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Sample records for quadrupole icp-ms optimisation

  1. 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

  2. Compariton of quadrupole ICP-MS and magnetic sector ICP-MS for the analysis of U-Th series isotopes in natural samples

    SciTech Connect

    Shaw, T.J.

    1995-12-01

    Inductively Coupled Plasma Mass Spectrometry (ICP-MS) provides an ideal method for the analysis of refractory elements such as U and Th in natural samples. The excellent sensitivity and relative absence of interferences in the high mass ranges has made the analysis of the more abundant isotopes of uranium and thorium routine. However, the analysis of daughter isotopes such as {sup 230}Th, {sup 231}Pa, and {sup 234}U present more complex problems related to abundance sensitivity, hydride generation and detector dynamic range. Tailing of high abundance isotopes (e.g., {sup 232}Th) into neighboring masses is a problem for measurement of mother daughter pairs in the U-Th series. Detector dynamic range is also a major problem when measuring both high and low abundance isotopes using conventional ion multipliers. This paper considers the relative merits of the current generation of quadrupole ICP-MS and magnetic sector ICP-MS instruments for these analyses.

  3. 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

  4. Uranium isotope measurements by quadrupole ICP-MS for process monitoring of enrichment

    SciTech Connect

    Policke, T.A.; Bolin, R.N.; Harris, T.L.

    1998-12-31

    Historically, uranium isotopic ratio measurements in the nuclear industry have been performed using Thermal Ionization Mass Spectrometry (TIMS); primarily due to the high level of precision that can be achieved. TIMS analysis, however, requires sample purification and intricate sample loading. Quadrupole (low resolution, single detector) inductively coupled plasma--mass spectrometry, Q-ICP-MS, overcomes these disadvantages and is a cost-effective alternative, i.e., in terms of initial capital, maintenance, and operating costs. This paper presents a simple, single standard approach for measuring uranium isotope content in various solid and liquid nuclear materials along with some comparison data of Q-ICP-MS and TIMS. Intensity ratios of {sup 234}U, {sup 235}U, {sup 236}U, and {sup 238}U to total U intensity are produced, providing the enrichment level or percent {sup 235}U. A detailed description of the instrument and data collection parameters are also provided. Optimal precision and accuracy are achieved through the use of a single standard which is closely matched to the enrichment and concentration of the samples. Depending upon the standard chosen, enrichments between depleted and 97% can be quantified. Standard deviations for the major uranium isotopes are typically within 0.02 absolute and at least an order of magnitude lower for the minor U isotope abundances.

  5. 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.

  6. 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.

  7. Determination of trace element concentrations and stable lead, uranium and thorium isotope ratios by quadrupole-ICP-MS in NORM and NORM-polluted sample leachates.

    PubMed

    Mas, J L; Villa, M; Hurtado, S; García-Tenorio, R

    2012-02-29

    This work focuses on the monitoring of the potential pollution in scenarios that involve NORM-related industrial activities (environmental or in-door scenarios). The objective was to develop a method to determine extent and origin of the contamination, suitable for monitoring (i.e. simple, fast and economical) and avoiding the use of too many different instruments. It is presented a radiochemical method that allows the determination of trace element concentrations and 206Pb/207Pb/208Pb, 238U/234U and 232Th/230Th isotope ratios using a single sample aliquot and a single instrument (ICP-QMS). Eichrom UTEVA® extraction chromatography minicolumns were used to separate uranium and thorium in sample leachates. Independent ICP-MS determinations of uranium and thorium isotope ratios were carried out afterwards. Previously a small aliquot of the leachate was used for the determination of trace element concentrations and lead isotope ratios. Several radiochemical arrangements were tested to get maximum performances and simplicity of the method. The performances of the method were studied in terms of chemical yields of uranium and thorium and removal of the potentially interfering elements. The established method was applied to samples from a chemical industry and sediments collected in a NORM-polluted scenario. The results obtained from our method allowed us to infer not only the extent, but also the sources of the contamination in the area. PMID:22230754

  8. Measurement of total Zn and Zn isotope ratios by quadrupole ICP-MS for evaluation of Zn uptake in gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss)

    USGS Publications Warehouse

    Wolf, R.E.; Todd, A.S.; Brinkman, S.; Lamothe, P.J.; Smith, K.S.; Ranville, J.F.

    2009-01-01

    This study evaluates the potential use of stable zinc isotopes in toxicity studies measuring zinc uptake by the gills of brown trout (Salmo trutta) and rainbow trout (Oncorhynchus mykiss). The use of stable isotopes in such studies has several advantages over the use of radioisotopes, including cost, ease of handling, elimination of permit requirements, and waste disposal. A pilot study using brown trout was performed to evaluate sample preparation methods and the ability of a quadrupole inductively coupled plasma mass spectrometer (ICP-MS) system to successfully measure changes in the 67Zn/66Zn ratios for planned exposure levels and duration. After completion of the pilot study, a full-scale zinc exposure study using rainbow trout was performed. The results of these studies indicate that there are several factors that affect the precision of the measured 67Zn/66Zn ratios in the sample digests, including variations in sample size, endogenous zinc levels, and zinc uptake rates by individual fish. However, since these factors were incorporated in the calculation of the total zinc accumulated by the gills during the exposures, the data obtained were adequate for their intended use in calculating zinc binding and evaluating the influences of differences in water quality parameters.

  9. Optimization of the in-situ U-Pb age dating method via LA-Quadrupole-ICP-MS with applications to the timing of U-Zr-Mo mineralization in the Poços de Caldas Alkaline Complex, SE Brazil

    NASA Astrophysics Data System (ADS)

    Takenaka, Lynthener Bianca; Lana, Cristiano; Scholz, Ricardo; Nalini, Herminio Arias, Jr.; de Abreu, Adriana Tropia

    2015-10-01

    The high spatial resolution of the LA-ICP-MS systems allows rapid extraction of vital isotopic information from individual growth zones of minerals. This paper describes in detail the optimization of a relatively inexpensive LA-ICP-MS system consisting of a UV 213 Laser Ablation and a Quadrupole ICP-MS. The results of optimization take into account laser energy, beam diameter, frequency and ICP-MS gas conditions. The optimized conditions were tested for precision and accuracy on a number of well-characterized zircons, commonly used as primary and secondary quality control standards. The acquisition of the U-Pb data is carried out in automated mode (pre-set points) for up to 12 h/day with only minimal operator presence. Individual U-Pb zircon analysis lasts 80 s. The 2σ uncertainties of the standards ranged between 1.4 and 8.2%, and overall their relative deviations ranged from 0.02 to 0.87%. The results are comparable to techniques that use more complex and time-consuming approaches such as LA-MC-ICP-MS and ion-microprobe. We have applied this method to obtain ages of numerous granitoid rocks from the Southern São Francisco Craton and a well-known Archean granitoid of the Kaapvaal Craton, South Africa. We furthermore provide the first results of U-Pb age dating of U-Zr-Mo mineralization in the Poços de Caldas Alkaline Complex, SE Brazil, with a U-Pb age of 85 ± 3 Ma for zircon-bearing hydrothermal veins.

  10. 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.

  11. 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.

  12. ICP-MS Data Analysis Software

    Energy Science and Technology Software Center (ESTSC)

    1999-01-14

    VG2Xl - this program reads binary data files generated by VG instrumentals inductively coupled plasma-mass spectrometers using PlasmaQuad Software Version 4.2.1 and 4.2.2 running under IBM OS/2. ICPCalc - this module is a macro for Microsoft Excel written in VBA (Virtual Basic for Applications) that performs data analysis for ICP-MS data required for nuclear materials that cannot readily be done with the vendor''s software. VG2GRAMS - This program reads binary data files generated by VGmore » instruments inductively coupled plasma mass spectrometers using PlasmaQuad software versions 4.2.1 and 4.2.2 running under IBM OS/2.« less

  13. BROMIDE INTERFERENCE ON ARSENIC AND SELENIUM IN ICP-MS

    EPA Science Inventory

    Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a complex analytical technology with multielement capabilities, wide linear range, and low detection limits. Though the ICP-MS offers many positive advantages, it is necessary that analysts, whether performing drinking wat...

  14. Determination of technetium-99, neptunium-237 and isotopes of thorium in uranyl nitrate solutions from a reprocessing plant, using double-focusing ICP-MS

    SciTech Connect

    Mitterrand, B.; Leprovost, P.; Delaunay, J.; Vian, A.M.

    1998-12-31

    The determination of some radionuclides in uranyl nitrate solutions from a reprocessing plant through chemical or radiochemical methods may be tedious, with poor precision. Quadrupole ICP-MS and, more recently, double-focusing ICP-MS, with high resolution capabilities, have proved to be very efficient tools for such determinations. These improvements will be illustrated by the examples of Technetium-99, Neptunium-237 and Thorium.

  15. 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.

  16. Arsenic speciation in chinese seaweeds using HPLC-ICP-MS and HPLC-ES-MS.

    PubMed

    Van Hulle, Marijn; Zhang, Chao; Zhang, Xinrong; Cornelis, Rita

    2002-05-01

    Three common Chinese edible seaweeds, one brown (Laminaria japonica) and two red (Porphyra crispata and Eucheuma denticulatum), were examined for their total arsenic content. The As species were extracted with yields of 76.4, 69.8 and 25.0%, respectively. Anion-exchange and cation-exchange high-performance liquid chromatography (HPLC) in combination with inductively coupled plasma mass spectrometry (ICP-MS) were used for the separation of the different arsenic species in two of the three seaweed extracts (Laminaria and Porphyra). The main arsenic species in the algal extracts are arseno sugars, although it has been shown that the Laminaria seaweed contains significant amounts of dimethylarsinic acid (DMA). HPLC was coupled with electrospray mass spectrometry (ES-MS) for structural confirmation of the arsenic species. The mass spectrometer settings for the arseno sugars were optimised using standards. The conclusions drawn on the basis of HPLC-ICP-MS were confirmed by the HPLC-ES-MS data. The HPLC-ES-MS method is capable of determining both arseno sugars and DMA in the seaweeds. The unknown compounds seen in the HPLC-ICP-MS chromatogram of Laminaria could not be ascribed to trimethylarsenic oxide or tetramethylarsonium ion. PMID:12081041

  17. 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

    2016-05-01

    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. PMID:27055808

  18. 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

  19. 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.

  20. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2014-11-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionization of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary both can easily be applied to the routine operations of an analytical lab.

  1. Alkali element background reduction in laser ICP-MS

    NASA Astrophysics Data System (ADS)

    Magee, C. W., Jr.; Norris, C. A.

    2015-03-01

    Alkali backgrounds in laser ablation ICP-MS analyses can be enhanced by electron-induced ionisation of alkali contamination on the skimmer cone, reducing effective detection limits for these elements. Traditionally, this problem is addressed by isolating analyses of high-alkali materials onto a designated cone set, or by operating the ICP-MS in a "soft extraction" mode, which reduces the energy of electrons repelled into the potentially contaminated sampling cone by the extraction field. Here we present a novel approach, where we replace the traditional alkali glass tuning standards with synthetic low-alkali glass reference materials. Using this vitreous tuning solution, we find that this approach reduces the amount of alkali contamination produced, halving backgrounds for the heavy alkali elements without any change to analytical procedures. Using segregated cones is still the most effective method for reducing lithium backgrounds, but since the procedures are complimentary, both can easily be applied to the routine operations of an analytical lab.

  2. Measuring sulfur isotopes by multicollector ICP-MS

    NASA Astrophysics Data System (ADS)

    Sessions, A. L.; Adkins, J. F.

    2011-12-01

    The stable isotopes of sulfur have traditionally been measured by converting analytes to SO2, which is then introduced to a gas-source isotope ratio mass spectrometer (IRMS). Recently, we and several other groups have begun measuring S isotopes using a multicollector inductively-coupled plasma mass spectrometer (MC-ICP-MS). The approach offers several advantages, including decreased reliance on preparatory chemical conversion (including combustion) of analytes, greater flexibility of sample introduction, and increased sensitivity. Sulfur is measured as monoatomic S+ ions produced in the plasma source, and can be introduced in a variety of forms including dissolved sulfate or sulfide, or as organosulfur compounds either in solution or in the gas phase. A primary requirement for accurate measurements is resolving isobaric interferences from O2+, which requires a mass analyzer with resolution > 4000. Using a Thermo Neptune system, we document accuracy and precision for δ34S near the shot-noise limit (ie, counting statistics) for both aqueous solutions and gas streams. For samples containing 50 pmol S (as gaseous SF6), this corresponds to ~0.3%; for 50 nmol S (as aqueous SO4) this is ~0.02%. One important application of this new analytical approach is the measurement of S isotopes in volatile and semivolatile organic compounds. No IRMS-based methods for measuring compound-specific S isotopes currently exist. We have demonstrated this capability by coupling a capillary gas chromatograph (GC) directly to the ICP-MS via a heated transfer line. Isotope ratios (δ34S values) are calculated relative to co-injected peaks of SF6 reference gas, in the same manner as is used by GC-combustion-IRMS approaches. As a demonstration of this capability, we measured the δ34S values of individual thiophene isomers separated by GC from a crude oil, which range over 20% for compounds from the same oil. A second application of ICP-MS to sulfur isotopes is the measurement of dissolved

  3. 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.

  4. 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

  5. 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).

  6. Particle analysis of car exhaust by ETV-ICP-MS.

    PubMed

    Lüdke, C; Hoffmann, E; Skole, J; Artelt, S

    1996-06-01

    Particulates of platinum group elements (Pt, Rh, Pd, Ir) emitted in automotive catalyst exhaust were measured down to the pg/m(3) level. Samples were taken from a standard type three-way catalyst equipped gasoline engine, running on a computer controlled dynamometer. Particulates in catalyzed car exhaust were sampled fractionated according to size by using the cascade impactor with separate targets mounted underneath each nozzle. The targets, small flat discs made of pure graphite, were subsequently analyzed by ETV-ICP-MS without any preparatory steps. PMID:15045379

  7. Reduction of Solvent Effect in Reverse Phase Gradient Elution LC-ICP-MS

    SciTech Connect

    Patrick Allen Sullivan

    2005-12-17

    %-35% (simulated) and 8%-32% (actual). Quadrupole (low resolution) and sector field (high resolution) ICP-MS instrumentation were utilized in these studies. Once an AIS pair is determined, quantification studies can be performed. First, an analysis is performed by adding both elements of the AIS pair post-column while performing the gradient elution without sample injection. A comparison of the ratio of the measured intensities to the atomic ratio of the two standards is used to determine a correction factor that can be used to account for the matrix effects caused by the mobile phase. Then, organic and/or biological molecules containing one of the two elements in the AIS pair are injected into the LC column. A gradient method is used to vary the methanol-water mixture in the mobile phase and to separate out the compounds in a given sample. A standard solution of the second ion in the AIS pair is added continuously post-column. By comparing the ratio of the measured intensities to the atomic ratio of the eluting compound and internal standard, the concentration of the injected compound can be determined.

