaceuticals.

  2. Practical limitations of single particle ICP-MS in the determination of nanoparticle size distributions and dissolution: case of rare earth oxides.

    PubMed

    Fréchette-Viens, Laurie; Hadioui, Madjid; Wilkinson, Kevin J

    2017-01-15

    The applicability of single particle ICP-MS (SP-ICP-MS) for the analysis of nanoparticle size distributions and the determination of particle numbers was evaluated using the rare earth oxide, La2O3, as a model particle. The composition of the storage containers, as well as the ICP-MS sample introduction system were found to significantly impact SP-ICP-MS analysis. While La2O3 nanoparticles (La2O3 NP) did not appear to interact strongly with sample containers, adsorptive losses of La(3+)(over 24h) were substantial (>72%) for fluorinated ethylene propylene bottles as opposed to polypropylene (<10%). Furthermore, each part of the sample introduction system (nebulizers made of perfluoroalkoxy alkane (PFA) or glass, PFA capillary tubing, and polyvinyl chloride (PVC) peristaltic pump tubing) contributed to La(3+) adsorptive losses. On the other hand, the presence of natural organic matter in the nanoparticle suspensions led to a decreased adsorptive loss in both the sample containers and the introduction system, suggesting that SP-ICP-MS may nonetheless be appropriate for NP analysis in environmental matrices. Coupling of an ion-exchange resin to the SP-ICP-MS led to more accurate determinations of the La2O3 NP size distributions.

  3. A miniaturized laser-ablation mass spectrometer for in-situ measurements of isotope composition on solar body surfaces

    NASA Astrophysics Data System (ADS)

    Riedo, A.; Meyer, S.; Tulej, M.; Neuland, M.; Bieler, A.; Iakovleva, M.; Wurz, P.

    2012-04-01

    space instrument would have a cylindrical shape with a length of 120 mm, and a diameter of 60 mm, and a weight of about 1.5 kg (all electronics included). The mass analyzer supports high dynamic range of about 107 and a typical mass resolution of m/Δm~700. A computer-controlled optimizer controls the reproducibility of the performance of the mass analyzer, the laser fluence and the positioning of the sample. The system supports highly sensitive studies of elemental composition with sub-ppm detection limits. Our studies show that high accuracy and precision measurements can also be achieved in the investigations of isotopic patterns. Our initial studies of lead isotopic pattern indicated an accuracy and precision in the per mile range, which are comparable to that achieved by other - well known in isotopic analysis - mass spectrometric techniques, i.e., TIMS, SIMS, LA-ICP-MS used in the laboratory. The initial studies were conducted with Galena minerals and NIST standards. Hence, the miniaturized laser ablation time-of-flight mass spectrometer is a powerful instrument for in-situ measurements for the further investigation in surface characterization.

  4. Label-free DNA hybridization detection and single base-mismatch discrimination using CE-ICP-MS assay.

    PubMed

    Li, Yan; Sun, Shao-kai; Yang, Jia-lin; Jiang, Yan

    2011-12-07

    Detecting a specific DNA sequence and discriminating single base-mismatch is critical to clinical diagnosis, paternity testing, forensic sciences, food and drug industry, pathology, genetics, environmental monitoring, and anti-bioterrorism. To this end, capillary electrophoresis (CE) coupled with the inductively coupled plasma mass spectrometry (ICP-MS) method is developed using the displacing interaction between the target ssDNA and the competitor Hg(2+) for the first time. The thymine-rich capture ssDNA 1 is interacted with the competitor Hg(2+), forming an assembled complex in a hairpin-structure between the thymine bases arrangement at both sides of the capture ssDNA 1. In the presence of a target ssDNA with stronger affinity than that of the competitor Hg(2+), the energetically favorable hybridization between capture ssDNA 1 and the target ssDNA destroys the hairpin-structure and releases the competitor as free Hg(2+), which was then read out and accurately quantified by CE-ICP-MS assay. Under the optimal CE separation conditions, free Hg(2+) ions and its capture ssDNA 1 adduct were baseline separated and detected on-line by ICP-MS; the increased peak intensity of free Hg(2+) against the concentration of perfectly complementary target ssDNA was linear over the concentration range of 30-600 nmol L(-1) with a limit of detection of 8 nmol L(-1) (3s, n = 11) in the pre-incubated mixture containing 1 μmol L(-1) Hg(2+) and 0.2 μmol L(-1) capture ssDNA 1. This new assay method is simple in design since any target ssDNA binding can in principle result in free Hg(2+) release by 6-fold Hg(2+) signal amplification, avoiding oligonucleotide labeling or assistance by excess signal transducer and signal reporter to read out the target. Due to element-specific detection of ICP-MS in our assay procedure, the interference from the autofluorescence of substrata was eliminated.

  5. Focused microwave-induced combustion for digestion of botanical samples and metals determination by ICP OES and ICP-MS.

    PubMed

    Barin, J S; Pereira, J S F; Mello, P A; Knorr, C L; Moraes, D P; Mesko, M F; Nóbrega, J A; Korn, M G A; Flores, E M M

    2012-05-30

    The advantages and shortcomings of focused microwave-induced combustion (FMIC) for digestion of plant samples were studied. The effects of sample mass, absorbing solution, oxygen gas flow-rate, and time of reflux step on recoveries of major, minor and trace metals were systematically evaluated. Afterwards, Al, Ba, Ca, Co, Cr, Cu, Mg, Mn, Ni, Sr, V, and Zn were determined by inductively coupled plasma optical emission spectrometry (ICP OES) and by inductively coupled plasma mass spectrometry (ICP-MS). The main advantages of FMIC when compared to microwave-assisted wet digestion (MAWD) and focused-microwave-assisted wet digestion (FMAWD) are the possibility to digest larger masses of samples (up to 3g) using shorter heating times and diluted nitric acid solution for absorbing all analytes. Using the selected experimental conditions for FMIC, residual carbon content was lower than 0.7% for all samples and relative standard deviation (RSD) varied from 1.5 to 14.1%. Certified reference materials (NIST 1515 apple leaves and NIST 1547 peach leaves) were used for checking accuracy and determined values for all metals were in agreement with certified values at a 95% confidence level. No statistical difference (ANOVA, 95% of confidence level) was observed for results obtained by FMIC, FMAWD, and MAWD. Limits of detection were lower when using FMIC in the range of 0.02-0.15 μg g(-1) for ICP OES and 0.001-0.01 μg g(-1) for ICP-MS, which were about 3 and 6 times lower than the values obtained by FMAWD and MAWD, respectively. It is important to point out that FMIC was a suitable sample preparation method for major, minor and trace metals by both determination techniques (ICP OES and ICP-MS). Additionally, since it allows lower LODs (because up to 3g of sample can be digested) and diluted acid solutions are used (without any further dilution), the use of ICP-MS is not mandatory.

  6. Accurate determination of ultra-trace levels of Ti in blood serum using ICP-MS/MS.

    PubMed

    Balcaen, Lieve; Bolea-Fernandez, Eduardo; Resano, Martín; Vanhaecke, Frank

    2014-01-27

    Ti is frequently used in implants and prostheses and it has been shown before that the presence of these in the human body can lead to elevated Ti concentrations in body fluids such as serum and urine. As identification of the exact mechanisms responsible for this increase in Ti concentrations, and the risks associated with it, are not fully understood, it is important to have sound analytical methods that enable straightforward quantification of Ti levels in body fluids (for both implanted and non-implanted individuals). Until now, only double-focusing sector field ICP-mass spectrometry (SF-ICP-MS) offered limits of detection that are good enough to deal with the very low basal levels of Ti in human serum. This work reports on the development of a novel method for the accurate and precise determination of trace levels of Ti in human serum samples, based on the use of ICP-MS/MS. O2 and NH3/He have been compared as reaction gases. While the use of O2 did not enable to overcome all spectral interferences, it has been shown that conversion of Ti(+) ions into Ti(NH3)6(+) cluster ions by using NH3/He as a reaction gas in an ICP-QQQ-MS system, operated in MS/MS mode, provided interference-free conditions and sufficiently low limits of detection, down to 3 ng L(-1) (instrumental detection limit obtained for the most abundant Ti isotope). The accuracy of the method proposed was evaluated by analysis of a Seronorm Trace Elements Serum L-1 reference material and by comparing the results obtained with those achieved by means of SF-ICP-MS. As a proof-of-concept, the newly developed method was successfully applied to the determination of Ti in serum samples obtained from individuals with and without Ti-based implants. All results were found to be in good agreement with those obtained by means of SF-ICP-MS. The typical basal Ti level in human serum was found to be <1 μg L(-1), while values in the range of 2-6 μg L(-1) were observed for implanted patients.

  7. Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

    PubMed Central

    Platzner, Thomas I.; Segal, Irina

    2007-01-01

    The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

  8. Determination of impurities in uranium matrices by time-of-flight ICP-MS using matrix-matched method

    SciTech Connect

    Buerger, Stefan; Riciputi, Lee R; Bostick, Debra A

    2007-01-01

    The analysis of impurities in uranium matrices is performed in a variety of fields, e.g. for quality control in the production stream converting uranium ores to fuels, as element signatures in nuclear forensics and safeguards, and for non-proliferation control. We have investigated the capabilities of time-of-flight ICP-MS for the analysis of impurities in uranium matrices using a matrix-matched method. The method was applied to the New Brunswick Laboratory CRM 124(1-7) series. For the seven certified reference materials, an overall precision and accuracy of approximately 5% and 14%, respectively, were obtained for 18 analyzed elements.

  9. Analysis of IAEA Environmental Samples for Plutonium and Uranium by ICP/MS in Support Of International Safeguards

    SciTech Connect

    Farmer, Orville T.; Olsen, Khris B.; Thomas, May-Lin P.; Garofoli, Stephanie J.