  8. 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 Central

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

    2015-01-01

    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. PMID:26664120

  9. LA-ICP-MS for Pu source identification at Mayak PA, the Urals, Russia.

    PubMed

    Cagno, S; Hellemans, K; Lind, O C; Skipperud, L; Janssens, K; Salbu, B

    2014-02-01

    Information on Pu in environmental samples is traditionally based on the determination of the (240+239)Pu activity via Alpha Spectrometry (AS). A large number of alpha spectrometry sources (planchettes) containing radiochemically separated Pu are therefore stored worldwide and are available for further analyses. These archive samples represent a resource from which valuable information on isotopic composition of alpha emitters including Pu can be obtained. The relative abundances of Pu isotopes can be used to trace specific Pu sources and characterize the relative contributions of different Pu sources in a sample. Thus, in addition to the total (239+240)Pu activity, determination of the (240)Pu/(239)Pu ratio can provide valuable information on the nature of the Pu emitting sources. The Pu isotopic ratios can be determined by mass spectrometry techniques such as Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICPMS) or Accelerator Mass Spectrometry (AMS) that require dissolution and complete destruction of the material deposited on the planchettes. In this study Laser Ablation (LA)-quadrupole-ICP-MS has been employed for the analysis of (239)Pu/(240)Pu ratios from alpha-planchettes prepared from samples originating from the Mayak PA nuclear facility, Russia. The results are compared with data from AMS and show that the (240)Pu/(239)Pu ratios obtained by LA-ICP-MS can be utilized to distinguish weapons-grade Pu from civil reprocessing sources. Moreover, isotope ratio mapping can also be performed across the planchettes, allowing e.g. the visualization of possible inhomogeneities in the Pu-isotope distribution on their surface. Thus, this solid sample technique can be applied to extract additional information from existing archives of samples. PMID:24424783

  10. Biomonitoring of hair samples by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

    NASA Astrophysics Data System (ADS)

    Sela, H.; Karpas, Z.; Zoriy, M.; Pickhardt, C.; Becker, J. S.

    2007-03-01

    An analytical method for determining essential elements (Zn, Fe and Cu) and toxic elements (Cr, Pb and U) on single hair strands by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-SFMS) using a double focusing sector field mass spectrometer was developed. Results obtained directly using LA-ICP-SFMS of hair were compared with those measured by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) of solutions of digested hair samples and the analytical methods were found to agree well. Different quantification strategies for trace element determination in hair samples such as external calibration, standard addition and isotope dilution were compared and demonstrated for uranium. For uranium determination in powdered hair by LA-ICP-MS solution-based calibration was applied by coupling the laser ablation chamber to an ultrasonic nebulizer. The significance of single hair analysis by LA-ICP-SFMS was demonstrated by a case study of a person who changed living environment. Differences in the uranium content observed along the single hair strand correlated with the changes in the level of uranium in drinking water. The uranium concentration in a single hair decreased from 212 to 18 ng g-1 with a change in the uranium concentration in drinking water from 2000 to 30 ng l-1. In addition, measurements of uranium isotope ratios showed a natural isotopic composition throughout the whole period in the drinking water, as well as in the hair samples. This paper demonstrates the potential use of laser ablation ICP-MS to provide measurements on a single hair strand and its potential to become a very powerful tool in hair analysis for biological monitoring.

  11. 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.

  12. 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+). PMID:23052867

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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 76Ge isotope. Both an ultra-low radioactivity background environment and active techniques to abate the residual background are required to reach the background index (of 10-3 counts/keV kg y) at the Qββ. 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

  14. 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. PMID:22265498

  15. 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.

  16. 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. PMID:25724197

  17. 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.

  18. 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

  19. 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. PMID:26895346

  20. Micronebulization for trace analysis of lanthanides in small biological specimens by ICP-MS

    NASA Astrophysics Data System (ADS)

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

    2007-10-01

    This work deals with the development of a mass spectrometric method for the determination of lanthanides (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) at ng g-1 levels in small amounts of biological specimens by inductively coupled plasma-mass spectrometry (ICP-MS) after microwave digestion. Two different systems were investigated for introducing the aqueous solutions of the sample into the plasma: a desolvating system (APEX) with micronebulizer and a nano-volume flow injection system combined with a total consumption nebulizer (DS-5). Both solution introduction systems were used together with a quadrupole ICP mass spectrometer. The performances of the investigated nebulizers were compared to that of the MicroMist nebulizer, which was fitted to a mini cyclonic spray chamber. The solution uptake rate was: 700 [mu]L min-1 for MicroMist, 330 [mu]L min-1 for APEX and 8 [mu]L min-1 for DS-5. By using the APEX and the DS-5 nebulizers the oxides formation rate is reduced compared to MicroMist nebulizer, but to a larger extent by APEX. The relative detection limits for lanthanides ranged from 0.57 to 6.1 ng L-1 and 30 to 170 ng L-1 for the APEX and the DS-5 nebulizer, respectively. The absolute detection limits were in the range of 6.7 to 54 pg for APEX and 3.1 to 7.6 fg for DS-5. The method was applied for lanthanides determination in mussel tissue (BCR 668) and in slugs organs. Good precision and accuracy were obtained with the use of APEX, since the oxide interference is markedly reduced. Slight interference was still observed with the use the DS-5 nebulizer, mainly by Ba oxides. By using the nano-volume flow injection nebulizer, lanthanide determination in small amounts of slug tissue was possible, only requiring 76 nL of digested sample solution into the plasma of ICP-MS.

  1. 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. PMID:23232960

  2. 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

  3. Application of laser microdissection ICP-MS for high resolution elemental mapping in mouse brain tissue: a comparative study with laser ablation ICP-MS.

    PubMed

    Sussulini, Alessandra; Becker, J Sabine

    2015-01-01

    Mapping of elements in biological tissue by laser induced mass spectrometry is a fast growing analytical methodology in life sciences. This method provides a multitude of useful information of metal, nonmetal, metalloid and isotopic distribution at major, minor and trace concentration ranges, usually with a lateral resolution of 12-160 µm. Selected applications in medical research require an improved lateral resolution of laser induced mass spectrometric technique at the low micrometre scale and below. The present work demonstrates the applicability of a recently developed analytical methodology - laser microdissection associated to inductively coupled plasma mass spectrometry (LMD ICP-MS) - to obtain elemental images of different solid biological samples at high lateral resolution. LMD ICP-MS images of mouse brain tissue samples stained with uranium and native are shown, and a direct comparison of LMD and laser ablation (LA) ICP-MS imaging methodologies, in terms of elemental quantification, is performed. PMID:25476347

  4. An exploration hydrogeochemical study at the giant Pebble porphyry Cu-Au-Mo deposit, Alaska, USA, using high-resolution ICP-MS

    USGS Publications Warehouse

    Eppinger, Robert G.; Fey, David L.; Giles, Stuart A.; Kelley, Karen D.; Smith, Steven M.

    2012-01-01

    A hydrogeochemical study using high resolution ICP-MS was undertaken at the giant Pebble porphyry Cu-Au-Mo deposit and surrounding mineral occurrences. Surface water and groundwater samples from regional background and the deposit area were collected at 168 sites. Rigorous quality control reveals impressive results at low nanogram per litre (ng/l) levels. Sites with pH values below 5.1 are from ponds in the Pebble West area, where sulphide-bearing rubble crop is thinly covered. Relative to other study area waters, anomalous concentrations of Cu, Cd, K, Ni, Re, the REE, Tl, SO42− and F− are present in water samples from Pebble West. Samples from circum-neutral waters at Pebble East and parts of Pebble West, where cover is much thicker, have anomalous concentrations of Ag, As, In, Mn, Mo, Sb, Th, U, V, and W. Low-level anomalous concentrations for most of these elements were also found in waters surrounding nearby porphyry and skarn mineral occurrences. Many of these elements are present in low ng/l concentration ranges and would not have been detected using traditional quadrupole ICP-MS. Hydrogeochemical exploration paired with high resolution ICP-MS is a powerful new tool in the search for concealed deposits.

  5. 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. PMID:27334719

  6. Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

    SciTech Connect

    Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.; Farmer, Orville T.

    2006-05-09

    99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samples and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.

  7. Trace element analysis of rough diamond by LA-ICP-MS: a case of source discrimination?

    PubMed

    Dalpé, Claude; Hudon, Pierre; Ballantyne, David J; Williams, Darrell; Marcotte, Denis

    2010-11-01

    Current profiling of rough diamond source is performed using different physical and/or morphological techniques that require strong knowledge and experience in the field. More recently, chemical impurities have been used to discriminate diamond source and with the advance of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) empirical profiling of rough diamonds is possible to some extent. In this study, we present a LA-ICP-MS methodology that we developed for analyzing ultra-trace element impurities in rough diamond for origin determination ("profiling"). Diamonds from two sources were analyzed by LA-ICP-MS and were statistically classified by accepted methods. For the two diamond populations analyzed in this study, binomial logistic regression produced a better overall correct classification than linear discriminant analysis. The results suggest that an anticipated matrix match reference material would improve the robustness of our methodology for forensic applications. PMID:20681965

  8. Low level detection of Cs-135 and Cs-137 in environmental samples by ICP-MS

    SciTech Connect

    Liezers, Martin; Farmer, Orville T.; Thomas, Linda MP

    2009-10-01

    The measurement of the fission product cesium isotopes 135Cs and 137Cs at low femtogram (fg) 10-15 levels in ground water by Inductively Coupled Plasma-Mass Spectrometry ICP-MS is reported. To eliminate the potential natural barium isobaric interference on the cesium isotopes, in-line chromatographic separation of the cesium from barium was performed followed by high sensitivity ICP-MS analysis. A high efficiency desolvating nebulizer system was employed to maximize ICP-MS sensitivity ~10cps/femtogram. The three sigma detection limit measured for 135Cs was 2fg/ml (0.1uBq/ml) and for 137Cs 0.9fg/ml (0.0027Bq/ml) with analysis time of less than 30 minutes/sample. Cesium detection and 135/137 isotope ratio measurement at very low femtogram levels using this method in a ground water matrix is also demonstrated.

  9. [Determination and uncertainty evaluation of microelements in flaxseed by using ICP-MS under two modes].

    PubMed

    Xing, Li; Wang, Mei; Zhao, Feng-Min; Cao, You-Fu; Zhang, Xiao-Yan; Cai, Zhi-Yong

    2014-01-01

    Copper, iron, zinc and manganese in flaxseed were determined by inductively coupled plasma mass spectrometry (ICP-MS). After digestion by microwave-assisted, Cu, Fe, Zn and Mn were analyzed by using Standard and KED modes. In the present study, testing effectiveness of the two modes was compared. On this base, valid determination mode was selected for each of the elements and uncertainty evaluations of the four microelements were explored. According to JJF1059-1999 (Evaluation and Expression of Uncertainty in Measurement), the main influence factors were analyzed one by one. Each of the uncertainties was calculated separately. It was showed that the results of Cu, Fe, Zn and Mn in flaxseed determined by ICP-MS method were satisfactory. At the same time, the results obtained in this work were considered to be valuable as a reference for the evaluation of uncertainty in measurement of Fe, Cu, Zn and Mn with ICP-MS. PMID:24783566

  10. Element-tagged immunoassay with ICP-MS detection: evaluation and comparison to conventional immunoassays

    PubMed Central

    Razumienko, Eva; Ornatsky, Olga; Kinach, Robert; Milyavsky, Michael; Lechman, Eric; Baranov, Vladimir; Winnik, Mitchell A.; Tanner, Scott D.

    2008-01-01

    We have investigated the possibility of using element-tagged antibodies for protein detection and quantification in microplate format using Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and compared the results to conventional immunoassays, such as Enzyme-Linked Immunosorbent Assay (ELISA) and Western blotting. The technique was further employed to detect low levels and measure DNA-binding activity of transcription factor p53 in leukemia cell lysates through its interaction with immobilized oligonucleotides and recognition by element-tagged antibodies. The advantages of ICP-MS detection for routine performance of immunoassays include increased sensitivity, wide dynamic range, minimal interference from complex matrices, and high throughput. Our approach advances the ICP-MS technology and demonstrates its applicability to proteomic studies through the use of antibodies directly labeled with polymer tags bearing multiple atoms of lanthanides. Development of this novel methodology will enable fast and quantitative identification of multiple analytes in a single well. PMID:18456275

  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. ICP-MS-Based Multiplex Profiling of Glycoproteins Using Lectins Conjugated to Lanthanide-Chelating Polymers

    PubMed Central

    Leipold, Michael D.; Herrera, Isaac; Ornatsky, Olga; Baranov, Vladimir; Nitz, Mark

    2009-01-01

    Lectins have been increasingly important in the study of glycoproteins. Here we report a glycoprofiling method based on the covalent attachment of metal-chelating polymers to lectins for use in an ICP-MS-based assays. The labeled lectins are able to distinguish between glycoproteins covalently attached to a microtiter plate and their binding can be directly quantified by ICP-MS. Since each conjugate contains a different lanthanide, the assays can be conducted in a single or multiplex fashion, and may be readily elaborated to many different assay formats. PMID:19072657

  13. 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

  14. 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.

  15. 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. PMID:18969975

  16. 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. PMID:23598013

  17. Potassium stable isotopic compositions measured by high-resolution MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Morgan, L. E.; Lloyd, N. S.; Ellam, R. M.; Simon, J. I.

    2012-12-01

    Potassium isotopic (41K/39K) 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 40K/39K ratio can provide precise values but assume identical 40K/39K ratios (e.g. 0.05‰ (1σ) in [1]); this is appropriate in some cases (e.g. identifying excess 41K) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25‰ precisions (1σ) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as 38ArH+ and 40ArH+ and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2‰ (1σ, 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 41K/39K ratio measurements with 0.07‰ precisions (1σ). 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 41K). Although ICP-MS does not yield accurate 41K/39K 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 41K/39K values can be precisely determined via sample-standard bracketing. As cold plasma

  18. 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

  19. 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

  20. Ultra-trace determination of (90)Sr, (137)Cs, (238)Pu, (239)Pu, and (240)Pu by triple quadruple collision/reaction cell-ICP-MS/MS: Establishing a baseline for global fallout in Qatar soil and sediments.

    PubMed

    Amr, Mohamed A; Helal, Abdul-Fattah I; Al-Kinani, Athab T; Balakrishnan, Perumal

    2016-03-01

    The development of practical, fast, and reliable methods for the ultra-trace determination of anthropogenic radionuclides (90)Sr, (137)Cs, (238)Pu, (239)Pu, and (240)Pu by triple quadruple collision/reaction cell inductively coupled plasma mass spectrometry (CRC-ICP-MS/MS) were investigated in term of its accuracy and precision for producing reliable results. The radionuclides were extracted from 1 kg of the environmental soil samples by concentrated nitric and hydrochloric acids. The leachate solutions were measured directly by triple quadrupole CRC-ICP-MS/MS. For quality assurance, a chemical separation of the concerned radionuclides was conducted and then measured by single quadrupole-ICP-MS. The developed methods were next applied to measure the anthropogenic radionuclides (90)Sr, (137)Cs, (238)Pu, (239)Pu, and (240)Pu in soil samples collected throughout the State of Qatar. The average concentrations of (90)Sr, (137)Cs, (238)Pu, (239)Pu, and (240)Pu were 0.606 fg/g (3.364 Bq/kg), 0.619 fg/g (2.038 Bq/kg), 0.034 fg/g (0.0195 Bq/kg), 65.59 fg/g (0.150 Bq/kg), and 12.06 fg/g (0.103 Bq/kg), respectively. PMID:26736181

  1. Use of ICP/MS with ultrasonic nebulizer for routine determination of uranium activity ratios in natural water

    USGS Publications Warehouse

    Kraemer, T.F.; Doughten, M.W.; Bullen, T.D.

    2002-01-01

    A method is described that allows precise determination of 234U/238U activity ratios (UAR) in most natural waters using commonly available inductively coupled plasma/mass spectrometry (ICP/MS) instrumentation and accessories. The precision achieved by this technique (??0.5% RSD, 1 sigma) is intermediate between thermal ionization mass spectrometry (??0.25% RSID, 1 sigma) and alpha particle spectrometry (??5% RSD, 1 sigma). It is precise and rapid enough to allow analysis of a large number of samples in a short period of time at low cost using standard, commercially available quadrupole instrumentation with ultrasonic nebulizer and desolvator accessories. UARs have been analyzed successfully in fresh to moderately saline waters with U concentrations of from less than 1 ??g/L to nearly 100 ??g/L. An example of the uses of these data is shown for a study of surface-water mixing in the North Platte River in western Nebraska. This rapid and easy technique should encourage the wider use of uranium isotopes in surface-water and groundwater investigations, both for qualitative (e.g. identifying sources of water) and quantitative (e.g. determining end-member mixing ratios purposes.

  2. The production of ultra-high purity single isotopes or tailored isotope mixtures by ICP-MS

    SciTech Connect

    Liezers, Martin; Farmer, Orville T.; Dion, Michael P.; Thomas, Linda MP; Eiden, Gregory C.

    2015-01-01

    We report the development and testing of a simple collector arrangement for a commercial quadrupole ICP-MS that for the first time has been used to produce small quantities of highly enriched (>99.99%) single isotopes, with deposition rates >10 ng/hour. The collector assembly replaces the standard instrument detector allowing for implantation with simultaneous monitoring of the incident ion current. Even under zero bias implant conditions, low energy (<10 eV), ion collection efficiency was observed to be very high ~99%. 151Eu ion currents of 0.1-0.5 nA were collected on a simple, planar foil without resorting to any type of cup configuration. Recovery of the enriched isotope from such foils is much simpler than from a more complex cup configuration. High rejection of adjacent mass isotopes was demonstrated by selectively implanting 167Er without any discernible co-implantation of 166Er and 168Er. The important analytical possibilities of the new approach to isotope ratio measurement, tracer purification and radiation measurements are discussed.

  3. 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

  4. Isotope ratios of uranium using high resolution inductively coupled plasma-mass spectrometry (ICP-MS)

    SciTech Connect

    Hearn, R.; Wildner, H.

    1998-12-31

    Actinide element isotope ratios have been determined in environmental samples using high resolution ICP-MS with ultrasonic nebulization. Precisions as low as 0.1% RSD have been achieved using various methods of acquisition. The methodology has been used for environmental monitoring of uranium isotope ratios as an indicator of nuclear activity. Also, it has been applied to calcite dating studies as a measure of past geochemical disturbances.

  5. Direct determination of halogens in powdered geological and environmental samples using isotope dilution laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Boulyga, Sergei F.; Heumann, Klaus G.

    2005-04-01

    Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) with a special laser ablation system for bulk analyses (LINA-Spark(TM)-Atomiser) was applied for direct determinations of chlorine, bromine, and iodine in rock and sediment samples. Special attention was focused on possible inter-halogen fractionations and analyte/spike isotope fractionations by using LA-ICP-MS and LA-ICP-IDMS, respectively. A variation of Br/Cl and I/Cl element intensity ratios by a factor of 1.3-3 was observed when changing the nebulizer gas flow rate in the range of 0.84-1.0 L min-1 and the laser power density in the range of 2-10 GW cm-2, respectively. When using an internal standard for halogen quantification in LA-ICP-MS, this inter-element fractionation can cause systematic errors, which can be avoided by applying the isotope dilution technique. However, at high laser power densities (>5.7 GW cm-2 for iodine and >4.0 GW cm-2 for bromine and chlorine) the corresponding measured isotope ratio of the isotope-diluted sample deviates significantly from the target value. Under optimised conditions concentrations in the range of 30 [mu]g g-1-16 × 103 [mu]g g-1 for chlorine, <2-140 [mu]g g-1 for bromine, and <0.1-31 [mu]g g-1 for iodine were determined by LA-ICP-IDMS in two sediment reference materials (SRM 1646, SRM 2704) and three rock reference samples (GS-N, Granite; BX-N, Bauxite; DT-N, Disthene), which have not been certified for these halogens. The sediment results agree well within the given uncertainties with indicative values by different methods and the results of the rock samples with those obtained by negative thermal ionisation isotope dilution mass spectrometry. The detection limits of LA-ICP-IDMS are 8 [mu]g g-1 for chlorine, 1.7 [mu]g g-1 for bromine, and 0.1 [mu]g g-1 for iodine.

  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. 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.

  8. Determination of boron isotope ratios and rare earth elements by ETC-ICP-MS

    SciTech Connect

    Richner, P.; Wanner, B.

    1994-12-31

    Matrix modifiers play an important role in ETV-ICP-MS as they do in GF-AAS. In ETV-ICP-MS matrix modifiers, which are used as carriers for the analyte from the furnace to the ICP, enhance both sensitivity and reproducibility. Furthermore, matrix modifiers can be used to bring the element investigated into a specific compound with certain properties. The graphite furnace plays the role of a chemical reactor. In GF-AAS volatile elements are transformed into refractory compounds in order to prevent loss during the ashing stage of the temperature program. In ETV-ICP-MS, refractory elements can be transformed into volatile compounds with the help of matrix modifiers. Both B and the REE`s are known to form refractory compounds such as carbides and oxides which make them difficult to analyze by GF-AAS. However, halides of both B and the REE`s have boiling points below 2000{degrees}C. If these compounds are formed within the furnace the analyte elements can then be effectively transported into the ICP where they will be consequentially atomized and ionized. The technique will be applied to the determination of boron isotope ratios in a tracer study of the boron metabolism in vegetables, using NH4F as a matrix modifier, and the determination of REE`s in geological samples, with CHF{sub 3} as matrix modifier.

  9. 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. PMID:25630637

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

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

    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.

  11. 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.

  12. 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.

  13. Application of a new HPLC-ICP-MS method for simultaneous determination of Al(3+) and aluminium fluoride complexes.

    PubMed

    Zioła-Frankowska, Anetta; Kuta, Jan; Frankowski, Marcin

    2015-10-01

    The paper presents the new HPLC-ICP-MS method used for conducting speciation analysis of aluminum as free Al(3+) and aluminum fluoride complexes during one analysis. In the study, 5% HNO3 was used as a derivative reagent in order to minimize the possibility of clogging the torch in ICP-MS. Using the new HPLC-ICP-MS method, speciation analysis of aluminum and aluminum fluoride complexes was conducted on the basis of model solutions and real samples (soil-water extracts and groundwater samples). The analysis in the presented analytical system lasts only 4 min. PMID:27441221

  14. 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

  15. 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

    2014-09-01

    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

  16. Characterization Of Nuclear Materials Using Time-Of-Flight ICP-MS

    SciTech Connect

    Buerger, Stefan; Riciputi, Lee R; Bostick, Debra A; Duckworth, Douglas {Doug} C

    2006-01-01

    The investigation of illicit trafficking of nuclear materials, nuclear safeguards analysis, and non-proliferation control requires sensitive and isotope-selective detection methods to gain crucial nuclear forensic information like isotope 'fingerprints' and multi-element signatures. The advantage of time-of-flight (TOF) mass spectrometry - quasi-simultaneous multi-mass analysis - combined with an inductively coupled plasma (ICP) ion source provides an analytical instrument with multi-element and multi-isotope capability and good detection limits. A TOF-ICP-MS system thus appears to be an advantageous choice for the investigation and characterization of nuclear materials. We present here results using a GBC OptiMass 8000 time-of-flight ICP-MS for the isotope screening of solid samples by laser ablation and the multi-element determination of impurities in uranium ore concentrates using matrix matched standards. A laser ablation system (New Wave Research, UP 213) coupled to the TOF-ICP-MS instrument has been used to optimize the system for analysis of non-radioactive metal samples of natural isotopic composition for a variety of elements including Cu, Sr, Zr, Mo, Cd, In, Ba, Ta, W, Re, Pt, and Pb in pure metals, alloys, and glasses to explore precision, accuracy, and detection limits. Similar methods were then applied to measure uranium. When the laser system is optimized, no mass bias correction is required. Precision and accuracy for the determination of the isotopic composition is typically 1 - 3% for elemental concentrations of as little as 50 ppm in the matrix, with no requirement for sample preparation. The laser ablation precision and accuracy are within ~10x of the instrumental limits for liquid analysis (0.1%). We have investigated the capabilities of the TOF-ICP-MS for the analysis of impurities in uranium matrices. Matrix matching has been used to develop calibration curves for a range of impurities (alkaline, earth-alkaline, transition metals, and rare

  17. Association of glass fragments by their trace elemental content using ICP-MS and LA-ICP-MS in the analysis scheme

    NASA Astrophysics Data System (ADS)

    Almirall, Jose R.; Montero, Shirly; Furton, Kenneth G.

    2002-08-01

    The importance of glass as evidence of association between a crime event and a suspect has been recognized for some time. 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. The physical and chemical properties of glass can be used to differentiate between possible sources and as evidence of association between two fragments of glass thought to originate from the same source. Refractive index (RI) comparisons have been used for this purpose but due to the improved control over glass manufacturing processes, RI values often cannot differentiate glasses, even if the glass originates from different sources. Elemental analysis methods such as NAA, XRF, ICP-AES, and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) have also been used for the comparison of trace elemental compositions and these techniques have been shown to provide an improvement in the discrimination of glass fragments over RI comparisons alone. 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 methodology for solution analysis (digestion procedure) and solid sample analysis (laser ablation) of glass is reported and the analytical results are compared. An isotope dilution method is also reported as a high precision technique for elemental analysis of glass fragments. The optimum sampling parameters for laser ablation, for semi-quantitative analysis and element ratio comparisons are also presented. Finally, the results of a case involving the breaking of 15 vehicle windows in an airport parking lot and the association of a suspect to the breakings by the glass fragments found on his person are also presented.

  18. 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

  19. Characterization of Silver Nanoparticles Internalized by Arabidopsis Plants Using Single Particle ICP-MS Analysis

    PubMed Central

    Bao, Dongping; Oh, Zhen Guo; Chen, Zhong

    2016-01-01

    Plants act as a crucial interface between humans and their environment. The wide use of nanoparticles (NPs) has raised great concerns about their potential impacts on crop health and food safety, leading to an emerging research theme about the interaction between plants and NPs. However, up to this day even the basic issues concerning the eventual fate and characteristics of NPs after internalization are not clearly delineated due to the lack of a well-established technique for the quantitative analysis of NPs in plant tissues. We endeavored to combine a quantitative approach for NP analysis in plant tissues with TEM to localize the NPs. After using an enzymatic digestion to release the NPs from plant matrices, single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) is employed to determine the size distribution of silver nanoparticles (Ag NPs) in tissues of the model plant Arabidopsis thaliana after exposure to 10 nm Ag NPs. Our results show that Macerozyme R-10 treatment can release Ag NPs from Arabidopsis plants without changing the size of Ag NPs. The characteristics of Ag NPs obtained by SP-ICP-MS in both roots and shoots are in agreement with our transmission electron micrographs, demonstrating that the combination of an enzymatic digestion procedure with SP-ICP-MS is a powerful technique for quantitative determination of NPs in plant tissues. Our data reveal that Ag NPs tend to accumulate predominantly in the apoplast of root tissues whereby a minor portion is transported to shoot tissues. Furthermore, the fact that the measured size distribution of Ag NPs in plant tissue is centered at around 20.70 nm, which is larger than the initial 12.84 nm NP diameter, strongly implies that many internalized Ag NPs do not exist as intact individual particles anymore but are aggregated and/or biotransformed in the plant instead. PMID:26870057

  20. 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.

  1. 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

  2. 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

  3. Dissolution and nanoparticle generation behavior of Be-associated materials in synthetic lung fluid (SLF) using ICP-MS and FFF-ICP-MS

    NASA Astrophysics Data System (ADS)

    Johnson, W. P.; Huang, W.; Fernandez, D.; Rudd, A.; Deubner, D.; Sabey, P.; Larsen, R.; Storrs, J.

    2010-12-01

    Various Be-containing micro-particle suspensions were equilibrated with simulated lung fluid (SLF) to examine their dissolution behavior as well as the potential generation of nanoparticles. The motivation for this study was to explore the relationship between dissolution/particle generation behaviors of Be-containing materials relevant to Be-ore processing, and their epidemiologically-indicated inhalation toxicities. Limited data suggests that BeO is associated with higher rates of beryllium sensitization (BS) and chronic beryllium disease (CBD) relative to the other five relevant materials studied: bertrandite-containing ore, beryl-containing ore, frit (a processing intermediate), Be(OH)2 (a processing intermediate), and silica (control). These materials were equilibrated with SLF at two pH values (4.5 and 7.2) to reflect inter- and intra-cellular environments in lung tissue. Concentrations of Be, Al, and Si in SLF (< 450 nm) increased linearly during the first 20 days of equilibration, and then rose slowly, or in some cases reached a maximum, and subsequently decreased. Relative to the other materials, BeO produced relatively low Be concentration in solution (< 450 nm) at pH 7.2; and relatively high Be concentration in solution at pH 4.5 during the first 20 days of equilibration. For both pH values; however, the Be concentration in SLF (< 450 nm) normalized to Be content of the material was lowest for BeO, demonstrating that BeO was distinct among the four other Be-containing materials in terms of its persistence as a source of Be to the SLF solution. Following 149 days of equilibration, the SLF solutions were fractionated using flow field flow fractionation (FlFFF) with detection via ICP-MS. For all materials, nanoparticles (which were formed during equilibration) were dominantly distributed in the 10-100 nm size range. Notably, BeO produced the least nanoparticle-associated Be mass (other than silica) at both pH values. Furthermore, BeO produced the highest Be

  4. Standards for Quantitative Metalloproteomic Analysis Using Size Exclusion ICP-MS.

    PubMed

    Lothian, Amber; Roberts, Blaine R

    2016-01-01

    Metals are essential for protein function as cofactors to catalyze chemical reactions. Disruption of metal homeostasis is implicated in a number of diseases including Alzheimer's and Parkinson's disease, but the exact role these metals play is yet to be fully elucidated. Identification of metalloproteins encounters many challenges and difficulties. Here we report an approach that allows metalloproteins in complex samples to be quantified. This is achieved using size exclusion chromatography coupled with inductively coupled plasma - mass spectrometry (SEC-ICP-MS). Using six known metalloproteins, the size exclusion column can be calibrated and the respective trace elements (iron, copper, zinc, cobalt, iodine) can be used for quantification. SEC-ICP-MS traces of human brain and plasma are presented. The use of these metalloprotein standards provides the means to quantitatively compare metalloprotein abundances between biological samples. This technique is poised to help shed light on the role of metalloproteins in neurodegenerative disease as well as other diseases where imbalances in trace elements are implicated. PMID:27167680

  5. 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

  6. A lead isotope distribution study in swine tissue using ICP-MS

    USGS Publications Warehouse

    May, T.W.; Wiedmeyer, R.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.