    2008-05-01

    A method for the separation and determination of total and isotopic uranium and plutonium by ICP-MS was developed for IAEA samples on cellulose-based media. Preparation of the IAEA samples involved a series of redox chemistries and separations using TRU® resin (Eichrom). The sample introduction system, an APEX nebulizer (Elemental Scientific, Inc), provided enhanced nebulization for a several-fold increase in sensitivity and reduction in background. Application of mass bias (ALPHA) correction factors greatly improved the precision of the data. By combining the enhancements of chemical separation, instrumentation and data processing, detection levels for uranium and plutonium approached high attogram levels.

  10. Development of sulfide calibration standards for the laser ablation inductively-coupled plasma mass spectrometry technique

    USGS Publications Warehouse

    Wilson, S.A.; Ridley, W.I.; Koenig, A.E.

    2002-01-01

    The requirements of standard materials for LA-ICP-MS analysis have been difficult to meet for the determination of trace elements in sulfides. We describe a method for the production of synthetic sulfides by precipitation from solution. The method is detailed by the production of approximately 200 g of a material, PS-1, with a suite of chalcophilic trace elements in an Fe-Zn-Cu-S matrix. Preliminary composition data, together with an evaluation of the homogeneity for individual elements, suggests that this type of material meets the requirements for a sulfide calibration standard that allows for quantitative analysis. Contamination of the standard with Na suggests that H2S gas may prove a better sulfur source for future experiments. We recommend that calibration data be collected in whatever mode is closest to that employed for the analysis of the unknown material, because of variable fractionation effects as a function of analytical mode. For instance, if individual spot analyses are attempted on unknown sample, then a raster of several individual spot analyses, not a continuous scan, should be collected and averaged for the standard. Hg and Au are exceptions to the above and calibration data should always be collected in a scanning mode. Au is more heterogeneously distributed than other trace metals and large-area scans are required to provide an average value for calibration purposes. We emphasize that the values given in Table 1 are preliminary values. Further chemical characterization of this standard, through a round-robin analysis program, will allow the USGS to provide both certified and recommended values for individual elements. The USGS has developed PS-1 as a potential new LA-ICP-MS standard for use by the analytical community, and requests for this material should be addressed to S. Wilson. However, it is stressed that an important aspect of the method described here is the flexibility for individual investigators to produce sulfides with a wide range

  11. Hybrid Imaging Labels: Providing the Link Between Mass Spectrometry-Based Molecular Pathology and Theranostics

    PubMed Central

    Buckle, Tessa; van der Wal, Steffen; van Malderen, Stijn J.M.; Müller, Larissa; Kuil, Joeri; van Unen, Vincent; Peters, Ruud J.B.; van Bemmel, Margaretha E.M.; McDonnell, Liam A.; Velders, Aldrik H.; Koning, Frits; Vanhaeke, Frank; van Leeuwen, Fijs W. B.

    2017-01-01

    Background: Development of theranostic concepts that include inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) imaging can be hindered by the lack of a direct comparison to more standardly used methods for in vitro and in vivo evaluation; e.g. fluorescence or nuclear medicine. In this study a bimodal (or rather, hybrid) tracer that contains both a fluorescent dye and a chelate was used to evaluate the existence of a direct link between mass spectrometry (MS) and in vitro and in vivo molecular imaging findings using fluorescence and radioisotopes. At the same time, the hybrid label was used to determine whether the use of a single isotope label would allow for MS-based diagnostics. Methods: A hybrid label that contained both a DTPA chelate (that was coordinated with either 165Ho or 111In) and a Cy5 fluorescent dye was coupled to the chemokine receptor 4 (CXCR4) targeting peptide Ac-TZ14011 (hybrid-Cy5-Ac-TZ4011). This receptor targeting tracer was used to 1) validate the efficacy of (165Ho-based) mass-cytometry in determining the receptor affinity via comparison with fluorescence-based flow cytometry (Cy5), 2) evaluate the microscopic binding pattern of the tracer in tumor cells using both fluorescence confocal imaging (Cy5) and LA-ICP-MS-imaging (165Ho), 3) compare in vivo biodistribution patterns obtained with ICP-MS (165Ho) and radiodetection (111In) after intravenous administration of hybrid-Cy5-Ac-TZ4011 in tumor-bearing mice. Finally, LA-ICP-MS-imaging (165Ho) was linked to fluorescence-based analysis of excised tissue samples (Cy5). Results: Analysis with both mass-cytometry and flow cytometry revealed a similar receptor affinity, respectively 352 ± 141 nM and 245 ± 65 nM (p = 0.08), but with a much lower detection sensitivity for the first modality. In vitro LA-ICP-MS imaging (165Ho) enabled clear discrimination between CXCR4 positive and negative cells, but fluorescence microscopy was required to determine the

  12. Quantification of 60Fe atoms by MC-ICP-MS for the redetermination of the half-life.

    PubMed

    Kivel, Niko; Schumann, Dorothea; Günther-Leopold, Ines

    2013-03-01

    In many scientific fields, the half-life of radionuclides plays an important role. The accurate knowledge of this parameter has direct impact on, e.g., age determination of archeological artifacts and of the elemental synthesis in the universe. In order to derive the half-life of a long-lived radionuclide, the activity and the absolute number of atoms have to be analyzed. Whereas conventional radiation measurement methods are typically applied for activity determinations, the latter can be determined with high accuracy by mass spectrometric techniques. Over the past years, the half-lives of several radionuclides have been specified by means of multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) complementary to the earlier reported values mainly derived by accelerator mass spectrometry. The present paper discusses all critical aspects (amount of material, radiochemical sample preparation, interference correction, isotope dilution mass spectrometry, calculation of measurement uncertainty) for a precise analysis of the number of atoms by MC-ICP-MS exemplified for the recently published half-life determination of 60Fe (Rugel et al, Phys Rev Lett 103:072502, 2009).

  13. [Study on the determination of 28 inorganic elements in sunflower seeds by ICP-OES/ICP-MS].

    PubMed

    Liu, Hong-Wei; Qin, Zong-Hui; Xie, Hua-Lin; Cao, Shu

    2013-01-01

    The present paper describes a simple method for the determination of trace elements in sunflower seeds by using inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma spectrometry (ICP-MS). HNO3 + H2O2 were used to achieve the complete decomposition of the organic matrix in a closed-vessel microwave oven. The contents of 10 trace elements (Al, B, Ca, Fe, K, Mg, Na, Si, P and S) in sunflower seeds were determined by ICP-OES while 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sr, Sn, Sb, Ti, V and Zn) were determined by ICP-MS. The rice reference material (GBW10045) was used as standard reference materials. The results showed a good agreement between measured and certified values for all analytes. The concentrations of necessary micro elements Ca, K, Mg, P and S were higher. This method was simple, sensitive and precise and can perform simultaneous multi-elements determination of sunflower seeds.

  14. Preparation of hair for measurement of elements by inductively coupled plasma-mass spectrometry (ICP-MS).

    PubMed

    Puchyr, R F; Bass, D A; Gajewski, R; Calvin, M; Marquardt, W; Urek, K; Druyan, M E; Quig, D

    1998-06-01

    The preparation of hair for the determination of elements is a critical component of the analysis procedure. Open-beaker, closed-vessel microwave, and flowthrough microwave digestion are methods that have been used for sample preparation and are discussed. A new digestion method for use with inductively coupled plasma-mass spectrometry (ICP-MS) has been developed. The method uses 0.2 g of hair and 3 mL of concentrated nitric acid in an atmospheric pressure-low-temperature microwave digestion (APLTMD) system. This preparation method is useful in handling a large numbers of samples per day and may be adapted to hair sample weights ranging from 0.08 to 0.3 g. After digestion, samples are analyzed by ICP-MS to determine the concentration of Li, Be, B, Na, Mg, Al, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As, Se, Rb, Sr, Zr, Mo, Pd, Ag, Cd, Sn, Sb, I, Cs, Ba, Pt, Au, Hg, Tl, Pb, Bi, Th, and U. Benefits of the APLTMD include reduced contamination and sample handling, and increased precision, reliability, and sample throughput.

  15. Elemental fingerprinting of soils using ICP-MS and multivariate statistics: a study for and by forensic chemistry majors.

    PubMed

    Reidy, Lorlyn; Bu, Kaixuan; Godfrey, Murrell; Cizdziel, James V

    2013-12-10

    Students in an instrumental analysis course with a forensic emphasis were presented with a mock scenario in which soil was collected from a murder suspect's car mat, from the crime scene, from adjacent areas, and from more distant locations. Students were then asked to conduct a comparative analysis using the soil's elemental distribution fingerprints. The soil was collected from Lafayette County, Mississippi, USA and categorized as sandy loam. Eight student groups determined twenty-two elements (Li, Be, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Cs, Ba, Pb, U) in seven samples of soil and one sample of sediment by microwave-assisted acid digestion and inductively coupled plasma-mass spectrometry (ICP-MS). Data were combined and evaluated using multivariate statistical analyses. All eight student groups correctly classified their unknown among the different locations. Students learn, however, that whereas their results suggest that the elemental fingerprinting approach can be used to distinguish soils from different land-use areas and geographic locations, applying the methodology in forensic investigations is more complicated and has potential pitfalls. Overall, the inquiry-based pedagogy enthused the students and provided learning opportunities in analytical chemistry, including sample preparation, ICP-MS, figures-of-merit, and multivariate statistics.

  16. Chromium and its speciation in water samples by HPLC/ICP-MS--technique establishing metrological traceability: a review since 2000.

    PubMed

    Markiewicz, Barbara; Komorowicz, Izabela; Sajnóg, Adam; Belter, Magdalena; Barałkiewicz, Danuta

    2015-01-01

    Chromium holds a special position among living organisms because depending on its species it can be either essential or toxic. Cr(VI) even at very low concentrations is harmful and carcinogenic, while Cr(III) is a necessary microelement for cellular metabolism. Therefore, a simple analysis of Cr concentration in collected samples will not be able to distinguish these differences effectively: for a proper chemical analysis we need to perform a reliable detection and quantification of Cr species. Separation and detection of chromium can be accomplished with high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS) in a one-step. Our review assembles articles published since 2000 regarding chromium speciation in water samples with the use of HPLC/ICP-MS. It addresses the following issues: chromium chemistry, the possibilities of dealing with interferences, metrological aspects, analytical performance and speciated isotope dilution mass spectrometry (SIDMS) which is a definitive measurement method. The authors would like to advocate this hyphenated advanced technique as well as the metrological approach in speciation analysis of chromium.