  7. Determination of arsenic species and arsenosugars in marine samples by HPLC-ICP-MS.

    PubMed

    Hirata, Shizuko; Toshimitsu, Hideki

    2005-10-01

    Arsenic-speciation analysis in marine samples was performed by high-pressure liquid chromatography (HPLC) with ICP-MS detection. Separation of eight arsenic species--As(III), MMA, DMA, As(V), AB, TMAO, AC and TeMAs(+)--was achieved on a C(18) column with isocratic elution (pH 3.0), under which conditions As(III) and MMA co-eluted. The entire separation was accomplished in 15 min. The HPLC-ICP-MS detection limits for the eight arsenic species were in the range 0.03-0.23 microg L(-1) based on 3 sigma for the blank response (n=5). The precision was calculated to be 2.4-8.0% (RSD) for the eight species. The method was successfully applied to several marine samples, e.g. oysters, fish, shrimps, and marine algae. Low-power microwave digestion was employed for extraction of arsenic from seafood products; ultrasonic extraction was employed for the extraction of arsenic from seaweeds. Separation of arsenosugars was achieved on an anion-exchange column. Concentrations of arsenosugars 2, 3, and 4 in marine algae were in the range 0.18-9.59 microg g(-1). PMID:16132126

  8. Determination of arsenic species in marine samples by HPLC-ICP-MS.

    PubMed

    Hirata, Shizuko; Toshimitsu, Hideki; Aihara, Masato

    2006-01-01

    Arsenic speciation analysis in marine samples was performed using high performance liquid chromatography (HPLC) with ICP-MS detection. The separation of eight arsenic species viz. arsenite (As(III)), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenate (As(V)), arsenobetaine, trimethylarsine oxide (TMAO), arsenocholine and tetramethylarsonium ion (TeMAs) was achieved on a Shiseido Capcell Pak C18 column by using an isocratic eluent (pH 3.0), in which condition As(III) and MMA were co-eluted. The entire separation was accomplished in 15 min. The detection limits for 8 arsenic species by HPLC/ICP-MS were in the range of 0.02 - 0.10 microg L(-1) based on 3sigma of blank response (n=9). The precision was calculated to be 3.1-7.3% (RSD) for all eight species. The method then successfully applied to several marine samples e.g., oyster, scallop, fish, and shrimps. For the extraction of arsenic species from seafood products, the low power microwave digestion was employed. The extraction efficiency was in the range of 52.9 - 112.3%. Total arsenic concentrations were analyzed by using the microwave acid digestion. The total arsenics in the certified reference materials (DORM-2 and TORT-2) were analyzed and agreed with the certified values. The concentrations of arsenics in marine samples were in the range 6.6 - 35.1 microg g(-1). PMID:16429770

  9. Determination of trace elements in rat organs implanted with endodontic repair materials by ICP-MS.

    PubMed

    Simsek, Neslihan; Bulut, Elçin Tekin; Ahmetoğlu, Fuat; Alan, Hilal

    2016-03-01

    To investigate the levels of seven elements using an inductively coupled plasma-mass spectrometry (ICP-MS) method in rat organs after the implantation of Micro Mega Mineral Trioxide Aggregate (MM-MTA), Bioaggregate (BA) and Biodentine (BD) materials. MM-MTA, BA and BD were implanted into the subcutaneous tissue of 15 Wistar albino rats; three control animals had no operation. After 45 days, the rats were sacrificed and their brains, kidneys and livers were removed. The ICP-MS analysis was used to determine trace elements. Data were analysed using the Kruskal-Wallis and Connover post hoc tests. There was no significant difference between the control groups and the MM-MTA, BA and BD groups according to the concentration of aluminum, calcium, arsenic and lead in the rats' organs. Beryllium was not detected in all tissue samples. Chromium levels of these materials were higher than the control group in brain and kidney samples (P = 0.038 and P = 0.037); magnesium levels were higher than the control group in kidney and liver samples (P = 0.030 and P = 0.008). MM-MTA, BA and BD were nontoxic according to trace element levels in brain, kidney and liver samples of rats. Further investigation is required to understand the systemic effects of these materials. PMID:26758893

  10. Mass spectrometric imaging - Quantification strategies for created bio-images measured by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Draxler, Johannes; Zitek, Andreas; Tschegg, Stefanie; Mingler, Bernhard; Weinberg, Annelie; Prohaska, Thomas

    2014-05-01

    Mass spectrometric imaging (MSI) using laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS) has been an emerging methodology in the analysis of biological matrices. A challenging step is the quantification and data processing to generate quantitative displays (bio-images) by avoiding analytical artefacts derived from image processing. Moreover, the procedure gets more challenging when features to be monitored are in the range or even smaller as compared to the size of the laser spot as the spatial resolution of the laser ablation system typically lies in the µm range (2 - 300 µm spot size). Here, we present the application of LA-ICP-MSI to biological tissues (bones) for the investigation of the distribution of alloying elements in bone material after the implantation of a Mg-based pin into the femur of rats. For the quantification of the elemental content, in-house standards were prepared by co-precipitation of the alloying elements (Mg, Ca, P, Mn, Zn, Zr, and Yb) in a hydroxyapatite matrix. The capability of this quantification approach was validated by comparative measurements of certified reference materials (SRM 1486, pressed into pellets for direct LA-ICP-MS analysis). ArcGIS® was used for the first time as standard tool for the spatially distinct statistical analysis of chemical data in so called "zones of interest".

  11. Standards for Quantitative Metalloproteomic Analysis Using Size Exclusion ICP-MS

    PubMed Central

    Lothian, Amber; Roberts, Blaine R.

    2016-01-01

    Metals are essential for protein function as cofactors to catalyze chemical reactions. Disruption of metal homeostasis is implicated in a number of diseases including Alzheimer's and Parkinson's disease, but the exact role these metals play is yet to be fully elucidated. Identification of metalloproteins encounters many challenges and difficulties. Here we report an approach that allows metalloproteins in complex samples to be quantified. This is achieved using size exclusion chromatography coupled with inductively coupled plasma - mass spectrometry (SEC-ICP-MS). Using six known metalloproteins, the size exclusion column can be calibrated and the respective trace elements (iron, copper, zinc, cobalt, iodine) can be used for quantification. SEC-ICP-MS traces of human brain and plasma are presented. The use of these metalloprotein standards provides the means to quantitatively compare metalloprotein abundances between biological samples. This technique is poised to help shed light on the role of metalloproteins in neurodegenerative disease as well as other diseases where imbalances in trace elements are implicated. PMID:27167680

  12. A chemical mechanism to explain matrix effects in multi-collector ICP-MS

    NASA Astrophysics Data System (ADS)

    Mueller, B.

    2012-12-01

    A chemical mechanism is presented to explain many of the matrix effects observed in multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). It suggests that breakdown products of the ion exchange resins used to remove sample matrix co-elute with samples and subsequently contaminates the uptake tubing and nebulizer of the ICP-MS. The sample path then contains stationary ligands and acts as a mini-column causing memory or carry-over that lead to the observed matrix effects. The minicolumn mechanism is used to explain: variations in sensitivity between samples and standards, variations in sensitivity on the addition of inorganic or organic matrix, changes in mass bias on the addition of matrix elements or column matrix, the coupling of sensitivity changes with mass bias changes, light isotope backgrounds, changes in mass bias with changes in analyte concentration, the poor reproducibility of the matrix effects, the reduction of mass bias with increasing matrix load and variations in mass bias across isotopes of the same element.

  13. [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. PMID:27141662

  14. 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.

  15. 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

  16. The Determination of Metals in Sediment Pore Waters and in 1N HCl-Extracted Sediments by ICP-MS

    USGS Publications Warehouse

    May, T.W.; Wiedmeyer, R.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.

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

    PubMed

    Krzciuk, Karina

    2016-07-01

    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. PMID:26517237

  18. Impact of and correction for instrument sensitivity drift on nanoparticle size measurements by single-particle ICP-MS.

    PubMed

    El Hadri, Hind; Petersen, Elijah J; Winchester, Michael R

    2016-07-01

    The effect of ICP-MS instrument sensitivity drift on the accuracy of nanoparticle (NP) size measurements using single particle (sp)ICP-MS is investigated. Theoretical modeling and experimental measurements of the impact of instrument sensitivity drift are in agreement and indicate that drift can impact the measured size of spherical NPs by up to 25 %. Given this substantial bias in the measured size, a method was developed using an internal standard to correct for the impact of drift and was shown to accurately correct for a decrease in instrument sensitivity of up to 50 % for 30 and 60 nm gold nanoparticles. Graphical Abstract Correction of nanoparticle size measurement by spICP-MS using an internal standard. PMID:26894759

  19. 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.

  20. Clinical applications of HPLC-ICP-MS element speciation: A review.

    PubMed

    Delafiori, Jeany; Ring, Gavin; Furey, Ambrose

    2016-06-01

    Arsenic (As), Selenium (Se) and Mercury (Hg) are three trace elements that have been the subject of much analytical discussion and investigation over the last three decades. While Selenium (Se) is among the list of essential trace elements necessary for the regulation of metabolic processes and overall health, As and Hg are not, and have been the centre of various cases surrounding the contamination of food, water and the environment. The focus of this review is to explore the area of chemical speciation, particularly as it relates to the measurement of these elements in various clinical matrices by HPLC-ICP-MS. This review will highlight the importance of accurately identifying the various chemical species of each of these elements, especially when considering their respective toxicological impacts on human health. PMID:27130123

  1. 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

  2. The Approach to Reducing the Detection Limit for LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Poteshin, S. S.; Sysoev, Alexey A.; Torbotryas, R.

    This work is a part of the RED-100 big project. The aim of the RED-100 experiment is to detect the presently undiscovered coherent neutrino scattering off xenon atomic nuclei. The manufacture of such detectors requires ultrapure materials with very low content of natural radioactive elements. So the pure titanium was selected to assay the uranium and thorium contaminations on 1 ng/g level. In this paper we investigate the possibility of reducing the LOD for LA-ICP-MS analysis by increasing the pulse repetition rate of solid-state laser irradiation up to 4,000 Hz and appropriate adjusting the irradiation power. LODs for U and Th in titanium matrix estimation fell in the sub 10-10 g g- 1 level.

  3. Geographical origin identification of Romanian wines by ICP-MS elemental analysis.

    PubMed

    Geana, Irina; Iordache, Andreea; Ionete, Roxana; Marinescu, Adrian; Ranca, Aurora; Culea, Monica

    2013-06-01

    Trace elemental analysis, besides its ability to determine stable isotopes ratios, represents a possible complementary tool useful to differentiate wines based on their regional origins. Wines and their provenance soils from two major wine producing areas in Southeast Romania ('Valea Calugareasca' and 'Murfatlar'), and also wine from the region of Moldova (Eastern Romania) were analyzed by inductively coupled plasma mass spectrometry (ICP-MS), and statistical data of elemental composition was used to differentiate these wines according to grape type and geographical origin. Moreover, this study gathers relevant elemental trace composition of wines produced in most important Romanian vineyards, thus offering a useful wine differentiation tool by their production district. The results show that the differentiation of Romanian wines according to their provenance is based on the following main elements: Ni, Ag, Cr, Sr, Zn, and Cu for Valea Calugareasca, Rb, Zn, and Mn for Murfatlar, and Pb, Co, and V for Moldova. PMID:23411223

  4. 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.

  5. 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)

  6. 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. PMID:22079960

  7. Fingerprinting of ground water by ICP-MS. Progress report, January 1, 1995--March 31, 1995

    SciTech Connect

    Stetzenbach, K.

    1995-05-01

    This report contains the results of the chemical analysis of water from springs in Ash Meadows National Wildlife Refuge, Nevada. Each spring was sampled two to five times between July, 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. Chemical analyses 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. The concentrations of the analytes range from the part per million (ppm) levels for the major cations and anions to the sub part per trillion (ppt) levels for a number of the trace elements. Approximately nine orders of magnitude are covered from the highest to the lowest concentrations. The formation of molecular species in the ICP-MS, plasma produces false positives for a number of elements. None of the elements reported here, that the HRC is aware of, are subject to these isobaric interferences, with the exception of europium (Eu). Europium values are reported for samplings four and five where the HRC used an extraction procedure that extracted Eu but not barium (Ba), whose oxides cause the interference. In order to overcome matrix effects in the samples from high concentrations of cations and other elements, the method of standard additions was instituted for the analysis of samplings four and five as an alternative to external standardization. It is believed that these data, and those for the Death Valley Spring reported in January, 1995 are the first efforts 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.

  8. 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

  9. Analysis of 34S in Individual Organic Compounds by Coupled GC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Sessions, A. L.; Amrani, A.; Adkins, J. F.

    2009-12-01

    The abundances of 2H, 13C, and 15N in organic compounds have been extremely useful in many aspects of biogeochemistry. While sulfur plays an equally important role in many earth-surface processes, the isotopes of sulfur in organic matter have not been extensively employed in large part because there has been no direct route to the analysis of 34S in individual organic compounds. To remedy this, we have developed a highly sensitive and robust method for the analysis of 34S in individual organic compounds by coupled gas chromatography (GC) and multicollector inductively-coupled plasma mass spectrometry (ICP-MS). Isobaric interference from O2+ is minimized by employing dry plasma conditions, and is cleanly resolved at all masses using medium resolution on the Thermo Neptune ICP-MS. Correction for mass bias is accomplished using standard-sample bracketing with peaks of SF6 reference gas. The precision of measured δ34S values approaches 0.1‰ for analytes containing >40 pmol S, and is better than 0.5‰ for those containing as little as 6 pmol S. External accuracy is better than 0.3‰. Integrating only the center of chromatographic peaks, rather than the entire peak, offers significant gain in precision and chromatographic resolution with minimal effect on accuracy, but requires further study for verification as a routine method. Coelution of organic compounds that do not contain S can cause degraded analytical precision and accuracy. As a demonstration of the potential for this new method, we will present data from 3 sample types: individual organosulfur compounds from crude oil, dimethyl sulfide from seawater, and trace H2S from bacterial culture headspace.

  10. Laser ablation MC-ICP-MS U/Pb geochronology of ocean basement calcium carbonate veins

    NASA Astrophysics Data System (ADS)

    Harris, M.; Coggon, R. M.; Teagle, D. A. H.; Roberts, N. M. W.; Parrish, R. R.

    2014-12-01

    Given the vast areas of mid ocean ridge flanks, even small chemical changes dues to fluid-rock interaction on the flanks may significantly influence global geochemical cycles. A conductive heat flow anomaly associated with hydrothermal circulation in ocean crust exists until on average 65Ma, but it is not known whether the thermal signature is accompanied by continued fluid-rock chemical exchange. Constraining the duration of fluid-rock chemical exchange is critical for calculating robust chemical fluxes associated with ridge flank hydrothermal circulation. Calcium carbonate veins form during relatively late-stage hydrothermal alteration and can be used to estimate the duration of ridge flank hydrothermal circulation. LA-MC-ICP-MS U/Pb geochronology provides a novel and independent approach to date calcium carbonate veins, and is advantageous over using the seawater Sr isotope curve that is in part non-unique and requires assumptions about the contribution of MORB Sr from fluid-rock exchange. LA-MC-ICP-MS U/Pb analyses have been undertaken on a suite of calcium carbonate veins from a range of basement ages (1.6 - 170 Ma), spreading rates and sediment thickness. Preliminary results indicate that the temperature of formation of calcium carbonate veins place a strong control on achieving a successful U/Pb isochron. This is likely related to the temperature dependent geochemical evolution of basement fluids due to fluid-rock reaction, and the partitioning of U and Pb into calcite/aragonite. Successful U/Pb isochrons have been achieved for a range of crustal ages and spreading rates, and indicate that calcium carbonate precipitation occurs within 25Myrs of crustal formation. This is substantially shorter than 65Ma, the average extent of the conductive heat flow anomaly, and will allow for more robust estimates of the contribution of hydrothermal chemical fluxes to global geochemical cycles.