  17. [Determination of thirty three elements in lung cancer tissues of patients with lung cancer by microwave digestion-ICP-MS].

    PubMed

    Zhang, Lin-Lin; Ma, Qian-Li; Huang, Yun-Chao; Wu, Guo-Ping; Wei, Fu-Sheng

    2009-12-01

    A method for determining 33 elements in lung tissues of patients with lung cancer was developed by using vacuum freeze-drying microwave digestion-ICP-MS. The lung tissue samples were treated by vacuum freeze-drying equipment. After microwave digestion in HNO3-H2O2 solution system, the samples were diluted with the method of constant volume. Under the optimized conditions the samples were analyzed by ICP-MS. The double internal standard elements Rh and Re were used to compensate for matrix suppression effect and sensitivity drift. The analytical results showed that the detection limits of the 33 elements were 0.01-0.45 ng x mL(-1). The national standard reference material GBW(E)080193 bovine liver was analyzed by the described method and the measured element values accorded with the standard values or the reference values. The relative standard deviation (RSD) of the method was 2.1%-14.3%. The recovery rates of the studied elements were 90.1%-117.5%. The contents of 33 elements in lung cancer tissues, paracancerous lung tissues and benign lung tissues of 6 patients with lung cancer were determined by the method. It was indicated that the method is rapid, simple and accurate for determining multi-elements in human lung tissue and other biological samples.

  18. Determination of gallium originated from a gallium-based anticancer drug in human urine using ICP-MS.

    PubMed

    Filatova, Darya G; Seregina, Irina F; Foteeva, Lidia S; Pukhov, Vladimir V; Timerbaev, Andrei R; Bolshov, Mikhail A

    2011-05-01

    Urine analysis gives an insight into the excretion of the administered drug which is related to its reactivity and toxicity. In this work, the capability of inductively coupled plasma mass spectrometry (ICP-MS) to measure ultratrace metal levels was utilized for rapid assaying of gallium originating from the novel gallium anticancer drug, tris(8-quinolinolato)gallium(III) (GaQ(3)), in human urine. Sample dilution with 1% (v/v) HNO(3) as the only required pre-treatment was shown to prevent contamination of the sample introduction system and to reduce polyatomic interferences from sample components. The origin of the blank signal at masses of gallium isotopes, 71 and 69, was investigated using high-resolution ICP-MS and attributed, respectively, to the formation of (36)Ar(35)Cl(+) and (40)Ar(31)P(+) ions and, tentatively, to a triplet of doubly charged ions of Ba, La, and Ce. The accuracy and precision performance was tested by evaluating a set of parameters for analytical method validation. The developed assay has been applied for the determination of gallium in urine samples spiked with GaQ(3). The achieved recoveries (95-102%) and quantification limit of 0.2 μg L(-1) emphasize the practical applicability of the presented analytical approach to monitor renal elimination of GaQ(3) at all dose levels in clinical trials that are currently in progress.

  19. Evaluation of nebulizer performance within the ICP-MS measurement system for analysis of SRS radiological waste tank simulated solutions

    SciTech Connect

    Jones, V.D.

    1998-12-31

    High level radioactive waste tanks at the Savannah River Site are high in salt content. The average Total Dissolved Solids (TDS) content is approximately 25%. For ICP-MS optimum signal stability and to reduce blockage of nebulizers and sampling orifices, it is usual to limit analyte solutions to a TDS content of nominally < 0.2%. Dilution to this level to reduce the matrix effect may push some analytes of interest below detectable levels. Five commercially available nebulizers were evaluated in a field study as part of the ICP-MS measurement system for their performance in a high salt matrix. The nebulizers surveyed were a meinhard concentric, cross-flow, micro-concentric (MCN), V-groove, and a direct injection nebulizer (DIN). Analytes spiked into non-radioactive diluted salt solutions ranging from nominal 0.25--1.0% TDS were repetitively analyzed with the goal of determining stability of response signal and magnitude of any signal loss/suppression resulting from the diluted salt matrix. The cross-flow nebulizer provided the most stable signal for all salt matrices with the smallest signal loss/suppression due to this matrix. The DIN exhibited a serious lack of tolerance for TDS; possibly due to physical de-tuning of the nebulizer efficiency.

  20. [Determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS].

    PubMed

    Hu, Zhao-chu; Gao, Shan; Liu, Xiao-ming; Yuan, Hong-lin; Liu, Ye; Diwu, Chun-rong

    2007-12-01

    The authors studied in detail the memory effect of Bi, Sb, As and Te in ICP-MS. The produced memory effects of these element were in the order of Bi>Sb>Te>As. Bi was seriously adsorbed by the polypropylene sample storing bottle and the sample introduction system in the low nitric acid medium (0.01%-1% HNO3). The washout effect of 0.1% HF was found to be better than those of 6% HNO3 and 0.1% HClO4. Under the given experiment conditions, the instrumental limit of detection was 0.001 and 0.0001 ng x mL(-1) for Sb and Bi, respectively. The authors report the determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS (including AGV-2, BHVO-2, BCR-2, etc.). Most of the results were found to be in reasonable agreement with the reported values in the literature. The authors' determined values of Sb for GSR-1 (granite; 0.30 microg x g(-1)) and JP-1 (peridotite; 0.045 microg x g(-1)) are obviously higher than those reported values. This is attributed to the efficient pressurized acid digestion, which is generally much more efficient than conventional wet digestions for insoluble minerals.

  1. Study of tungstate-protein interaction in human serum by LC-ICP-MS and MALDI-TOF.

    PubMed

    Rodríguez-Fariñas, Nuria; Gomez-Gomez, M Milagros; Camara-Rica, Carmen

    2008-01-01

    Oral administration of sodium tungstate is an effective treatment for type 1 and 2 diabetes in animal models; it does not incur significant side effects, and it may constitute an alternative to insulin. However, the mechanism by which tungstate exerts its observed metabolic effects in vivo is still not completely understood. In this work, serum-containing proteins which bind tungstate have been characterized. Size exclusion chromatography (SEC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) with a Phenomenex Bio-Sep-S 2000 column and 20 mM HEPES and 150 mM NaCl at pH 7.4 as the mobile phase was chosen as the most appropriate methodology to screen for tungsten-protein complexes. When human serum was incubated with tungstate, three analytical peaks were observed, one related to tungstate-albumin binding, one to free tungstate, and one to an unknown protein binding (MW higher than 300 kDa). Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometric analysis of the tungsten-containing fractions collected from SEC-ICP-MS chromatograms, after desalting and preconcentration processes, confirmed the association of tungstate with albumin and the other unknown protein. [figure: see text

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

    USGS Publications Warehouse

    Wolf, Ruth E.; Adams, Monique

    2015-01-01

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

  3. Isotopic signature of selected lanthanides for nuclear activities profiling using cloud point extraction and ICP-MS/MS.

    PubMed

    Labrecque, Charles; Lebed, Pablo J; Larivière, Dominic

    2016-05-01

    The presence of fission products, which include numerous isotopes of lanthanides, can impact the isotopic ratios of these elements in the environment. A cloud point extraction (CPE) method was used as a preconcentration/separation strategy prior to measurement of isotopic ratios of three lanthanides (Nd, Sm, and Eu) by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). To minimise polyatomic interference, the combination of interferents removal by CPE, reaction/collision cell conditions in He and NH3 mode and tandem quadrupole configuration was investigated and provided optimal results for the determination of isotopic ratio in environmental samples. Isotopic ratios were initially measured in San Joaquin soil (NIST-2709a), an area with little contamination of nuclear origin. Finally, samples collected from three sites with known nuclear activities (Fangataufa Lagoon in French Polynesia, Chernobyl and the Ottawa River near Chalk River Laboratory) were analysed and all exhibited altered isotopic ratios for (143/145)Nd, (147/149)Sm, and (151/153)Eu. These results demonstrate the potential of CPE and ICP-MS/MS for the detection of altered isotopic ratio in environmental samples collected in area subjected to nuclear anthropogenic contamination. The detection of variations in these isotopic ratios of fission products represents the first application of CPE in nuclear forensic investigations of environmental samples.

  4. Determination of traces of 237Np in environmental samples by ICP-MS after separation using TOA extraction chromatography.

    PubMed

    Ji, Y Q; Li, J Y; Luo, S G; Wu, T; Liu, J L

    2001-09-01

    A simple, rapid, cost-efficient, and robust method for separation of 237Np with an extraction chromatographic column (TOA: tri-n-octylamine on Teflon powder) is outlined in detail and further improved for direct ICP-MS analysis. The column efficiently retained 237Np in 2 mol L(-1) HNO3 medium and all of the 237Np was easily eluted with 0.02 mol L(-1) oxalic acid in 0.16 mol L(-1) HNO3 at 95 degrees C. The separated solutions were free from most matrix elements and were aspirated into the ICP-MS directly. The decontamination factor for 238U is more than 10(4). The instrumental detection limit for 237Np was 0.46 pg mL(-1), which corresponds to 1.2 x 10(-5) Bq mL(-1). The method is more rapid than traditional radiometric techniques. It is also considered to be more suitable for environmental monitoring than existing methods based on TOA.

  5. In situ laser ablation ICP-MS analyses of dimict diogenites: Further evidence for harzburgitic and orthopyroxenitic lithologies

    NASA Astrophysics Data System (ADS)

    Beck, Andrew W.; McSween, Harry Y.; Bodnar, Robert J.