  11. Metal particles produced by laser ablation for ICP-MS measurements.

    PubMed

    Gonzalez, Jhanis J; Liu, Chunyi; Wen, Sy-Bor; Mao, Xianglei; Russo, Richard E

    2007-09-30

    Pulsed laser ablation (266nm) was used to generate metal particles of Zn and Al alloys using femtosecond (150fs) and nanosecond (4ns) laser pulses with identical fluences of 50Jcm(-2). Characterization of particles and correlation with inductively coupled plasma mass spectrometer (ICP-MS) performance was investigated. Particles produced by nanosecond laser ablation were mainly primary particles with irregular shape and hard agglomerates (without internal voids). Particles produced by femtosecond laser ablation consisted of spherical primary particles and soft agglomerates formed from numerous small particles. Examination of the craters by white light interferometric microscopy showed that there is a rim of material surrounding the craters formed after nanosecond laser ablation. The determination of the crater volume by white light interferometric microscopy, considering the rim of material surrounding ablation craters, revealed that the volume ratio (fs/ns) of the craters on the selected samples was approximately 9 (Zn), 7 (NIST627 alloy) and 5 (NIST1711 alloy) times more ablated mass with femtosecond pulsed ablation compared to nanosecond pulsed ablation. In addition, an increase of Al concentration from 0 to 5% in Zn base alloys caused a large increase in the diameter of the particles, up to 65% while using nanosecond laser pulses. When the ablated particles were carried in argon into an ICP-MS, the Zn and Al signals intensities were greater by factors of approximately 50 and approximately 12 for fs versus ns ablation. Femtosecond pulsed ablation also reduced temporal fluctuations in the (66)Zn transient signal by a factor of 10 compared to nanosecond laser pulses. PMID:19073072

  12. Determination of stable and long-lived radioactive halides using high resolution ICP-MS

    SciTech Connect

    Kerl, W.; Hoppstock, K.; Becker, J.S.; Dietze, H.J.

    1996-09-01

    Routine control of radioactive waste demands efficient techniques which allow many samples to be analyzed per day with high precision and accuracy. ICP-MS is well established as a trace analytical method and permits the extremely sensitive and fast detection of stable and long-lived radioactive nuclides. Though ICP-MS is rarely used for the determination of halides, the author`s investigation shows that a sufficient low detection limit can be achieved (e.g., for the declaration of {sup 129}I in radioactive waste samples.). In this work, a double focusing mass spectrometer with an ICP ion source ({open_quotes}ELEMENT{close_quotes}, Finnigan MAT) is used for the determination of halides (Cl, Br and I) in biological standard reference materials as well as {sup 129}I in low-activity radioactive waste samples. A method was developed for the determination of halides in the {mu}g/mL-range for bromine and chlorine and the ng/mL-range for iodine including isotopic analysis of stable and radioactive halides. Possible interferences of atomic ions with other ions (e.g., {sup 129}I{sup +} with {sup 129}Xe{sup +}) were investigated and possibilities for correction of these interferences will be discussed. To achieve a lower detection limit a new method for iodine sample introduction was developed. The iodide ion in an aqueous sample is oxidized to elemental iodine and introduced directly into the ICP by a special introduction system. Iodine ({sup 127}I or {sup 129}I) can be measured by this new method even in the lower ng/mL-range. The studies were extended to include the determination of bromine and chlorine.

  13. Analysis of ceramic layer for solid oxide fuel cells by LA-ICP-MS

    SciTech Connect

    Westheide, J.; Becker, J.S.; Dietze, H.J.; Broekaert, J.A.C.

    1996-09-01

    Among the different analytical techniques, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is well established as a solid-state mass spectrometric method for the trace analysis of conducting and nonconducting material. Furthermore, LA-ICP-MS enables ceramic layers with thickness > few {mu}m and a lateral resolution of >10 {mu}m to be analyzed. In this paper, trace analysis on the ceramic layers of solid oxide fuel cells (SOFC) (e.g., La{sub y{center_dot}x}Sr{sub x}MnO{sub 3}, yttrium-stabilized ZrO{sub 2}) is described. Due to a lack of standard reference materials for the analysis of perovskites, the quantification of analytical results can be facilitated by the use of prepared synthetic standards. The synthetic standard samples were prepared by mixing powdered inorganic compounds of ultra-high-purity (e.g., preparation of a stoichiometric mixture of high-purity La{sub 2}(CO{sub 3}){sub 3}, SrCO{sub 3} and MnO{sub 2} mixed with ultrapure graphite as binder). In order to determine the relative sensitivity coefficients (RSC) or calibration curves elemental spikes (high-purity compounds of 30 elements in the concentration range of 50-2000 ppm) were added to these mixtures. The use of UV laser (frequency-quadrupled Nd:YAG laser) improved the laser ablation process in regard to better reproducibility and accuracy in comparison with an infrared system. Results of quantitative measurements of trace elements of sintered La{sub y{center_dot}x}Sr{sub x}MnO{sub 3} and yttrium-stabilized zirconia layers are presented and compared with those of other methods.

  14. NHEXAS PHASE I MARYLAND STUDY--STANDARD OPERATING PROCEDURE FOR ANALYSIS OF METALS BY ICP-MS (L08)

    EPA Science Inventory

    This SOP describes the analysis of metals by inductively coupled plasma-mass spectrometry (ICP/MS) in environmental samples, namely air filters, soil, dermal wipes, and dust by vacuum. The analysis was carried out in the Trace Metals Laboratory at Harvard School of Public Healt...

  15. 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...

  16. Volatile Element Abundances in Chondrules Revisited: An LA-ICP-MS Study of QUE 97008 (LL3.05)

    NASA Astrophysics Data System (ADS)

    Grossman, J. N.; Alexander, C. M. O'd.; Ash, R. D.; McDonough, W. F.

    2007-03-01

    The interiors of chondrules from QUE 97008 (LL3.05) were analyzed for 36 elements, including Rb, Cs, Bi, Pb, Zn, and Se, by LA-ICP-MS. Even the type I chondrules show only modest depletions in volatiles, constraining models for their formation.

  17. 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

  18. 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

  19. 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

  20. Elemental bioimaging of Cisplatin in Caenorhabditis elegans by LA-ICP-MS

    PubMed Central

    Crone, Barbara; Aschner, Michael; Schwerdtle, Tanja; Karst, Uwe; Bornhorst, Julia

    2015-01-01

    Cis-diamminedichloroplatinum(II) (Cisplatin) is one of the most important and frequently used cytostatic drugs for the treatment of various solid tumors. Herein, a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method incorporating a fast and simple sample preparation protocol was developed for the elemental mapping of Cisplatin in the model organism Caenorhabditis elegans (C. elegans). The method allows imaging of the spatially-resolved elemental distribution of platinum in the whole organism with respect to the anatomic structure in L4 stage worms at a lateral resolution of 5 µm. In addition, a dose- and time-dependent Cisplatin uptake was corroborated quantitatively by a total reflection X-ray fluorescence spectroscopy (TXRF) method, and the elemental mapping indicated that Cisplatin is located in the intestine and in the head of the worms. Better understanding of the distribution of Cisplatin in this well-established model organism will be instrumental in deciphering Cisplatin toxicity and pharmacokinetics. Since the cytostatic effect of Cisplatin is based on binding the DNA by forming intra- and interstrand crosslinks, the response of poly(ADP-ribose)metabolism enzyme 1 (pme-1) deletion mutants to Cisplatin was also examined. Loss of pme-1, which is the C. elegans ortholog of human poly(ADP-ribose) polymerase 1 (PARP-1) led to disturbed DNA damage response. With respect to survival and brood size, pme-1 deletion mutants were more sensitive to Cisplatin as compared to wildtype worms, while Cisplatin uptake was indistinguishable. PMID:25996669

  1. 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. PMID:23195433

  2. Speciation of heavy metals in environmental water by ion chromatography coupled to ICP-MS.

    PubMed

    Ammann, Adrian A

    2002-02-01

    Biogenic (e.g. phytochelatins, porphyrins, DOM) as well as anthropogenic (e.g. NTA, EDTA, phosphonates) chelators affect the mobility and cycling of heavy metals in environmental waters. Since such chelators can form strongly bound anionic heavy metal complexes that are stable and highly mobile, anion-exchange chromatography coupled to ICP-MS was investigated. A narrow bore HPLC system was connected to a micro concentric nebuliser for in-line sample introduction. A new chromatographic procedure based on a synthetic hydrophilic quaternary ammonium anion exchanger in combination with nitrate as a strong eluent anion, and gradient elution, provided high separation selectivity and a large analytical window. Low detection limits (nmol L(-1)) were achieved by on-column matrix removal and sample preconcentration. This allowed the method to be successfully applied to different environmental research areas. In ecotoxicological studies of heavy metal effects on algae low concentrations of metal EDTA complexes were determined in nutrient solutions without interference from high (buffer) salt concentrations. In groundwater, infiltrated by a polluted river, mobile metal EDTA species were observed. In river water of different pollution levels beside CuEDTA other anionic Cu-complexes were found in nmol L(-1) concentrations. PMID:11939532

  3. ICP-MS determination of toxic-metal release from pumping systems for food processing.

    PubMed

    Tubaro, Franco; Barbangelo, Francesco; Toniolo, Rosanna; Di Narda, Francesca; Susmel, Sabina; Bontempelli, Gino

    2002-03-01

    The release of heavy metals from uncovered and nickel-covered brass pumps has been evaluated by ICP-MS analysis in both simple ultrapure water and 3% acetic acid solution (mimic of neutral and acid edible liquids, respectively), following a procedure similar to that recommended by the National Sanitation Foundation (NSF) International, Test Procedure P203. The results found highlight that the main release regards zinc, copper and lead, i.e. the three major metals present in brass alloys. The first contact of brass surfaces with the extraction solvent leads to an extensive Pb release which is comparable with that observed for Cu and Zn. Subsequent washings reduce markedly the Pb release, thus rising in evidence a progressive surface passivation. In particular, the Pb release found after four repeated washings turns out to approach the limit set by both Italian and USA governments for liquids used for food purposes when determined in neutral media, while it remains quite higher when evaluated in acid media. Release analyses conducted on nickel-covered brass pumps point out that the Niploy nickel coating process is very effective for brass surface protection, in that the Pb release is reduced of about three orders of magnitude, but a Ni release exceeding the relevant permitted level is in this case observed. PMID:12025513

  4. Depth profiling (ICP-MS) study of trace metal 'grains' in solid asphaltenes.

    PubMed

    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. PMID:21953195

  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. PMID:27228779

  7. Characterization of selenium species in Brazil nuts by HPLC-ICP-MS and ES-MS.

    PubMed

    Vonderheide, Anne P; Wrobel, Kazimierz; Kannamkumarath, Sasi S; B'Hymer, Clayton; Montes-Bayón, Maria; Ponce De León, Claudia; Caruso, Joseph A

    2002-09-25

    Brazil nuts have been classified as the foodstuffs that contain the highest level of unadulterated selenium, an essential trace element that appears to prevent cancer. To date, characterization of the selenium species in brazil nuts has not yet been investigated. In this work, various sample preparation approaches, including microwave extractions and enzymatic treatments, are examined with the goal of species preservation and subsequent selenium speciation; of these approaches, an enzymatic treatment with Proteinase K proved most effective. High-performance liquid chromatography (HPLC) separation strategies and inductively coupled plasma mass spectrometry (ICP-MS) detection schemes will also be presented. Extracts are evaluated against available standards for the commercially obtainable seleno-amino acids, selenomethionine (SeMet), selenoethionine (SeEt), and selenocystine (SeCys); selenomethionine was demonstrated to be the most abundant of these seleno-amino acids. Further characterization of unidentified selenium-containing peaks is attempted by the employment of several procedures, including electrospray-mass spectrometry (ES-MS). A peptide structure was identified; however, this was considered a tentative proposal due to the large background produced by the extremely complicated brazil nut matrix. PMID:12236705

  8. [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. PMID:19798987

  9. 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

  10. [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. PMID:19123423

  11. 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

  12. U-Th-Pb in petroleum by LA-ICP-MS: Source rocks-crude oils comparison.

    NASA Astrophysics Data System (ADS)

    Gourlan, Alexandra T.; Ricard, Estelle; Prinzhofer, Alain; Christophe, Pecheyran; Donard, Olivier X. C.

    2010-05-01

    The U, Th elemental and Pb isotopic ratios in petroleum source rocks have been determined for the first time and compared with crude oils from different regions in the World using a femtosecond laser ablation (high ablation rates) coupled to an ICP-MS and direct analysis of digested samples on ICP-MS. The advantage of femtosecond compared to nanosecond laser ablation is that it drastically reduces thermal effects, minimizes isotope and elemental fractionation and matrix effects during chemical analysis of solid samples. Fs-Laser Ablation coupled to an ICP-MS is therefore a potentially valuable tool for the determination of trace metals in crude oils as well as in solid samples such as source rocks. The principal problems encountered arise from the lack of isotopic lead standards in organic matrixes and the heterogeneity of source rocks which contain sulphides with high natural U and Th concentrations. Therefore, to determine exactly the U, Th and Pb contents in source rocks, two analytical techniques have to be compared. In one, the use of the laser ablation allows us to analyze in-situ small parts of the organic materials and to determine the proportions of two end members: pure kerogene and pure sulphides. In the other, the use of the conventional dissolution of the same pellets involves total consumption of the sample and gives an average value of the isotopic lead ratios and U, Th and Pb concentrations of the bulk sample. For the two cases a "sample-standard bracketing" procedure was applied using NIST 612 glass standard for ablation and NIST 981 in aqueous solution for the mineralization. Due to the lack of organic matrix standards, the fs-LA-ICP-MS technique produces only qualitative trace element (U, Th and Pb) and isotopic analysis of source rocks. Our results obtained on both crude oils and associated source rocks have shown that Th, U, Pb systematics determined using the two analytical methods (mineralization of kerogen directly analyzed on ICP-MS or MC

  13. Development and Validation of Simultaneous Analysis of Minerals and Toxic Elements in Foods by ICP-MS.

    PubMed

    Yutani, Aiko; Kishi, Eri; Ozaki, Asako; Shinya, Masanao; Ooshima, Tomoko; Yamano, Tetsuo

    2016-01-01

    We have developed and validated an inductively coupled plasma-mass spectrometry (ICP-MS) method for the simultaneous analysis of minerals and toxic elements in foods. Food samples were digested by microwave irradiation to prepare solutions for measurement by ICP-MS. Optimal gas mode and internal standard for each element were selected as appropriate. The method was validated for eighteen elements in total using three certified standard reference materials, namely, Typical Japanese Diet, Rice Flour-Unpolished and Infant/Adult Nutritional Formula, according to the guidelines of the Ministry of Health, Labour and Welfare of Japan. The trueness and precision of the method were all within the acceptable limits, except for Na in Rice Flour-Unpolished. PMID:27211920

  14. 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. PMID:10879843

  15. Routine analysis of ultra pure water by ICP-MS in the low- and sub-ng/L level.

    PubMed

    Hoelzl, R; Fabry, L; Kotz, L; Pahlke, S

    2000-01-01

    The chemical analysis with inductively coupled plasma-mass spectrometry (ICP-MS) can help to examine the purity of ultra pure water (UPW) down to 10 part per trillion (ng/L) and lower. For a proper determination of a high number of samples per week the analysis must be divided into two parts: the routine analysis and the reference water analysis. The routine analysis is done by direct measurement of the ultra pure water samples. Applying a standard addition method under particular clean conditions, the reference water analysis leads to the definition of the accurate zero. A quick evaluation scheme is also presented for the reference water analysis. The method is tested for its fitness for application by examining LOD (for relevant element < 2 ng/L), reproducibility and linearity of calibration. The ICP-MS was optimized according to the methodology of G. Taguchi to improve reproducibility and LOD. PMID:11225818

  16. Validation of Gold and Silver Nanoparticle Analysis in Fruit Juices by Single-Particle ICP-MS without Sample Pretreatment.

    PubMed

    Witzler, Markus; Küllmer, Fabian; Hirtz, Annika; Günther, Klaus

    2016-05-25

    With the increasing use of nanoparticles in consumer products, the need for validated quantitation methods also rises. This becomes even more urgent because the risks of nanomaterials are still not conclusively assessed. Fast, accurate, and robust single-particle (sp) ICP-MS is a promising technique as it is capable of counting and sizing particles at very low concentrations at the same time. Another feature is the simultaneous distinction between dissolved and particulate analytes. The present study shows, for the first time to our knowledge, a method validation for the rapid analysis of silver and gold nanoparticles with sp-ICP-MS in fruit juices without sample preparation. The investigated matrices water, orange juice, and apple juice were spiked with particles and only diluted prior to measurement without using a digestion reagent. The validations regarding particle size are successful according to the German GTFCh's guideline with deviations of accuracy and precision below 15%. PMID:27132879

  17. 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.