    2013-06-01

    Trace element concentrations in pyroxene, plagioclase, and olivine were measured in five diogenite breccias previously identified as containing distinct harzburgitic (ol+opx) and orthopyroxenitic (opx) lithologies (dimict). Three samples show two distinct populations of pyroxene trace element abundances, supporting their classification as dimict. These three meteorites show increases in Y, Yb, and HREE concentrations from harzburgitic to orthopyroxenitic pyroxenes, supporting the hypothesis that the lithologies are related through fractional crystallization whereby harzburgite olivine and pyroxene crystallized from the magma first followed by orthopyroxenite pyroxene. Depletions in LREE and Eu concentrations in the orthopyroxenitic lithology are most likely due to equilibration with LREE and Eu-rich phases, likely plagioclase, which is found primarily in that lithology. Two samples do not show evidence supporting a dimict classification. Large pyroxene trace element variation in one sample indicates that it is polymict, while uniform trace element distribution in the other suggests that it may be a monomict breccia.

  6. Laser-Ablation ICP-MS Analyses of Meteoritic Metal Grains in Lunar Impact-Melt Breccias

    NASA Technical Reports Server (NTRS)

    Korotev, R. L.; Jolliff, B. L.; Campbell, A. J.; Humayun, M.

    2003-01-01

    Lunar impact-melt breccias contain metal grains from the meteorites that formed the breccias. Because the breccias contain clastic material that may derive from older breccias, metal grains from earlier impacts may be present, too. The large subset of moderately mafic (8 - 12% FeO), KREEP-rich ("LKFM") melt breccias is particularly important because: (1) these are the melt breccias most likely to have been produced in basin-forming impacts, (2) it is from these breccias that many of the approx. 3.9 Gyr ages that are so common in lunar samples derive, (3) the breccias contain large proportions of FeNi metal, more than 1% in some types of Apollo 16 breccias, and (4) the metal potentially provides information about the impactors causing the apparent cataclysm at 3.9 Gyr.

  7. Feasibility of asymmetric flow field-flow fractionation coupled to ICP-MS for the characterization of wear metal particles and metalloproteins in biofluids from hip replacement patients.

    PubMed

    Loeschner, Katrin; Harrington, Chris F; Kearney, Jacque-Lucca; Langton, David J; Larsen, Erik H

    2015-06-01

    Hip replacements are used to improve the quality of life of people with orthopaedic conditions, but the use of metal-on-metal (MoM) arthroplasty has led to poor outcomes for some patients. These problems are related to the generation of micro- to nanosized metal wear particles containing Cr, Co or other elements, but the current analytical methods used to investigate the processes involved do not provide sufficient information to understand the size or composition of the wear particles generated in vivo. In this qualitative feasibility study, asymmetric flow field-flow fractionation (AF(4)) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was used to investigate metal protein binding and the size and composition of wear metal particles present in serum and hip aspirates from MoM hip replacement patients. A well-established HPLC anion exchange chromatography (AEC) separation system coupled to ICP-MS was used to confirm the metal-protein associations in the serum samples. Off-line single particle ICP-MS (spICP-MS) analysis was used to confirm the approximate size distribution indicated by AF(4) of the wear particles in hip aspirates. In the serum samples, AF(4) -ICP-MS suggested that Cr was associated with transferrin (Tf) and Co with albumin (Alb) and an unidentified species; AEC-ICP-MS confirmed these associations and also indicated an association of Cr with Alb. In the hip aspirate sample, AF(4)-ICP-MS suggested that Cr was associated with Alb and Tf and that Co was associated with Alb and two unidentified compounds; AEC analysis confirmed the Cr results and the association of Co with Alb and a second compound. Enzymatic digestion of the hip aspirate sample, followed by separation using AF(4) with detection by UV absorption (280 nm), multi-angle light scattering and ICP-MS, suggested that the sizes of the Cr-, Co- and Mo-containing wear particles in a hip aspirate sample were in the range 40-150 nm. Off-line spICP-MS was used to confirm these

  8. A miniaturised laser ablation/ionisation analyser for investigation of elemental/isotopic composition with the sub-ppm detection sensitivity

    NASA Astrophysics Data System (ADS)

    Tulej, M.; Riedo, A.; Meyer, S.; Iakovleva, M.; Neuland, M.; Wurz, P.

    2012-04-01

    analysis of solid materials on the planetary surfaces (Rohner et al., 2003). Initial laboratory tests that were conducted with an IR laser radiation for the ablation, atomisation and ionisation of the material, indicated a high performance of the instrument in terms of sensitivity, dynamic range and mass resolution (Tulej et al., 2011). After some technical improvements and implementation of a computer-controlled performance optimiser we have achieved further improvements of both, the instrumental sensitivity down to sub-ppm level and reproducibility of the measurements. We will demonstrate the potential of the mass analyser to perform the quantitative elemental analysis of solids with a spatial (vertical, lateral) resolution commensurate with typical grain sizes, and its capabilities for investigation of isotopic patterns with accuracy and precision comparable to that of large analytical laboratory instruments, e.g., TIMS, SIMS, LA-ICP-MS. The results can be of considerable interest for in situ dating or investigation of other fine isotopic fractionation effects including studies of bio-markers.

  9. Measurement by ICP-MS of lead in plasma and whole blood of lead workers and controls.

    PubMed Central

    Schütz, A; Bergdahl, I A; Ekholm, A; Skerfving, S

    1996-01-01

    OBJECTIVES: To test a simple procedure for preparing samples for measurement of lead in blood plasma (P-Pb) and whole blood (B-Pb) by inductively coupled plasma mass spectrometry (ICP-MS), to measure P-Pb and B-Pb in lead workers and controls, and to evaluate any differences in the relation between B-Pb and P-Pb between people. METHODS: P-Pb and B-Pb were measured by ICP-MS in 43 male lead smelter workers and seven controls without occupational exposure to lead. For analysis, plasma and whole blood were diluted 1 in 4 and 1 in 9, respectively, with a diluted ammonia solution containing Triton-X 100 and EDTA. The samples were handled under routine laboratory conditions, without clean room facilities. RESULTS: P-Pb was measured with good precision (CV = 5%) even at concentrations present in the controls. Freeze storage of the samples had no effect on the results. The detection limit was 0.015 microgram/l. The P-Pb was 0.15 (range 0.1-0.3) microgram/l in controls and 1.2 (0.3-3.6) micrograms/l in lead workers, although the corresponding B-Pbs were 40 (24-59) micrograms/l and 281 (60-530) micrograms/l (1 microgram Pb/I = 4.8 nmol/l). B-Pb was closely associated with P-Pb (r = 0.90). The association was evidently non-linear; the ratio B-Pb/P-Pb decreased with increasing P-Pb. CONCLUSIONS: By means of ICP-MS and a simple dilution procedure, P-Pb may be measured accurately and with good precision down to concentrations present in controls. Contamination of blood at sampling and analysis is no major problem. With increasing P-Pb, the percentage of lead in plasma increases. In studies of lead toxicity, P-Pb should be considered as a complement to current indicators of lead exposure and risk. PMID:9038796

  10. The potential of on-line continuous leach ICP-MS analysis for linking trace elements to mineralogy

    NASA Astrophysics Data System (ADS)

    Roskam, Gerlinde; Verheul, Marc; Moraetis, Daniel; Giannakis, George; van Gaans, Pauline

    2014-05-01

    A set of five soil samples was subjected to an on-line continuous leach inductively coupled plasma mass spectrometry experiment, with progressively reactive solvents (0.01M CaCl2, 0.1 M HNO3, 1M HNO3, 4M HNO3) Each sample was packed in a quartz tube (Ø= 1 cm, length 2 cm) and diluted 1:1 with acid washed quartz to prevent clogging. The gas that was produced during the extraction was removed by leading the effluent into a small container, from where the sample was directly pumped into the ICP-MS. 115In was used as an internal standard. Continuous leach experiments have the advantage of real time (every 2 seconds) full elemental analysis. Mineral breakdown reactions can be monitored via the major elements. The trace elements associated with the minerals are monitored simultaneously, thus eliminating the uncertainties of host mineral-trace element combinations in traditional off-line sequential extractions. The continuous leach experimental data are correlated to XRD-results for mineralogy and total elemental concentrations. The soil samples used were collected from different sites in the Koiliaris River watershed, Crete, Greece 1). The selection of the sites was based on variability in bedrock (limestone, metamorphic and alluvial sediments) and current land use (grape farming, olive trees). Soils were sampled at two depths: at the surface and just above the bedrock. No large differences in the major elements between the two depths were measured. To provide background to the on-line sequential data, also total concentrations of the major elements were analysed by XRF and the mineralogy was analysed by XRD. The fraction <2mm was sieved and digested with HF, HClO4 and HNO3 for additional trace element analysis. 1) See related abstract Roskam et al., 2014: REE profiles in continuous leach ICP-MS (CL-ICP-MS) experiments in soil, linked to REE profiles in surface water in the Koiliaris River Critical Zone Observatory (CZO), Crete, Greece.

  11. Evaluation of bromine and iodine content of milk whey proteins combining digestion by microwave-induced combustion and ICP-MS determination.

    PubMed

    da Silva, Sabrina Vieira; Picoloto, Rochele Sogari; Flores, Erico Marlon Moraes; Wagner, Roger; dos Santos Richards, Neila Silvia Pereira; Barin, Juliano Smanioto

    2016-01-01

    The bromine and iodine content of whey protein concentrate (WPC), hydrolysate (WPH), and isolate (WPI) was evaluated combining microwave-induced combustion (MIC) digestion with inductively coupled plasma mass spectrometry (ICP-MS) determination. MIC digestion allowed the decomposition of up to 500 mg of samples using diluted NH4OH solution (25 mmol L(-1)) for absorption of analytes, assuring the compatibility with ICP-MS determination. Accuracy was evaluated using milk powder certified reference material (NIST 8435) with good agreements for Br and I (102% and 105%, respectively). For Br and I, the limit of quantification obtained by ICP-MS was 7 and 281 times lower in comparison with ion chromatography determination, respectively. Iodine could be enriched in whey protein production and up to 70% of the tolerable upper intake level was found, thus revealing the need to monitor it in whey proteins. On the other hand, the concentration of Br was below its acceptable daily intake.