  18. Detecting art forgeries using LA-ICP-MS incorporating the in situ application of laser-based collection technology.

    PubMed

    Smith, Kari; Horton, Kristin; Watling, R John; Scoullar, Natalie

    2005-08-15

    The nature of art lends itself to forgery as a skilled and determined forger can mimic the techniques and styles of an artist to a level where even an expert can be duped. The authentication of paintings is a subjective process, but modern techniques may provide the means to provenance artist pigments based on elemental composition. This study applies laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to the analysis of artist paints from different manufacturers to identify variation between the elemental association patterns of these materials. The technique facilitates comparison of the paints used by an artist with produced works of art to assist provenancing initiatives of questioned materials. The effects of the trace element profiles of the backing substrate and binder on analytical data were also identified. By applying the technique to paint scraped from real paintings, a limited database was created to allow comparison to be made with some of Australian artist, Kathleen O'Connor's artworks and assist in determining production chronology. Data from this study were able to facilitate comparison of blue paints from two different paintings and confirm their co-provenance consequently determining the relative production date of a separate painting of previously unknown age. Preliminary trials of a prototype collection device designed to reduce damage and allow for in situ sampling of artworks were also undertaken. The device, which allows direct laser-based sampling of a complete painting, was tested using a Francis Ryan painting. The prototype allows for the collection of debris directly generated by LA-ICP-MS of a predefined area of a painting prior to subsequent analysis using direct LA-ICP-MS. This collection method significantly minimizes the amount of damage produced by conventional sampling methods. Analyses of the debris collected, using the prototype, were found to be comparable to the scrapings of equivalent paint analysed using

  19. 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.

  20. Non-denaturating isoelectric focusing gel electrophoresis for uranium-protein complexes quantitative analysis with LA-ICP MS.

    PubMed

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

    2014-02-01

    A non-denaturating isoelectric focusing (ND-IEF) gel electrophoresis protocol has been developed to study and identify uranium (U)-protein complexes with laser ablation-inductively coupled plasma mass spectrometry (LA-ICP MS) and electrospray ionization mass spectrometry (ESI-MS). The ND-IEF-LA-ICP MS methodology set-up was initiated using in vitro U-protein complex standards (i.e., U-bovine serum albumin and U-transferrin) allowing the assessment of U recovery to 64.4 ± 0.4 %. This methodology enabled the quantification of U-protein complexes at 9.03 ± 0.23, 15.27 ± 0.36, and 177.31 ± 25.51 nmol U L(-1) in digestive gland cytosols of the crayfish, Procambarus clarkii, exposed respectively to 0, 0.12, and 2.5 μmol of waterborne depleted U L(-1) during 10 days. ND-IEF-LA-ICP MS limit of detection was 19.3 pmol U L(-1). Elemental ICP MS signals obtained both in ND-IEF electropherograms and in size exclusion chromatograms of in vivo U-protein complexes revealed interactions between U- and Fe- and Cu-proteins. Moreover, three proteins (hemocyanin, pseudohemocyanin-2, and arginine kinase) out of 42 were identified as potential uranium targets in waterborne-exposed crayfish cytosols by microbore reversed phase chromatography coupled to molecular mass spectrometry (µRPC-ESI-MS/MS) after ND-IEF separation. PMID:23665639

  1. Laser ablation-ICP-MS depth profiling to study ancient glass surface degradation.

    PubMed

    Panighello, Serena; Van Elteren, Johannes T; Orsega, Emilio F; Moretto, Ligia M

    2015-05-01

    In general the analysis of archeological glass represents a challenge for a wide variety of objects because of the presence of physical and/or chemical damage on the surface of the artifact, also known as weathering or corrosion. To retrieve accurate bulk elemental information by laser ablation-inductively coupled plasma-mass spectrometry (ICP-MS), the original, pristine glass needs to be "reached", thereby penetrating the alteration layer which is often more than 10 μm thick. To study this alteration layer the laser was operated in the drilling mode, either with a low (1 Hz) or a high (10 Hz) pulse repetition rate for a period of 50 s yielding detailed spatial information for ca. 20 elements over a shallow depth (ca. 5 μm) or less-detailed spatial information for 50-60 elements over a greater depth (ca. 50 μm). Quantitative elemental depth profiles (in wt%) were obtained with the so-called sum normalization calibration protocol, based on summation of the elements as their oxides to 100 wt%. We were able to associate the increase of SiO2 (in wt%) in the alteration layer to the volumetric mass density change in the glass as a result of depletion of Na2O and K2O. Also the interaction of the number of laser shots with the alteration layer is shown experimentally via depth measurements using profilometry. Chemical and physical changes in four ancient glass artifacts, directly and indirectly measureable by laser drilling, were studied as a function of internal and external factors such as age, composition, and exposure conditions. PMID:25716469

  2. Precise Measurement of Stable Neodymium Isotopes of Geological Materials by Using MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Ma, J.; Wei, G.; Liu, Y.; Ren, Z.; Xu, Y.

    2013-12-01

    A method has developed to determine high-precision high precision stable Nd isotopes in geological materials by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using sample-standard-bracketing (SSB) mode. Nd was pre-concentrated and purifed and through a two column ion-exchange chromatographic procedure, yeilding a recovery of >96% for Nd with the interferences such as Ce and Sm being removed to cause little influence on the stable Nd isotopic compositions. The internal precision for the stable Nd isotopic compositions, ɛ142Nd, ɛ145Nd, ɛ146Nd and ɛ148Nd were generally better than ×0.2 (2SEM: standard error of the mean), and the external precision were generally better than ×0.2 (1SD: standard deviation) for ɛ142Nd, ɛ145Nd and ɛ146Nd, and better than ×0.5 (1SD) for ɛ148Nd estimated by the long-term results of the Nd standard solutions, such as La Jolla, Nd-GIG and NIST 3135a. Such precision id comparable to those by double spike method. Our measured ɛ142Nd, ɛ145Nd, ɛ146Nd and ɛ148Nd results of La Jolla are indentical to those by double spike method winthin analytical error. Thus, our method can provide comparable results for stable Nd isotopes to those by double spike method, but free from the inconvenience of calibrationg double spikes. This provides a more convenient means for studying stabe Nd isotopes in geological processes. By using this method, the stable Nd isotopic compositions for a series of international rock standard references were measured.

  3. [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. PMID:26669139

  4. Metals detected by ICP/MS in wound tissue of war injuries without fragments in Gaza

    PubMed Central

    2010-01-01

    Background The amount and identity of metals incorporated into "weapons without fragments" remain undisclosed to health personnel. This poses a long-term risk of assumption and contributes to additional hazards for victims because of increased difficulties with clinical management. We assessed if there was evidence that metals are embedded in "wounds without fragments" of victims of the Israeli military operations in Gaza in 2006 and 2009. Methods Biopsies of "wounds without fragments" from clinically classified injuries, amputation (A), charred (C), burns (B), multiple piercing wounds by White Phosphorus (WP) (M), were analyzed by ICP/MS for content in 32 metals. Results Toxic and carcinogenic metals were detected in folds over control tissues in wound tissues from all injuries: in A and C wounds (Al, Ti, Cu, Sr, Ba, Co, Hg, V, Cs and Sn), in M wounds (Al, Ti, Cu, Sr, Ba, Co and Hg) and in B wounds (Co, Hg, Cs, and Sn); Pb and U in wounds of all classes; B, As, Mn, Rb, Cd, Cr, Zn in wounds of all classes, but M; Ni was in wounds of class A. Kind and amounts of metals correlate with clinical classification of injuries, exposing a specific metal signature, similar for 2006 and 2009 samples. Conclusions The presence of toxic and carcinogenic metals in wound tissue is indicative of the presence in weapon inducing the injury. Metal contamination of wounds carries unknown long term risks for survivors, and can imply effects on populations from environmental contamination. We discuss remediation strategies, and believe that these data suggest the need for epidemiological and environmental surveys. PMID:20579349

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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).

  10. Do ICP-MS based methods fulfill the EU monitoring requirements for the determination of elements in our environment?

    PubMed

    Tirez, Kristof; Vanhoof, Chris; Bronders, Jan; Seuntjens, Piet; Bleux, Nico; Berghmans, Patrick; De Brucker, Nicole; Vanhaecke, Frank

    2015-12-01

    Undoubtedly, the most important advance in the environmental regulatory monitoring of elements of the last decade is the widespread introduction of ICP-mass spectrometry (ICP-MS) due to standards developed by the European Committee for Standardization. The versatility of ICP-MS units as a tool for the determination of major, minor and trace elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, P, Pb, Sb, Se, Sn, Ti, V and Zn) in surface water, groundwater, river sediment, topsoil, subsoil, fine particulates and atmospheric deposition is illustrated in this paper. Ranges of background concentrations for major, minor and trace elements obtained from a regional case study (Flanders, Belgium) are summarized for all of these environmental compartments and discussed in the context of a harmonized implementation of European regulatory monitoring requirements. The results were derived from monitoring programs in support of EU environmental quality directives and were based on a selection of (non-polluted) background locations. Because of the availability of ICP-MS instruments nowadays, it can be argued that the main hindrance for meeting the European environmental monitoring requirements is no longer the technical feasibility of analysis at these concentration levels, but rather (i) potential contamination during sampling and analysis, (ii) too limited implementation of quality control programs, validating the routinely applied methods (including sampling and low level verification) and (iii) lack of harmonization in reporting of the chemical environmental status between the individual member states. PMID:26487336

  11. LA-ICP-MS-derived U-concentrations and microstructural domains within biogenic aragonite of Arctica islandica shell.

    PubMed

    Helama, Samuli; Heikkilä, Pasi; Rinne, Katja; Nielsen, Jan Kresten; Nielsen, Jesper Kresten

    2015-05-01

    Understanding of the uranium uptake processes (both in vivo and post-mortem) into the skeletal structures of marine calcifiers is a subject of multi-disciplinary interest. U-concentration changes within the molluscan shell may serve as a paleoceanographic proxy of the pH history. A proxy of this type is needed to track the effects of fossil fuel emissions to ocean acidification. Moreover, attaining reliable U-series dates using shell materials would be a geochronological breakthrough. Picturing the high-resolution changes of U-concentrations in shell profiles is now possible by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Here, we analyzed in situ U-concentration variations in sub-fossilized shells of ocean quahog (Arctica islandica), a commonly studied bivalve species in Quaternary geoscience, using LA-ICP-MS. Microstructural details of the shell profiles were achieved by the scanning electron microscopy (SEM). Comparison of the shell aragonite microstructure with the changes in U-concentration revealed that uranium of possibly secondary origin is concentrated into the porous granular layers of the shell. Our results reinforce the hypothesis that U-concentration variations can be linked with microstructural differences within the shell. A combination of LA-ICP-MS and SEM analyses is recommended as an interesting approach for understanding the U-concentration variations in similar materials. PMID:25877646

  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. [Research and Application of the ICP-MS Detection Technology for the Content of Nb and Ta in Geochemical Sample].

    PubMed

    Li, Zi-qiang; Li, Xiao-ying; Zhu, Kun; Xu, Xiao-xia; Yan, Zhi-yuan

    2015-08-01

    In order to provide the test analysis technology to support the exploration and development of niobium and tantalum resource, based on the special chemical properties of Nb and Ta in geochemical sample, we studied the detection methods for the content of Nb and Ta in geochemical sample by using inductively coupled plasma mass spectrometry (ICP-MS). The results show that the sample dissolution and instrumental parameter of ICP-MS, especially the former have significant influence? on detection results. Therefore, optimizing important parameters of sample dissolution is the key of the detection technology. The optimal parameters are that the weight of sample is 50 mg; the dosage of HF acid is 15 mL; the concentration of nitric acid and tartaric acid in the sample solution is 2% and 1.5%, respectively; the validity period of detection for sample solution ≤1 d. The detection method has been validated by the national geochemistry standard reference material. The precise and exaction of method meet the required of industry standards. The detection limits of method for Nb and Ta are 1.05 and 0.13 μg · g(-1), respectively. The experiment proved that the ICP-MS detection methods, which using certain preparation process of sample solutions, is suitable for accurate and rapid determination of Nb and Ta in geochemical sample, especially geochemical survey samples which with a large amount and low content of Nb and Ta. PMID:26672313

  15. 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. PMID:26347937

  16. 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. PMID:17111103

  17. High-Resolution Mg/Ca and Sr/Ca Records from Protothaca staminea Mollusc Shells Using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

    NASA Astrophysics Data System (ADS)

    Takesue, R. K.; van Geen, A.

    2001-12-01

    High resolutions records of past nearshore temperature, salinity, and nutrient enrichments at mid-latitudes would be valuable for reconstructing past changes in climate affecting coastal areas (e.g. changes in precipitation, the nature of wind-driven coastal upwelling or the El Niño-Southern Oscillation (ENSO)). We present here a potential archive of such records in growth-banded mollusc shells. The potential paleo-temperature proxy Mg/Ca, as well as Sr/Ca and stable isotopes (δ 18O, δ 13C) were measured in shells of the clam Protothaca staminea. This bivalve appears favorable for nearshore paleoclimate reconstructions because it occurs over a wide geographic range (Alaska to central America), grows for nearly 10 years, and is present in archeological and geological deposits. P. staminea shells were obtained from a tidal flat in Humboldt Bay, CA (40.8° N; modern), and from the Duncan's Point Cave shell midden (CA Dept. Parks and Recreation site SON-348/H) near Bodega Bay, CA (39.6° N; ~3,000 and ~9,000 cal yr BP). High-resolution (monthly to weekly) Mg/Ca and Sr/Ca measurements were made by (UV Excimer) laser-ablation inductively-coupled plasma (quadrupole) mass spectrometry (LA-ICP-MS) using a spot size of 90 μ m and sample spacing ranging from 100 to 300 μ m. The rapidity of LA-ICP-MS analysis made it possible to analyze a 4 cm-long section of shell within 1 day. Absolute scales for the Mg/Ca and Sr/Ca LA-ICP-MS records were obtained from shell powders drilled with a 0.5 or 0.7 mm burr then dissolved and analyzed by flame atomic absorbtion. Stable isotopes were measured on splits of the shell powders. The Mg/Ca record during the final four years of shell growth in the Humboldt Bay shell shows a regular seasonal pattern with highest values (3.5 mmol/mol) during summer and lowest values (2.5 mmol/mol) during winter corresponding to a nearshore climatological temperature range of 6° C. An abrupt shift in shell Mg/Ca values toward the end of each year

  18. 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

  19. 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

  20. 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

  1. High resolution minor and trace element measurements for mussel shells using LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Bian, N.; Paradis, G.; Martin, P. A.; Pfister, C. A.