  12. Standardless determination of Nd and Sr isotope ratios in geological samples using LA-MC-ICP-MS with a low-oxide molecular yield interface setup

    NASA Astrophysics Data System (ADS)

    Kimura, J.; Chang, Q.; Takahashi, T.; Kawabata, H.

    2013-12-01

    We investigated an appropriate instrumental setup for a laser-ablation multiple-collector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) and found that a reduced oxide setting allowed accurate and precise analyses of Sr and Nd isotope ratios in geological samples with concomitant interfering elements (Kr and Rb on Sr and Sm on Nd). We used an Aridus II solution-excimer laser dual-intake system. The ICP interface used normal sample and skimmer cones with torch shield switched-OFF and an additional large interface rotary pump. The setting accomplished reduced oxide levels NdO+/Nd+ <0.01%, without significant sacrifice of the instrumental sensitivity (c.a. 70%). Oxide molecular ions for the lighter elements were negligible and accurate internal mass bias corrections were achieved for Sr, Sm, and Nd using isotopic ratios derived from thermal ionization mass spectrometry measurements. However, elemental fractionation between Rb and Sr and Nd and Sm still exists due perhaps to elemental fractionation in the ICP preventing standardless determination of parent-daughter ratios. For Sr isotope measurement, a new analytical protocol was developed for correcting Kr baseline-induced biases. Residual analytical biases of 84Sr/86Sr and 87Sr/86Sr were observed after applying on-peak background subtractions and mass-fractionation corrections using internal normalization. The residual biases occurred only for samples analysed with LA and not for solution analyses using Aridus II with the same instrumental setup. We concluded that this was due to suppression and enhancement of the Kr baseline by loading of the LA sample aerosols and by the introduction of Kr from the samples, respectively. We found that both the 84Sr/86Sr and 87Sr/86Sr isotope ratios were affected proportionally by the baseline biases of the LA analyses of an isotopically homogeneous anorthite plagioclase, and similar result were seen in theoretical calculations. A theoretical bias correction for the 87

  13. Speciation analysis of selenium in plankton, Brazil nut and human urine samples by HPLC-ICP-MS.

    PubMed

    da Silva, Elidiane Gomes; Mataveli, Lidiane Raquel Verola; Arruda, Marco Aurélio Zezzi

    2013-06-15

    The HPLC (anion exchange)-ICP-MS technique was used for the identification (based on retention time of standards) and determination of four selenium species (selenite, selenate, selenomethionine and selenocystine) in plankton (BCR-414), Brazil nuts and urine samples. A recovery of 91% was attained for certified reference materials (BCR-414). Se(IV) was the predominant species in plankton, with the highest selenium concentration in the extract. The Brazil nuts showed only the organic species selenomethionine and selenocystine after water extraction, but after simulated gastrointestinal digestion, only selenomethionine was found as bioaccessible, corresponding to 74% of the total selenium (54.8±4.6 μg g(-1)). Analyses of the urine samples suggested the presence of selenocystine, and significant differences were observed between samples from men and women in terms of the concentration of this species after consumption of Brazil nuts (1 nut per day during 15 days).

  14. Determination of 241Am in Urine Using Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS)

    PubMed Central

    Xiao, Ge; Saunders, David; Jones, Robert L.; Caldwell, Kathleen L.

    2016-01-01

    Quantification of 241Am in urine at low levels is important for assessment of individuals’ or populations’ accidental, environmental, or terrorism-related internal contamination, but no convenient, precise method has been established to rapidly determine these low levels. Here we report a new analytical method to measure 241Am as developed and validated at the Centers for Disease Control and Prevention (CDC) by means of the selective retention of Am from urine directly on DGA resin, followed by SF-ICP-MS detection. The method provides rapid results with a Limit of Detection (LOD) of 0.22 pg/L (0.028 Bq/L), which is lower than 1/3 of the C/P CDG for 241Am at 5 days post-exposure. The results obtained by this method closely agree with CDC values as measured by Liquid Scintillation Counting, and with National Institute of Standards Technology (NIST) Certified Reference Materials (CRM) target values. PMID:27375308

  15. Determination of Sb(III) and Sb(V) by HPLC-Online isotopic dilution-ICP MS.

    PubMed

    Fontanella, Maria Chiara; Beone, Gian Maria

    2016-01-01

    This work provides a method with application of valid techniques to extract and determinate inorganic species of antimony (Sb) for water. The procedure involves•the simultaneous accumulation of Sb(III) and Sb(V) on passive samplers like Diffusive Gradient in Thin Films (DGT) with iron (Fe) oxide gel, eliminating the risk of speciation changes due to transport and storage;•application of less concentrated acid (50 mM Na2EDTA) for elution and preservation of Sb species from DGT resin;•subsequent analytical determination of inorganic species with High Performance Liquid Chromatography-Isotopic Dilution-Inductively Coupled Plasma Mass Spectrometer (HPLC-ID-ICP MS) based on determination of the isotope ratio ((123)Sb/(121)Sb) of isotopes in the samples after spiking with 123Sb enriched standard solution, reducing the effect of signal drift and matrix effect on the final value.

  16. [Determination of trace element silver in animal serum, tissues and organs by microwave digestion-ICP-MS].

    PubMed

    Yuan, Jun-Jie; Xie, You-Zhuan; Han, Chen; Sun, Wei; Zhang, Kai; Zhao, Jie; Lu, Xiao; Lu, Jian-Xi; Ren, Wei

    2014-09-01

    Nowadays, the silver is widely used in the biological field and its biological safety catches great attention. It is important to know the distribution of silver ions within the biological organism and the toxic threshold concentration in the tissue. Therefore, a highly sensitive method for measurement of trace amount of silver ion in the medical biological samples is needed. With its high sensitivity for detection of metal ions, inductively coupled plasma mass spectrometry (ICP-MS) method is well suited for quantification of trace amount of silver ion in such samples, but method development is still in its infancy. Consequently, a simple and convenient method for determination of trace amount of silver in the animal serum, tissues or organs was developed, in which the samples were subjected to the microwave digestion, followed by the ICP-MS analysis. To begin with, the samples of serum, muscle, bone marrow, bone, heart, liver, spleen, and kidney were sequently processed in 5 mL of HNO3 and 2 mL of H2O2 solution. Then the samples were completely digested by microwave with the power of 2 000 watts. The temperature was raised gradually by 3-step program. Moreover, the data achieved were reproducible and the method was time saving and especially for large amounts of sample processing. Then the digested solutions were diluted to constant volume. Finally, the concentration of 107Ag in the samples was analyzed by the method of ICP-MS under the optimized conditions. Element yttrium (Y) was used as the internal standard to compensate for matrix suppression effect and improve the accuracy of measurement. For one thing, the analytical results showed that the detection limit of the trace element 107Ag was 0.98 μg · kg(-1), and furthermore, the correlation coefficient of standard curve was 0.999 9. For another thing, the recovery rate of the silver element ranged from 98% to 107%, which was calculated according to measured quantity before adding standard, adding standard and

  17. A new HG/LT-GC/ICP-MS multi-element speciation technique for real samples in different matrices.

    PubMed

    Grüter, U M; Kresimon, J; Hirner, A V

    2000-09-01

    An improved speciation technique is presented for metal(loid)organic compounds, enabling identification and quantification of species from twelve elements: germanium, arsenic, selenium, molybdenum, tin, antimony, tellurium, iodine, tungsten, mercury, lead and bismuth. At this time it is possible to identify 29 species with boiling points between -88.5 degrees C and 250 C in gaseous, liquid and solid samples in a few minutes. This study shows as an example results from measurements of soil samples from municipal waste deposits. The HG/LT-GC/ICP-MS-(hydride generation/low temperature-gas chromatography/inductively coupled plasma-mass spectrometry) apparatus contains a home-built gas chromatograph that enables satisfactory separation of various species with a boiling point difference of > or = 14 degrees C. The absolute detection limits for the elements mentioned above were below 0.7 pg.

  18. Determination of toxic metals by ICP-MS in Asiatic and European medicinal plants and dietary supplements.

    PubMed

    Filipiak-Szok, Anna; Kurzawa, Marzanna; Szłyk, Edward

    2015-04-01

    The potentially toxic metals content was determined in selected plants, used in Traditional Chinese Medicine (Angelica sinensis, Bacopa monnieri, Bupleurum sinensis, Curcuma longa, Cola accuminata, Emblica officinalis, Garcinia cambogia, Mucuna pruriens, Ocimum sanctum, Panax ginseng, Pueraria lobata, Salvia miltiorrhiza, Schisandra sinensis, Scutellaria baicalensis, Siraitia grosvenorii, Terminalia arjuna and Terminalia chebula), and some European herbs (Echinacea purpurea, Hypericum perforatum, Vitis vinifera). Samples were mineralized in a closed microwave system using HNO3 and the concentrations of Cd, Pb, Al, As, Ba, Ni and Sb were determined by ICP-MS method. Some relevant aspects of potential toxicity of metallic elements and their compounds were also discussed. Results of metal content analysis in dietary supplements available on Polish market, containing studied plants, are presented as well. The results were analyzed by principal component analysis (PCA) and cluster analysis.

  19. Comprehensive Isotopic and Elemental Analysis of a Multi-Oxide Glass By Multicollector ICP-MS in Isotope Substitution Studies

    SciTech Connect

    v, Mitroshkov; JV, Ryan

    2016-04-07

    Multicollector ICP-MS was used to comprehensively analyze different types of isotopically-modified glass created in order to investigate the processes of glass corrosion in the water. The analytical methods were developed for the analyses of synthesized, isotopically-modified solid glass and the release of glass constituents upon contact with deionized water. To validate the methods, results from an acid digestion sample of the Analytical Reference Glass (ARG) showed good agreement when compared to data from multiple prior analyses on the same glass [Smith-1]. In this paper, we present the results of this comprehensive analysis from the acid digestion of six types of isotopically-modified glass and the release of glass constituents into water corrosion after one year of aqueous corrosion.