    2011-12-01

    The successively deposited calcium carbonate layers in mollusk shells could offer high resolution archives of the environmental conditions the mollusk has experienced during its life. Previous studies have shown that the elemental composition of mollusk shells is related to environmental parameters. Understanding the high resolution environmental conditions recorded in the mollusk shells requires a reliable high resolution analytical method of the trace and minor element composition in the shells. In this study, we investigated three methods using different instrumental configurations to generate high resolution records/time series of a suite of minor/ trace elements in mussel shells (Mytilus californianus) using laser ablation sector field inductively coupled plasma mass spectrometry (LA-ICP-MS) and compared their advantages and disadvantages. The three methods include running the ablated sample with dry plasma, running the ablated sample with diluted nitric acid blank solution and running the ablated sample with spiked solution. We concluded that running the ablated material with the spiked solution could yield the most reproducible signal and accurate data for Mg/Ca, Sr/Ca, Ba/Ca, La/Ca, Ce/Ca and Nd/Ca. To better understand the features of the laser ablation analytical method, we did a series of tests, such as scanning at different speeds, different directions, and applying different sampling strategies and explored the possible complications that could be encountered in using the laser ablation analytical method. In addition, we compared the results from the micromilled samples analyzed by the solution based method to the those obtained from the laser ablation method. Our results demonstrate that applying the slow ablation speed and simultaneously introducing the spiked solution (i.e. along with the ablated sample in the He carrier gas) could yield high resolution and reproducible time series of element/Ca ratios throughout the life span of the mussel. An

  2. [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. PMID:26978935

  3. On-line Sulfur Isotope Determination by Hydride Generation coupled to MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Callac, Nolwenn; Rouxel, Olivier; Ponzevera, Emmanuel; Godfroy, Anne

    2010-05-01

    In seafloor hydrothermal systems, Sulfur is an important element present in various forms such as sulfate, elemental sulfur or sulfide in hydrothermal fluids and pore waters. Sulfur, as either electron donor or acceptor, is one element that enables support for microbial life in the deep biosphere. Traditionally, measurements of 34S/32S ratios (δ34S) are performed using gas-source mass spectrometry (GS-MS) in which sulfur is introduced as gaseous SO2 or SF6 species. We recently developed an alternate technique for the accurate and precise determination of 34S/32S ratios in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) (Craddock et al, 2008; Chemical Geology 253 p102-113). We examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. In particular, the use of high resolution sector-field mass spectrometry has been shown to remove major isobaric interferences from O2+ while standard-sample bracketing allowed the correcting instrumental mass bias of unknown samples. Here, we evaluate a new method for the direct determination of S isotope in environmental samples using on-line generation of hydrogen sulfide coupled to MC-ICPMS. It is expected that the introduction of volatile S-species in the plasma torch will lower the minimum amounts of S required per analysis by more than 1 order of magnitude while permitting matrix-free isotope analysis. An important aim of this study was to determine optimal procedures to overcome analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and isotope fractionation induced during hydrogen sulfide generation. We initially applied this method to investigate the diversity of sulfur isotope fractionations during microbial sulfur-reducing or sulfate-reducing at

  4. Element-tracing of mineral matters in Dendrobium officinale using ICP-MS and multivariate analysis.

    PubMed

    Zhu, Nannan; Han, Shen; Yang, Chunning; Qu, Jixu; Sun, Zhirong; Liu, Wenjie; Zhang, Xiaomin

    2016-01-01

    Rare studies have been performed to trace the mineral elements in Dendrobium officinale. In this study, we aim to trace the mineral elements in D. officinale collected from ten geographical locations in China. ICP-MS system was used for simultaneous determination of mineral elements. Principal component analysis was performed using the obtained data in the quantification of mineral contents. Cluster analysis was performed using the Ward's method. Several of essential microelments were detected in D. officinale, including ferrum (Fe), manganese (Mn), zinc (Zn), chromium (Cr), nickel (Ni) and vanadium (V). Among these elements, three elements (i.e. Fe, Mn and Zn) were highly and simultaneously detected in the D. officinale collected from the ten locations. The level of Ni was positively associated with that of Zn (r = 0.986, P < 0.01). The level of titanium (Ti) was positively associated with that of V (r = 0.669, P < 0.05), and negatively associated with Cr (r = -0.710, P < 0.05). In addition, the level of Mn was positively associated with that of barium (r = 0.749, P < 0.05). Further, the level of Fe was positively associated with that of Ni (r = 0.664, P < 0.05), Zn (r = 0.742, P < 0.05), and rare earth elements (r = 0.847, P < 0.01), respectively. Three eigenvalues explained about 86.60 % of the total variance, which contributed significantly to the explanation of cumulative variance. Cluster analysis indicated the cultivars were categorized into 3 clusters. Ni, Zn, Fe, Cr, Ti and rare earth elements were designated as the characteristic elements. Cultivars collected from Yulin, Menghai, and Shaoguan ranked the top 3 in the comprehensive scores, indicating the content of the mineral elements was comparatively higher in these locations. PMID:27429889

  5. 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.

  6. [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. PMID:19248525

  7. [Determination of trace elements in waste beer yeasts by ICP-MS with microwave digestion].

    PubMed

    Cheng, Xian-zhong; Jin, Can; Zhang, Kai-cheng

    2008-10-01

    The waste beer yeast has rich nutritional compositions and is widely used in food, medical and forage industries. The security of the yeast plays an important role in everyone's daily life. But the yeast contanining microamount of lead, cadmium, chromium, arsenic and other harmful metals is endangering human health. A new method was developed for the direct determination of eight elements, namely copper, lead, zinc, iron, manganese, cadmium, chromium and arsenic in waste beer yeast by inductively coupled plasma-mass spectrometry (ICP-MS) with microwave digestion. The parameters of plasma system, mass system, vacuum system and spectrometer system were optimized. The spectral interferences were eliminated by selecting alternation analytical isotopes of 65Cu, 208Pb, 66Zn, 57Fe, 55Mn, 114Cd, 52Cr and 5As, and the internal standards of Rh was selected to compensate the drift of analytical signals. The samples were digested with concentrated nitric acid-hydrogen peroxide (2:1) mixed solution more rapidly and more effectively. The effects of the type of mixed acid , the volume of digesting solution, heating time, and heating power were investigated in detail. In the closed system, the complete digestion was performed using 4 mL HNO3 and 2mL H2O2 for 2.0 min at 0.5 MPa, 3 min at 1.0 MPa and 5 min at 1.5 MPa. The detection limits of these eight elements were 0.013-0.122 microg x L(-1). The relative standard deviation (RSD) was 0.94%-3.26% (n=9), and the addition standard recovery was 98.4%-102.6% for all elements. The proposed method has been applied to the determination of trace elements of Cu, Pb, Zn, Fe, Mn, Cd, Cr and As in waste beer yeast samples with satisfactory results. The determination results indicated that the content of trace elements of Cu, Pb, Cd and As in waste beer yeast samples are significantly low. PMID:19123421

  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, S.

    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. Tabs, figs, refs.

  9. 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. PMID:25640124

  10. Can we trust mass spectrometry for determination of arsenic peptides in plants: comparison of LC-ICP-MS and LC-ES-MS/ICP-MS with XANES/EXAFS in analysis of Thunbergia alata.

    PubMed

    Bluemlein, Katharina; Raab, Andrea; Meharg, Andrew A; Charnock, John M; Feldmann, Jörg

    2008-04-01

    The weakest step in the analytical procedure for speciation analysis is extraction from a biological material into an aqueous solution which undergoes HPLC separation and then simultaneous online detection by elemental and molecular mass spectrometry (ICP-MS/ES-MS). This paper describes a study to determine the speciation of arsenic and, in particular, the arsenite phytochelatin complexes in the root from an ornamental garden plant Thunbergia alata exposed to 1 mg As L(-1) as arsenate. The approach of formic acid extraction followed by HPLC-ES-MS/ICP-MS identified different As(III)-PC complexes in the extract of this plant and made their quantification via sulfur (m/z 32) and arsenic (m/z 75) possible. Although sulfur sensitivity could be significantly increased when xenon was used as collision gas in ICP-qMS, or when HR-ICP-MS was used in medium resolution, the As:S ratio gave misleading results in the identification of As(III)-PC complexes due to the relatively low resolution of the chromatography system in relation to the variety of As-peptides in plants. Hence only the parallel use of ES-MS/ICP-MS was able to prove the occurrence of such arsenite phytochelatin complexes. Between 55 and 64% of the arsenic was bound to the sulfur of peptides mainly as As(III)(PC(2))(2), As(III)(PC(3)) and As(III)(PC(4)). XANES (X-ray absorption near-edge spectroscopy) measurement, using the freshly exposed plant root directly, confirmed that most of the arsenic is trivalent and binds to S of peptides (53% As-S) while 38% occurred as arsenite and only 9% unchanged as arsenate. EXAFS data confirmed that As-S and As-O bonds occur in the plants. This study confirms, for the first time, that As-peptides can be extracted by formic acid and chromatographically separated on a reversed-phase column without significant decomposition or de-novo synthesis during the extraction step. PMID:18084749

  11. Quantification of Melt Inclusion Chemistry by LA-ICP-MS, EMP and SIMS: Advantages and Possible Limitations of Either Method

    NASA Astrophysics Data System (ADS)

    Pettke, T.; Halter, W. E.; Aigner-Torres, M.; Heinrich, C. A.

    2002-05-01

    Laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICP-MS) has unique advantages for chemical analysis of melt inclusions (MI), because it allows bulk compositional reconstitution of heterogeneous (crystallized) MI without prior thermal homogenization. Quantification is possible even if chemically complex minerals such as plagioclase or amphibole host the MI. We have analyzed glassy MI in plagioclase in one sample using EMP, SIMS (exposed MI) and 193 nm ArF Excimer LA-ICP-MS (unexposed MI), and rigorously compared the results in order to test the analytical accuracy of the data obtained by the various methods. We used a basalt sample, ALV-3352-7 (MORB from the East Pacific Rise, 17 - 19° S, STOWA cruise) with plagioclase phenocrysts ( ~10 vol-%, An82) in a glassy matrix. Plagioclase contains abundant glassy MI (10 - 300 μ m) some of which show a shrinkage bubble. The plagioclase phenocrysts, the matrix glass and the MI are chemically uniform. For the matrix glass, major element analyses by EMP ( ~0.1 to 50 wt-%) and trace-element analyses by SIMS ( ~2 to 100 ppm) are in excellent agreement (+/- 3% RSD on average) with LA-ICP-MS results obtained with a single 40-element menu. This demonstrates analytical accuracy of the three methods. Using MgO or FeO analyses from EMP of exposed MI as an internal standard for the quantification of LA-ICP-MS data of unexposed MI provides identical composition, hence the numerical re-integration of inlcusion compositions (Halter et al., 2002, Chem. Geol. 183, 63-86) is also accurate. Careful evaluation of the EMP data of exposed MI and matrix glass demonstrates significant chemical differences between the two; the glass in the MI apparently fractionated more plagioclase than did the matrix glass. Using MgO of the matrix glass as an internal standard for the quantification of MI analyzed by LA-ICP-MS (i.e., assuming that the MI and the matrix glass originally contained the same MgO concentration) indicates that

  12. High-resolution analysis of trace elements in encrusting coralline red algae by laser ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Hetzinger, S.; Halfar, J.; Zack, T.; Simon, K.; Kronz, A.; Adey, W.; Lebednik, P. A.; Steneck, R. S.; Schöne, B. R.

    2009-04-01

    Coralline red algae constitute an ideal biogenic marine climate recorder owing to their common occurrence in mid- to high latitude oceans and their continuous growth. Encrusting coralline red algae have great potential as paleoclimate archives because they deposit spatially fixed annual growth increments in a high Mg-calcite skeleton and can reach ages of up to several hundred years. Here we present high-resolution Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) trace elemental analyses (Mg, Sr, Ba, U) from several coralline red algal specimens of the genus Clathromorphum, collected from the North Atlantic and North Pacific Oceans, that display average growth rates of around 300 m/year. Elemental ratios (Mg/Ca, Sr/Ca, Ba/Ca, U/Ca) were measured in sub-monthly resolution for up to 65-year long segments of coralline red algal growth. Several overlapping transects were analyzed in order to assess the robustness of the proxy data. The reproducibility is excellent and LA-ICP-MS measured Mg/Ca ratios were validated by comparison to electron microprobe data. In addition, data accuracy was tested by comparison to solution ICP-OES data from a bulk sample manually removed parallel to the laser ablation and electron microprobe transects. In particular, algal Mg/Ca ratios show a high degree of correlation with local seawater temperature on different timescales, providing further evidence for the temperature dependency of algal Mg/Ca variations and their use as a valuable paleothermometer. Hence, this study demonstrates the feasibility of extracting high-resolution geochemical signals from encrusting coralline red algae (such as Clathromorphum sp.) using laser ablation ICP-MS. This analysis technique allows rapid continuous sampling of the algal surface with unprecedented resolution and provides a valuable tool for future analysis of algal-derived environmental records.

  13. High-resolution Analysis of Trace Elements in Encrusting Coralline Red Algae by Laser Ablation ICP-MS

    NASA Astrophysics Data System (ADS)

    Hetzinger, S.; Halfar, J.; Zack, T.; Simon, K.; Kronz, A.; Adey, W.; Lebednik, P. A.; Steneck, R. S.; Schoene, B. R.

    2009-05-01

    Coralline red algae constitute an ideal biogenic marine climate recorder owing to their common occurrence in mid- to high latitude oceans and their continuous growth. Encrusting coralline red algae have great potential as paleoclimate archives because they deposit spatially fixed annual growth increments in a high Mg-calcite skeleton and can reach ages of up to several hundred years. Here we present high-resolution Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) trace elemental analyses (Mg, Sr, Ba, U) from several coralline red algal specimens of the genus Clathromorphum, collected from the North Atlantic and North Pacific Oceans, that display average growth rates of around 300µm/year. Elemental ratios (Mg/Ca, Sr/Ca, Ba/Ca, U/Ca) were measured in sub-monthly resolution for up to century-long segments of coralline red algal growth. Several overlapping transects were analyzed in order to assess the robustness of the proxy data. The reproducibility is excellent and LA-ICP-MS measured Mg/Ca ratios were validated by comparison to electron microprobe data. In addition, data accuracy was tested by comparison to solution ICP-OES data from a bulk sample manually removed parallel to the laser ablation and electron microprobe transects. In particular, algal Mg/Ca ratios show a high degree of correlation with local seawater temperature on different timescales, providing further evidence for the temperature dependency of algal Mg/Ca variations and their use as a valuable paleothermometer. Hence, this study demonstrates the feasibility of extracting high-resolution geochemical signals from encrusting coralline red algae (such as Clathromorphum sp.) using laser ablation ICP-MS. This analysis technique allows rapid continuous sampling of the algal surface with unprecedented resolution and provides a valuable tool for future analysis of algal-derived environmental records.

  14. Determination of cadmium in food samples by ID-ICP-MS with solid phase extraction for eliminating spectral-interferences.

    PubMed

    Zhu, Yanbei; Chiba, Koichi

    2012-02-15

    A solid phase extraction (SPE) method using chelating resin was developed to separate Cd from spectral-interferences prior to the analysis of food samples by isotope-dilution inductively coupled plasma mass-spectrometry (ID-ICP-MS). Two syringe-driven chelating columns (SDCCs), Nobias Chelate PB-1M and InertSep ME-1, were investigated in the present experiment. The results of the pH dependence of Mo removal rates showed that separation of Cd and Mo could be obtained at pH conditions over 7. In addition, 0.6 mL of NH(4)OH solution added into each 10 mL of digested sample solution (in 0.3M HNO(3)) followed by SPE was enough to remove the interfering elements, i.e. Mo, Zr, and Sn, in ID-ICP-MS analysis of Cd. Furthermore, it was found that InertSep ME-1 was more effective for separating Cd from the interfering elements, with removal rates approximately 100% for Mo, Zr, and Sn while the recovery of Cd was approximately 100%. The optimized SPE operations were as follows: 0.6 mL of NH(4)OH was added into each 10 mL of digested sample solution; the sample solution was loaded into each pre-cleaned SDCCs at a flow rate of 5 mL min(-1); after 5 mL of ultrapure water was passed through the SDCC for washing, 2 mL of 0.3M HNO(3) was passed through to elute Cd and the eluent was subjected to ICP-MS measurement. The present method was validated by analyzing five certified reference materials (CRMs) produced by the National Metrology Institute of Japan (NMIJ), and then was applied to a soybean powder sample. PMID:22340116

  15. Simultaneous multielement analysis of Saudi Arabian petroleum by microemulsion inductively coupled plasma mass spectrometry (ICP/MS)

    SciTech Connect

    Al-Swaidan, H.M. )

    1994-01-01

    Traces of Pb, Cu, Cd, Zn, Fe and Co are determined by ICP/MS in Saudi Arabian crude oil from four different producing fields. A microemulsion procedure for sample pretreatment and standard addition method using oil soluble salts of trace elements are applied. Accuracy and precision data showed percentage relative standard deviation to be less than 5% and percentage recovery values ranging from 97-102.5% for all trace metals. The microemulsion as sample pretreatment proved to be a better technique in comparison to other sample introduction methods. 10 refs., 5 tabs.