  20. ICP/MS and ICP/AES elemental analysis (38 elements) of edible wild mushrooms growing in Poland.

    PubMed

    Falandysz, J; Szymczyk, K; Ichihashi, H; Bielawski, L; Gucia, M; Frankowska, A; Yamasaki, S

    2001-06-01

    Thirty-eight elements, including toxic cadmium, lead, mercury, silver and thallium, were determined in 18 species of wild edible mushrooms collected from several sites in Pomorskie Voivodeship in northern Poland in 1994. Elements were determined by double focused high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), after wet digestion of the dried samples with concentrated nitric acid in closed PTFE vessels using a microwave oven. K, P and Mg were present at levels of mg/g dry matter; Na, Zn, Ca, Fe, Cu, Mn, Rb, Ag, Cd, Hg, Pb, Cs, Sr, Al and Si were present at microg/g levels, while Tl, In, Bi, Th, U, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, La, Lu and Ba were present at ng/g levels.

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

    PubMed

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

    2010-05-01

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

  2. Determination of toxic elements in coal by ICP-MS after digestion using microwave-induced combustion.

    PubMed

    Antes, Fabiane G; Duarte, Fábio A; Mesko, Márcia F; Nunes, Matheus A G; Pereira, Vanda A; Müller, Edson I; Dressler, Valderi L; Flores, Erico M M

    2010-12-15

    A microwave-induced combustion (MIC) procedure was applied for coal digestion for subsequent determination of As, Cd and Pb by inductively coupled plasma mass spectrometry (ICP-MS) and Hg using cold vapor (CV) generation coupled to ICP-MS. Pellets of coal (500 mg) were combusted using 20 bar of oxygen and ammonium nitrate as aid for ignition. The use of nitric acid as absorbing solution (1.7, 3.5, 5.0, 7.0 and 14 mol L(-1)) was evaluated. For coal samples with higher ash content, better results were found using 7.0 mol L(-1) HNO(3) and an additional reflux step of 5 min after combustion step. For coal samples with ash content lower than 8%, 5.0 mol L(-1) nitric acid was suitable to the absorption of all analytes. Accuracy was evaluated using certified reference material (CRM) of coal and spikes. Agreement with certified values and recoveries was better than 95 and 97%, respectively, for all the analytes. For comparison of results, a procedure recommended by the American Society of Testing and Materials (ASTM) was used. Additionally, a conventional microwave-assisted digestion (MAD) in pressurized vessels was also performed. Using ASTM procedure, analyte losses were observed and a relatively long time was necessary for digestion (>6h). By comparison with MAD procedure, higher sample mass can be digested using MIC allowing better limits of detection. Additionally, the use of concentrated acids was not necessary that is an important aspect in order to obtain low blank levels and lower limits of detection, respectively. The residual carbon content in digests obtained by MAD and MIC was about 15% and <1%, respectively, showing the better digestion efficiency of MIC procedure. Using MIC it was possible to digest completely and simultaneously up to eight samples in only 25 min with relatively lower generation of laboratory effluents.

  3. Separation techniques for the clean-up of radioactive mixed waste for ICP-AES/ICP-MS analysis

    SciTech Connect

    Swafford, A.M.; Keller, J.M.

    1993-03-17

    Two separation techniques were investigated for the clean-up of typical radioactive mixed waste samples requiring elemental analysis by Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) or Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). These measurements frequently involve regulatory or compliance criteria which include the determination of elements on the EPA Target Analyte List (TAL). These samples usually consist of both an aqueous phase and a solid phase which is mostly an inorganic sludge. Frequently, samples taken from the waste tanks contain high levels of uranium and thorium which can cause spectral interferences in ICP-AES or ICP-MS analysis. The removal of these interferences is necessary to determine the presence of the EPA TAL elements in the sample. Two clean-up methods were studied on simulated aqueous waste samples containing the EPA TAL elements. The first method studied was a classical procedure based upon liquid-liquid extraction using tri-n- octylphosphine oxide (TOPO) dissolved in cyclohexane. The second method investigated was based on more recently developed techniques using extraction chromatography; specifically the use of a commercially available Eichrom TRU[center dot]Spec[trademark] column. Literature on these two methods indicates the efficient removal of uranium and thorium from properly prepared samples and provides considerable qualitative information on the extraction behavior of many other elements. However, there is a lack of quantitative data on the extraction behavior of elements on the EPA Target Analyte List. Experimental studies on these two methods consisted of determining whether any of the analytes were extracted by these methods and the recoveries obtained. Both methods produced similar results; the EPA target analytes were only slightly or not extracted. Advantages and disadvantages of each method were evaluated and found to be comparable.

  4. Application of HPLC-ICP-MS and HPLC-ESI-MS procedures for arsenic speciation in seaweeds.

    PubMed

    Hsieh, Yu-Jhe; Jiang, Shiuh-Jen

    2012-03-07

    Speciation of arsenic in seaweeds was carried out using ion chromatography (IC) for separation and inductively coupled mass spectrometry (ICP-MS) for detection. The arsenic species studied were arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine (AsB), and arsenocholine (AsC). Chromatographic separation of all the species was achieved in <9 min in gradient elution mode using (NH(4))(2)CO(3) and methanol at pH 8.5. The outlet of the IC column was directly connected to the nebulizer of ICP-MS for the determination of arsenic. The speciation of arsenic has been carried out in several seaweed samples. A microwave-assisted extraction method was used for the extraction of arsenic species from seaweed samples. With a mixture of mobile phase A and methanol as extractant, the extraction efficiency was >84%, and the recoveries from spiked samples were in the range of 90-106%. The unknown compounds detected in different seaweeds were identified by coupling IC directly with electrospray ionization-mass spectrometry (ESI-MS). Two arsenosugars and tetramethylarsonium ion (TETRA) were identified in different seaweeds. A fat-soluble arsenolipid compound was identified in the extract of certified reference material BCR-279 Ulva lactuca when 1% HNO(3) was used as the extractant. The precision between sample replicates was >9% for all determinations. The limits of detection were in the range of 0.006-0.015 μg L(-1) for various arsenic species based on peak height.

  5. [Determination of inorganic elements in rat serum, and vegetable and fruit ferment liquid by ICP-MS].

    PubMed

    Li, Xiang-yun; Lian, Hong-zhen; Chen, Yi-jun; Hu, Xin; Mao, Li; Lu, Ming; Cai, Yun-qing

    2008-09-01

    In the present paper, the contents of thirteen inorganic elements in rat serum, and vegetable and fruit ferment liquid (VFFL) were measured by ICP-MS in order to study the anti-tumor effect of VFFL. Serum or VFFL was digested in nitric and perchloric acids at room temperature and then heated until dryness. The residue was dissolved with 1% (phi) nitric acid prior to ICP-MS analysis. The element contents were quantitated by using 45Sc, 103Rh and 187Re as the internal standards, respectively, according to the rule of close mass number. Certificate references bovine serum (GBW(E)090006) and tea (GBW070605) were employed to validate the proposed method, and the analysis results of most elements in two certificate references were in agreement with their reference values. The intra-day and inter-day precisions of the method in terms of relative standard deviation (RSD) were mainly below 10% and below 15%, respectively. The spiked recoveries for most of studied elements were 80%-110% in rat serum and 90%-120% in VFFL. This method was rapid, highly sensitive, and especially suitable to being applied to small quantity of biological samples with greatly different elements contents. Therefore, we measured the content of thirteen elements in the sera of rats, where in were induced liver cancer by revulsant, and the rate were fed with different dosage of VFFL in intragastric infusion at the same time. It was preliminarily found that the concentrations of some elements in sera of different experiment groups of rats were significantly different, implying the potential anti-tumor effects of VFFL.

  6. Determination of trace elements in human liver biopsy samples by ICP-MS and TXRF: hepatic steatosis and nickel accumulation.

    PubMed

    Varga, Imre; Szebeni, Agnes; Szoboszlai, Norbert; Kovács, Béla

    2005-10-01

    Human liver biopsy samples, collected from 52 individuals, were analysed by inductively coupled plasma-mass spectrometry (ICP-MS) and total reflection X-ray fluorescence (TXRF) spectrometry in a retrospective study (i.e. patient selection and liver biopsy were not for the purpose of element analysis). The freeze-dried samples (typically 0.5-2 mg dry weight) were digested in a laboratory microwave digestion system and solutions with a final volume of 1 mL were prepared. The concentrations of Cr, Mn, Fe, Ni, Cu, Zn, Rb, and Pb were determined by use of a Thermo Elemental X7 ICP-MS spectrometer. TXRF measurements were performed with an Atomika Extra IIA spectrometer. Yttrium was employed as an internal standard, prepared by dissolution of 5N-purity yttria (Y(2)O(3)) in our laboratory. The accuracy was tested by analysis of NIST 1577a Bovine Liver certified reference material. The concentrations of Fe, Cu, Zn, and Rb determined in human liver biopsy samples were in good agreement with data published by other authors. The distribution of nickel in the samples was surprisingly uneven-nickel concentrations ranged from 0.7 to 12 microg g(-1) (dry weight) in 38 samples and in several samples were extremely high, 36-693 microg g(-1). Analysis of replicate procedural blanks and control measurements were performed to prevent misinterpretation of the data. For patients with steatosis (n=14) Ni concentrations were consistently high except for two who had levels close to those measured for the normal group. As far as we are aware no previous literature data are available on the association of steatosis with high concentration of nickel in human liver biopsies taken from living patients.

  7. Multielement analysis of micro-volume biological samples by ICP-MS with highly efficient sample introduction system.

    PubMed

    Takasaki, Yuka; Inagaki, Kazumi; Sabarudin, Akhmad; Fujii, Shin-Ichiro; Iwahata, Daigo; Takatsu, Akiko; Chiba, Koichi; Umemura, Tomonari

    2011-12-15

    A method for multielement analysis of micro-volume biological sample by inductively coupled plasma mass spectrometry (ICP-MS) with a highly efficient sample introduction system was presented. The sample introduction system was the combination of (1) an inert loop injection unit and (2) a high performance concentric nebulizer (HPCN) coupled with a temperature controllable cyclone chamber. The loop injection unit could introduce 20 μL samples into the carrier liquid flow of 10 μL min(-1) producing a stable signal for 100s without any dilution. The injection loop is continuously washed with 0.1M HNO(3) carrier solution during the measurement, thereby much improving sample throughput. The HPCN is a triple tube concentric nebulizer, which can generate fine aerosols and provide a stable and highly measurement sensitivity in ICP-MS at a liquid flow rate less than 10 μL min(-1). With the combination of the chamber heating at 60°C, the sensitivity obtained with the proposed sample introduction system at the liquid flow rate of 10 μL min(-1) was almost the same as that with a common concentric nebulizer and cyclone chamber system at the liquid flow rate of 1 mL min(-1), though the sample consumption rate of the HPCN was two orders of the magnitude lower than that of the common nebulizer. The validation of the proposed system was performed by analyzing the NIST SRM 1577b Bovine Liver. The observed values for 12 elements such as Na, P, S, K, Ca, Mn, Fe, Co, Cu, Zn, Mo, Cd were in good agreement with their certified values and information value. Satisfactory analytical results for 14 elements such as Na, Mg, P, S, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Y, Ba in Escherichia coli sample were also obtained. The proposed sample introduction system was quite effective in the cases when only micro-volume of biological sample is available.

  8. The performance of single and multi-collector ICP-MS instruments for fast and reliable 34S/32S isotope ratio measurements†

    PubMed Central

    Pröfrock, Daniel; Irrgeher, Johanna; Prohaska, Thomas

    2016-01-01

    The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3–0.5% (uc,rel), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement uc,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%). PMID:27812369

  9. The performance of single and multi-collector ICP-MS instruments for fast and reliable (34)S/(32)S isotope ratio measurements.

    PubMed

    Hanousek, Ondrej; Brunner, Marion; Pröfrock, Daniel; Irrgeher, Johanna; Prohaska, Thomas

    2016-11-14

    The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3-0.5% (uc,rel), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement uc,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%).

  10. Method validation for simultaneous determination of chromium, molybdenum and selenium in infant formulas by ICP-OES and ICP-MS.

    PubMed

    Khan, Naeem; Jeong, In Seon; Hwang, In Min; Kim, Jae Sung; Choi, Sung Hwa; Nho, Eun Yeong; Choi, Ji Yeon; Kwak, Byung-Man; Ahn, Jang-Hyuk; Yoon, Taehyung; Kim, Kyong Su

    2013-12-15

    This study aimed to validate the analytical method for simultaneous determination of chromium (Cr), molybdenum (Mo), and selenium (Se) in infant formulas available in South Korea. Various digestion methods of dry-ashing, wet-digestion and microwave were evaluated for samples preparation and both inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) were compared for analysis. The analytical techniques were validated by detection limits, precision, accuracy and recovery experiments. Results showed that wet-digestion and microwave methods were giving satisfactory results for sample preparation, while ICP-MS was found more sensitive and effective technique than ICP-OES. The recovery (%) of Se, Mo and Cr by ICP-OES were 40.9, 109.4 and 0, compared to 99.1, 98.7 and 98.4, respectively by ICP-MS. The contents of Cr, Mo and Se in infant formulas by ICP-MS were found in good nutritional values in accordance to nutrient standards for infant formulas CODEX values.

  11. DETECTION AND QUANTIFICATION OF A THIO-ARSENOSUGAR IN MARINE MOLLUSKS BY IC-ICP-MS WITH AN EMPHASIS ON THE INTERACTION OF ARSENOSUGARS WITH SULFIDE

    EPA Science Inventory

    Arsenosugars can make up a significant portion of the total arsenic in shellfish. These arsenosugars can be present in their oxide or sulfide form. IC-ICP-MS and IC-ESI-MS/MS data will be presented that indicates the presence of As(328-S) and As(328) in three species of marine ...

  12. Simultaneous determination of radiocesium ((135)Cs, (137)Cs) and plutonium ((239)Pu, (240)Pu) isotopes in river suspended particles by ICP-MS/MS and SF-ICP-MS.

    PubMed

    Cao, Liguo; Zheng, Jian; Tsukada, Hirofumi; Pan, Shaoming; Wang, Zhongtang; Tagami, Keiko; Uchida, Shigeo

    2016-10-01

    Due to radioisotope releases in the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident, long-term monitoring of radiocesium ((135)Cs and (137)Cs) and Pu isotopes ((239)Pu and (240)Pu) in river suspended particles is necessary to study the transport and fate of these long-lived radioisotopes in the land-ocean system. However, it is expensive and technically difficult to collect samples of suspended particles from river and ocean. Thus, simultaneous determination of multi-radionuclides remains as a challenging topic. In this study, for the first time, we report an analytical method for simultaneous determination of radiocesium and Pu isotopes in suspended particles with small sample size (1-2g). Radiocesium and Pu were sequentially pre-concentrated using ammonium molybdophosphate and ferric hydroxide co-precipitation, respectively. After the two-stage ion-exchange chromatography separation from the matrix elements, radiocesium and Pu isotopes were finally determined by ICP-MS/MS and SF-ICP-MS, respectively. The interfering elements of U ((238)U(1)H(+) and (238)U(2)H(+) for (239)Pu and (240)Pu, respectively) and Ba ((135)Ba(+) and (137)Ba(+) for (135)Cs and (137)Cs, respectively) were sufficiently removed with the decontamination factors of 1-8×10(6) and 1×10(4), respectively, with the developed method. Soil reference materials were utilized for method validation, and the obtained (135)Cs/(137)Cs and (240)Pu/(239)Pu atom ratios, and (239+240)Pu activities showed a good agreement with the certified/information values. In addition, the developed method was applied to analyze radiocesium and Pu in the suspended particles of land water samples collected from Fukushima Prefecture after the FDNPP accident. The (135)Cs/(137)Cs atom ratios (0.329-0.391) and (137)Cs activities (23.4-152Bq/g) suggested radiocesium contamination of the suspended particles mainly originated from the accident-released radioactive contaminates, while similar Pu contamination of suspended

  13. Interrogating the variation of element masses and distribution patterns in single cells using ICP-MS with a high efficiency cell introduction system.

    PubMed

    Wang, Hailong; Wang, Meng; Wang, Bing; Zheng, Lingna; Chen, Hanqing; Chai, Zhifang; Feng, Weiyue

    2017-02-01

    Cellular heterogeneity is an inherent condition of cell populations, which results from stochastic expression of genes, proteins, and metabolites. The heterogeneity of individual cells can dramatically influence cellular decision-making and cell fate. So far, our knowledge about how the variation of endogenous metals and non-metals in individual eukaryotic cells is limited. In this study, ICP-MS equipped with a high efficiency cell introduction system (HECIS) was developed as a method of single-cell ICP-MS (SC-ICP-MS). The method was applied to the single-cell analysis of Mn, Fe, Co, Cu, Zn, P, and S in human cancer cell lines (HeLa and A549) and normal human bronchial epithelial cell line (16HBE). The analysis showed obvious variation of the masses of Cu, Fe, Zn, and P in individual HeLa cells, and variation of Fe, Zn, and P in individual A549 cells. On the basis of the single-cell data, a multimodal distribution of the elements in the cell population was fitted, which showed marked differences among the various cell lines. Importantly, subpopulations of the elements were found in the cell populations, especially in the HeLa cancer cells. This study demonstrates that SC-ICP-MS is able to unravel the extent of variation of endogenous elements in individual cells, which will help to improve our fundamental understanding of cellular biology and reveal novel insights into human biology and medicine. Graphical abstract The variations of masses and distribution patterns of elements Mn, Fe, Co, Cu, Zn, P, and S in single cells were successfully detected by ICP-MS coupled with a high efficiency cell introduction system (HECIS).

  14. Fast and accurate determination of K, Ca, and Mg in human serum by sector field ICP-MS.

    PubMed

    Yu, Lee L; Davis, W Clay; Nuevo Ordonez, Yoana; Long, Stephen E

    2013-11-01

    Electrolytes in serum are important biomarkers for skeletal and cellular health. The levels of electrolytes are monitored by measuring the Ca, Mg, K, and Na in blood serum. Many reference methods have been developed for the determination of Ca, Mg, and K in clinical measurements; however, isotope dilution thermal ionization mass spectrometry (ID-TIMS) has traditionally been the primary reference method serving as an anchor for traceability and accuracy to these secondary reference methods. The sample matrix must be separated before ID-TIMS measurements, which is a slow and tedious process that hindered the adoption of the technique in routine clinical measurements. We have developed a fast and accurate method for the determination of Ca, Mg, and K in serum by taking advantage of the higher mass resolution capability of the modern sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). Each serum sample was spiked with a mixture containing enriched (44)Ca, (26)Mg, and (41)K, and the (42)Ca(+):(44)Ca(+), (24)Mg(+):(26)Mg(+), and (39)K(+):(41)K(+) ratios were measured. The Ca and Mg ratios were measured in medium resolution mode (m/Δm ≈ 4 500), and the K ratio in high resolution mode (m/Δm ≈ 10 000). Residual (40)Ar(1)H(+) interference was still observed but the deleterious effects of the interference were minimized by measuring the sample at K > 100 ng g(-1). The interferences of Sr(++) at the two Ca isotopes were less than 0.25 % of the analyte signal, and they were corrected with the (88)Sr(+) intensity by using the Sr(++):Sr(+) ratio. The sample preparation involved only simple dilutions, and the measurement using this sample preparation approach is known as dilution-and-shoot (DNS). The DNS approach was validated with samples prepared via the traditional acid digestion approach followed by ID-SF-ICP-MS measurement. DNS and digested samples of SRM 956c were measured with ID-SF-ICP-MS for quality assurance, and the results (mean

  15. Copper isotope variations of copper-rich minerals in seafloor hydrothermal deposits and igneous rocks, measured by a femtosecond LA-MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Ikehata, K.; Ishibashi, J.; Suzuki, R.; Hirata, T.

    2013-05-01

    In recent years, the copper isotope systematics has seen an increased interest as a potential tool for understanding copper sources and geochemical processes of copper transport and deposition in ore-forming systems. The copper isotope variations of primary and secondary copper-rich minerals from modern (Mariana Trough) and ancient (Besshi-type and Kuroko-type volcanogenic massive sulfide deposits, Japan) seafloor hydrothermal deposits have been analyzed by a femtosecond-pulsed laser ablation multiple collector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS). The δ65Cu (where δ65Cu = [(65Cu/63Cu)sample/ (65Cu/63Cu)NIST-SRM976-1] × 1000) values of copper-rich sulfide minerals of chimney samples from active seafloor hydrothermal deposits are significantly large (δ65Cu = -0.7 to 4.0‰) compared to those of copper-rich minerals in ancient submarine hydrothermal deposits (δ65Cu = -0.3 to 0.4‰; e.g., Ikehata et al., 2011) and in igneous rocks (δ65Cu = -0.3 to 0.3‰; e.g., Ikehata et al., 2012). These large copper isotopic variations in the chimney samples are most likely explained in terms of a redox-controlled isotope fractionation during hydrothermal reworking of copper sulfides below sea floor or alteration of primary hydrothermal copper sulfides by seawater, involving the preferential incorporation of heavy copper isotopes in secondary Cu(II) solutions. These results also suggest that sub-seafloor recrystallization and metamorphic reequilibration may have reduced the original range of copper isotopes. Secondary malachite (δ65Cu = 2.6 to 3.0‰) and native copper (δ65Cu = 1.4 to 1.7‰) in the Besshi-type deposits have heavier copper isotopic values compared to precursor copper-rich minerals. These variations are mainly due to isotope fractionations during redox reactions (weathering) at low temperatures involving the preferential incorporation of heavy copper isotopes in secondary Cu(II) solutions.

  16. Zircon U-Pb and trace element zoning characteristics in an anatectic granulite domain: Insights from LASS-ICP-MS depth profiling

    NASA Astrophysics Data System (ADS)

    Marsh, Jeffrey H.; Stockli, Daniel F.

    2015-12-01

    Understanding the geochemical characteristics of metamorphic zircon, and how they may be modified by recrystallization processes, is fundamental to defining the timescales of tectonic processes affecting continental lithosphere. We utilize laser ablation split-stream (LASS)-ICP-MS depth-profiling analysis to obtain a continuous rim-to-core record of the U-Pb ages and trace-element composition preserved within variably recrystallized zircon from different rock types within a well-studied granulite domain in the western Grenville Province, Canada. Detailed analysis of the depth-resolved signal enables definition of chemically distinct (homogeneous) internal domains and heterogeneous intervening zones that can generally be correlated with textural features observed in CL. Three age populations have been distinguished within the ~ 35 μm deep profiles that correlate well with the established timing of protolith formation, granulite-facies metamorphism, and amphibolite-facies shearing, respectively. The U-Pb isotopic system and Th/U ratios in much of the crystal interiors have undergone considerable modification, as evidenced by a linear correlation between 207Pb/206Pb age and Th/U ratio. Interior and rim domains commonly contain blurred or faded oscillatory zoning patterns, suggesting that solid-state recrystallization is at least partially responsible for the modified U-Th-Pb composition. A number of systematic trends in trace element composition are also observed between interior domains and recrystallized rims, including 1) decreased Th/U (to ~ 0.1), 2) tighter clustering of Hf concentrations, 3) decreased total REE, 4) unchanged Eu anomalies, and 5) a widened spread of HREE enrichment values (YbN/GdN). Both YbN/GdN vs. Th/U and U/Ce vs. Th plots show increasing degree of compositional differentiation from protolith zircon as a function of metamorphic reworking processes (i.e. sample type). The transition zones between interior and rim domains exhibit textural

  17. Cross calibration between XRF and ICP-MS for high spatial resolution analysis of ombrotrophic peat cores for palaeoclimatic studies.

    PubMed

    Poto, Luisa; Gabrieli, Jacopo; Crowhurst, Simon; Agostinelli, Claudio; Spolaor, Andrea; Cairns, Warren R L; Cozzi, Giulio; Barbante, Carlo

    2015-01-01

    Ombrotrophic peatlands are remarkable repositories of high-quality climatic signals because their only source of nutrients is precipitation. Although several analytical techniques are available for analysing inorganic components in peat samples, they generally provide only low-resolution data sets. Here we present a new analytical approach for producing high-resolution data on main and trace elements from ombrotrophic peat cores. Analyses were carried out on a 7-m-long peat core collected from Danta di Cadore, North-Eastern Italy (46° 34' 16″ N, 12° 29' 58″ E). Ca, Ti, Cr, Fe, Cu, Zn, Ga, Sr, Y, Cd, Ba and Pb were detected at a resolution of 2.5 mm with a non-destructive X-ray fluorescence core scanner (XRF-CS). Calibration and quantification of the XRF-CS intensities was obtained using collision reaction cell inductively coupled plasma quadruple mass spectrometry (CRC-ICP-QMS). CRC-ICP-QMS measurements were carried out on discrete samples at a resolution of 1 cm, after dissolution of 150-mg aliquots with 9 ml HNO3 and 1 ml HF at 220 °C in a microwave system. We compare qualitative XRF-CS and quantitative CRC-ICP-MS data and, however the several sources of variability of the data, develop a robust statistical approach to determine the R (2) and the coefficient of a simple regression model together with confidence intervals. Perfect positive correlations were estimated for Cd, Cr, Pb, Sr, Ti and Zn; high positive correlations for Ba (0.8954), Y (0.7378), Fe (0.7349) and Cu (0.7028); while moderate positive correlations for Ga (0.5951) and Ca (0.5435). With our results, we demonstrate that XRF scanning techniques can be used, together with other well-established geochemical techniques (such as ICP-MS), to produce high-resolution (up to 2.5 mm) quantitative data from ombrotrophic peat bog cores.

  18. Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC-ICP-MS.

    PubMed

    Ščančar, Janez; Berlinger, Balázs; Thomassen, Yngvar; Milačič, Radmila

    2015-09-01

    A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Linear gradient elution from 100% water to 100% 0.7 M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO4(2-) species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO4(2-), MoO4(2-) and WO4(2-) are present and were eluted in sharp chromatographic peaks, while VO4(3-) species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420 s, 320 to 370 s, 300 to 350 s and 240 to 360 s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02 ng Cr mL(-1)), molybdate (0.1 ng Mo mL(-1)), tungstate (0.1 ng W mL(-1)) and vanadate (0.2 ng V mL(-1)). The accuracy of analytical procedure for the determination of chromate was checked by analysis of

  19. Analysis of gold(I/III)-complexes by HPLC-ICP-MS demonstrates gold(III) stability in surface waters.

    PubMed

    Ta, Christine; Reith, Frank; Brugger, Joël; Pring, Allan; Lenehan, Claire E

    2014-05-20

    Understanding the form in which gold is transported in surface- and groundwaters underpins our understanding of gold dispersion and (bio)geochemical cycling. Yet, to date, there are no direct techniques capable of identifying the oxidation state and complexation of gold in natural waters. We present a reversed phase ion-pairing HPLC-ICP-MS method for the separation and determination of aqueous gold(III)-chloro-hydroxyl, gold(III)-bromo-hydroxyl, gold(I)-thiosulfate, and gold(I)-cyanide complexes. Detection limits for the gold species range from 0.05 to 0.30 μg L(-1). The [Au(CN)2](-) gold cyanide complex was detected in five of six waters from tailings and adjacent monitoring bores of working gold mines. Contrary to thermodynamic predictions, evidence was obtained for the existence of Au(III)-complexes in circumneutral, hypersaline waters of a natural lake overlying a gold deposit in Western Australia. This first direct evidence for the existence and stability of Au(III)-complexes in natural surface waters suggests that Au(III)-complexes may be important for the transport and biogeochemical cycling of gold in surface environments. Overall, these results show that near-μg L(-1) enrichments of Au in environmental waters result from metastable ligands (e.g., CN(-)) as well as kinetically controlled redox processes leading to the stability of highly soluble Au(III)-complexes.

  20. Multielemental analysis of purpleback flying squad using high resolution inductively coupled plasma-mass spectrometry (HR ICP-MS).

    PubMed

    Ichihashi, H; Kohno, H; Kannan, K; Tsumura, A; Yamasaki, S I

    2001-08-01

    Forty-four elements were analyzed in 21 tissues of purpleback flying squid, Sthenoteuthis oualaniensis, by high resolution inductively coupled plasma-mass spectrometry (HR ICP-MS) and inductively coupled plasma atomic emission spectrophotometry (ICP-AES). Greater concentrations of V, Fe, Co, Ni, Cu, Ag, Cd, Pb, and Bi were found in liver, pancreas, and ink sac than in other tissues. Ink sac concentrated remarkable levels of Ca and Sr in addition to the above-mentioned elements. Several alkalis, alkaline earth, and rare earth elements preferentially accumulated in muscle. Among the hard tissues, accumulation of V and U in beak, Ni, Zn, and Cd in gladius and Cr in skin was prominent. K, Rb, Cs, Pb, Bi and some transition elements (V, Co, Cu, Zn, Ag, Cd) were significantly (p < 0.05) higher in the livers of adult than in juvenile squids. Sodium, alkaline earth, and rare earth elements were higher in the livers of juveniles than in adult squids.