  16. 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. PMID:22608453

  17. 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

  18. Characterisation of bhringaraj and guduchi herb by ICP-MS analysis, optical absorption, infrared and EPR spectroscopic methods

    NASA Astrophysics Data System (ADS)

    Reddy, S. Lakshmi; Fayazuddin, Md.; Reddy, N. C. G.; Ahmad, Adeel; Reddy, G. Siva; Rao, P. Sambasiva; Reddy, B. Jagannatha; Frost, R. L.

    2008-11-01

    Leaves of bhringaraj and guduchi herb of Kadapa district of Andhra Pradesh, India, are dried and powdered. ICP-MS analysis of samples indicates that copper is present in both the samples. An EPR study of guduchi sample also confirms the presence of Fe(III) whereas Eclipta alba confirms the presence of Fe(III), Mn(II) and Cu(II). Optical absorption spectrum of guduchi indicates that Cu(II) is present in rhombically distorted octahedral environment. NIR and IR results are due to carbonate fundamentals.

  19. Geolaser probe - a versitile laser ablation system for the direct analysis of geological materials by ICP-MS

    SciTech Connect

    Zhu, J.J.; Brenner, I.B.

    1995-12-31

    A description will be given of a new laser ablation system, The CETAC LSX-100, designed specifically for geoanalysis using ICP-MS. The frequency quadrupled ultraviolet Nd-YAG laser, producing 5 - 1000 {mu}m crater diameters, allows the determination of both low elemental contents and isotope ratios in the minerals and isotopic variations and time-resolved measurements of fluid-solid inclusions. A unique feature is an optional high performance petrographic microscope providing both reflected and transmitted illumination for mineral identification prior to laser ablation. Results of studies will be presented.

  20. 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.

  1. 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.

  2. Laser ICP-MS study of trace element partitioning between olivine, plagioclase, orthopyroxene and melt

    NASA Astrophysics Data System (ADS)

    Laubier, M.; Grove, T. L.; Langmuir, C. H.

    2010-12-01

    Trace element contents in natural minerals such as plagioclase, olivine, clinopyroxene and orthopyroxene can be used to correct melt compositions for fractionation and estimate the redox state of magmas. In order to appropriately address fractionation in the different magmatic settings, high precision, fO2 controlled measurements at low pressures and variable temperature of mineral-melt trace element partition coefficients are needed. This study consists of 0.1 Mpa experiments on two starting compositions, a normal MORB AII96-18-1 from the Kane Fracture Zone and a basaltic andesite 85-44 from Mt Shasta. The starting compositions were enriched in 13 elements by addition of elemental standard solutions. The experiments were carried out at MIT in a vertical-tube DelTech quenching furnace with a CO2-H2 gas atmosphere. Both isothermal and cooling rate experiments, as well as non-doped experiments, were performed. The range in temperature was 1150-1175°C for the MORB and 1155-1190°C for the basaltic andesite. The different fO2 conditions were QFM, NNO, and NNO+2. Glasses, olivine, plagioclase and orthopyroxene crystals in the run products were analyzed by laser ICP-MS using a variety of calibration glass and mineral standards. Clinopyroxene crystals were too small to be analyzed accurately for their trace element contents. Fe and Na loss in our experiments is generally low and unlikely to have significant effects on the liquidus temperature. For the MORB composition, the average values for the Ol/Melt exchange distribution coefficient KD Fe-Mg (0.28±0.01), Cpx/Melt KD Fe-Mg (0.24±0.01) and Plg/Melt KD Ca-Na (0.94±0.03) attest for the achievement of chemical equilibrium. Similarly, for the basaltic andesite, the average values are Ol/Melt KD Fe-Mg = 0.28±0.01, Cpx/Melt KD Fe-Mg = 0.291±0.005, Opx/Melt KD Fe-Mg = 0.275±0.015 and Plg/Melt KD Ca-Na = 1.03±0.1. Cooling experiments systematically show different phase proportions, mineral compositions and partition

  3. Toward the resolution of microscopic seasonal variations in slow growing speleothems by ELA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Miller, N. R.; Wong, C. I.; Cunningham, M. T.; Banner, J. L.

    2011-12-01

    Speleothems constitute potential seasonal proxies of terrestrial environmental change over multi-decadal to millennial time-scales, but have highly variable growth rates that bear on the practical spatial resolution that is achievable by conventional analytical approaches. Although attractive as possible chronometers of long-term environmental change, slow growing speleothems pose particular challenges for representative sampling required to obtain robust high-resolution geochemical time series. U-series dates demonstrate that many central Texas speleothems are slow growing records, with growth rates commonly in the range of 5-30 μm/yr. In contrast to fast-growth speleothems (i.e. >0.5 mm/yr), banding at predicted seasonal stratigraphic frequencies is not apparent by petrographic inspection. Complementary UV imagery reveals that band thicknesses can vary over short distances by a factor of 40, consistent with the allowable range of U-series growth rate estimates, but also suggesting that significant short-term growth rate variations are possible, if not endemic, to such records. Excimer laser ablation, ELA-ICP-MS, offers potential solutions to the sampling challenges posed by finely banded speleothems, but signal to noise level at this small scale has not been widely explored. We present results of tests to improve fine-scale spatial resolution through optimization of conventional instrumental variables associated with measurement and hardware changes. The latter include adoption of rectangular slit apertures, a large-format laser cell with localized "fast" sampling of the ablation plume, and a high energy optical attenuator. We focus on two speleothems from the same locality, having median U-series growth rates of ~15 μm/year, and employ slow line scans using a narrow slit aperture. Our approach is to modulate instrumental parameters (laser power, rep rate, scan rate, He flow) to obtain symmetrical wash-in and wash-out times, while obtaining lowest possible RSDs

  4. 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.

  5. Feasibility of microwave-induced combustion for trace element determination in Engraulis anchoita by ICP-MS.

    PubMed

    Maciel, Juliana V; Knorr, Camila L; Flores, Erico M M; Müller, Edson I; Mesko, Marcia F; Primel, Ednei G; Duarte, Fabio A

    2014-02-15

    A method based on microwave-induced combustion (MIC) was developed for fish (Engraulis anchoita) digestion and subsequent determination of As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Se, and Zn by inductively coupled plasma mass spectrometry (ICP-MS). A reflux step (5 min) was applied to improve absorption and recovery of analytes. Nitric acid was investigated as absorbing solution and suitable results were achieved using 5 mol L⁻¹ HNO₃. Microwave-assisted digestion in closed vessels using concentrated HNO₃ was also evaluated for comparison of results. Both sample preparation methods were considered suitable for sample digestion but MIC was preferable not only because diluted HNO3 can be used as absorbing solution but also because it provides higher efficiency of digestion and also better limits of detection. Accuracy was evaluated by the analysis of certified reference materials (DORM-2 and TORT-2) after MIC digestion with subsequent determination by ICP-MS. Agreement with certified values was better than 94%. PMID:24128565

  6. 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. PMID:17316230

  7. [Determination of U, Th and Tl in fourteen Chinese traditional medicines by microwave digestion-ICP-MS].

    PubMed

    Sun, Wei-Min; Xue, Da-Fang; Li, Hong; Liu, Hui; Teng, Wen-Feng

    2009-01-01

    Fourteen Chinese traditional medicines were digested by microwave digestion, which are generally applied to treat tumor in clinic, and the contents of U, Th and Tl in the fourteen Chinese traditional medicines were determined by inductively coupled plasma mass spectrometry (ICP-MS), and the results show that the change ranges of the elements contents were: 0.005 153-0.1534 microg x g(-1) for U; 0.03501-0.4628 microg x g(-1) for Th; 0.00143-1.600 microg x g(-1) for Tl. The contents of U, Th and Tl in the fourteen Chinese traditional medicines were low, and not with one accord. The determination results of the fourteen Chinese traditional medicines were analyzed by SPSS 11.5, and the results show that there were not significant deviations(p>0.05) of the contents of U, Th and Tl between the medicine of treating the toxifying disease with poisonous agents and the medicines of heat-clearing. The study indicates that inductively coupled plasma mass spectrometry (ICP-MS) is a quick, accurate, sensitive method to determine the contents of U, Th and Tl in Chinese traditional medicine, and the results of this study provide reference data for using Chinese traditional medicine safely in clinic and developing Chinese traditional medicine. PMID:19385252

  8. 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.

  9. [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. PMID:18330312

  10. Precise and accurate measurement of U and Th isotopes via ICP-MS using a single solution

    NASA Astrophysics Data System (ADS)

    Mertz-Kraus, R.; Sharp, W. D.; Ludwig, K. R.

    2012-04-01

    U-series isotope measurements by ICP-MS commonly utilize separate runs for U and Th and standard-sample bracketing to determine correction factors for mass fractionation and ion counter yields. Here we present an approach where all information necessary to calculate an age (aside from background/baseline levels) is determined while analyzing a single solution containing both U and Th. This internally calibrated procedure should reduce any bias caused by distinct behavior of sample versus standard solutions during analysis and offers advantages including simplicity of operation, calculation of preliminary ages in real time, and simplified analysis of errors and their sources. Hellstrom (2003) developed a single-solution, internally-calibrated technique for an ICP-MS with multiple ion counters, but to our knowledge no such technique is available for an ICP-MS with a single ion counter. We use a Thermo Neptune Plus multi-collector ICP-MS with eight movable Faraday cups and a fixed center cup/ion counter equipped with a high abundance-sensitivity filter (RPQ). We use Faraday cups to measure all masses except 230 and 234, which are measured on the ion counter with the RPQ detuned (i.e., Suppressor voltage = 9950 V). 238U is maintained in a cup throughout the analysis to avoid reflections and is used to normalize signal instabilities related to sample introduction. Each analysis has a three-part structure, i.e. 1) background/baseline levels, 2) sample composition, and 3) peak-tails are sequentially determined. In step 1, multiplier dark noise/Faraday baselines plus background intensities at each mass are determined while aspirating running solution. During sample measurement in step 2, ion counter yields for Th and U are determined using signals of 300-400 kcps for 229Th and 233U by measuring 229Th/238U and 233U/238U ratios first with the minor masses on the ion counter and then with both masses in cups. Mass bias can be determined using the 233U/236U ratio of the spike

  11. 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

  12. Determination of Ti, Zr, Nb, V, W and Mo in seawater by a new online-preconcentration method and subsequent ICP-MS analysis

    NASA Astrophysics Data System (ADS)

    Poehle, Sandra; Schmidt, Katja; Koschinsky, Andrea

    2015-04-01

    We present a new method for the determination of Ti, Zr, Nb, V, W and Mo in seawater by adapting the online-preconcentration procedure with the system SeaFAST and subsequent analysis by ICP-MS to these metals. The trace elements Ti, Zr, Nb and W are present in seawater in ultratrace concentrations in the range of pmol kg-1, whereas Mo and V, which are biologically essential elements, are present in the concentration range of nmol kg-1. The online-preconcentration system we used consists of an autosampler, a sample loop, a preconcentration column and two valves controlling the sample loop and the preconcentration processes. The pre-packed preconcentration column contains a chelating resin with two functional groups, ethylenediamine triacetic acid (EDTriA) and iminodiacetic acid (IDA), immobilized on a polymer backbone. The preconcentration process was optimized for loading the sample and subsequent rinsing to remove residues of seawater matrix prior to elution with the optimized elution acid (0.5 M HNO3-0.002 M HF). We used acidified North Sea seawater (0.02 M HCl-0.002 M HF) for the method development. Samples and calibration standards were loaded onto the preconcentration column and after elution directly transferred to the quadrupole ICP-MS and measured immediately. Best results were achieved with matrix-matched calibration standards (0.6 M NaCl-0.02 M HCl-0.002 M HF) simulating acidified seawater samples. Titanium, Zr, Nb and W are measured simultaneously in one run, whereas V and Mo are determined simultaneously in a separate run. Low procedure blanks were calculated for Ti, Zr, Nb, W (635, 14.5, 1.35, 10.2 pmol kg-1) and for V and Mo, 9.79 and 5.61 nmol kg-1, respectively. Very good spike recoveries achieved with spiked North Sea water demonstrate the applicability for all six elements. Analysis of the seawater standard NASS-6 gave recoveries of 97-99% (0.9-2.2% standard deviation, SD) for Mo and V. We also provide Zr, Nb and W data for this reference standard

  13. Cross-validation and evaluation of the performance of methods for the elemental analysis of forensic glass by μ-XRF, ICP-MS, and LA-ICP-MS.

    PubMed

    Trejos, Tatiana; Koons, Robert; Becker, Stefan; Berman, Ted; Buscaglia, JoAnn; Duecking, Marc; Eckert-Lumsdon, Tiffany; Ernst, Troy; Hanlon, Christopher; Heydon, Alex; Mooney, Kim; Nelson, Randall; Olsson, Kristine; Palenik, Christopher; Pollock, Edward Chip; Rudell, David; Ryland, Scott; Tarifa, Anamary; Valadez, Melissa; Weis, Peter; Almirall, Jose

    2013-06-01

    Elemental analysis of glass was conducted by 16 forensic science laboratories, providing a direct comparison between three analytical methods [micro-x-ray fluorescence spectroscopy (μ-XRF), solution analysis using inductively coupled plasma mass spectrometry (ICP-MS), and laser ablation inductively coupled plasma mass spectrometry]. Interlaboratory studies using glass standard reference materials and other glass samples were designed to (a) evaluate the analytical performance between different laboratories using the same method, (b) evaluate the analytical performance of the different methods, (c) evaluate the capabilities of the methods to correctly associate glass that originated from the same source and to correctly discriminate glass samples that do not share the same source, and (d) standardize the methods of analysis and interpretation of results. Reference materials NIST 612, NIST 1831, FGS 1, and FGS 2 were employed to cross-validate these sensitive techniques and to optimize and standardize the analytical protocols. The resulting figures of merit for the ICP-MS methods include repeatability better than 5% RSD, reproducibility between laboratories better than 10% RSD, bias better than 10%, and limits of detection between 0.03 and 9 μg g(-1) for the majority of the elements monitored. The figures of merit for the μ-XRF methods include repeatability better than 11% RSD, reproducibility between laboratories after normalization of the data better than 16% RSD, and limits of detection between 5.8 and 7,400 μg g(-1). The results from this study also compare the analytical performance of different forensic science laboratories conducting elemental analysis of glass evidence fragments using the three analytical methods. PMID:23673570

  14. 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.

  15. 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

  16. Determination of Trace Cadmium in Geological Samples by Aerosol Dilution ICP-MS with Inverse Aqua Regia Extraction

    NASA Astrophysics Data System (ADS)

    Xu, Q.; Guo, W.; Jin, L.; Hu, S.; Chai, X.

    2015-12-01

    Cadmium (Cd) is a trace element that occurs at ppb level in most terrestrial materials. The determination of Cd in geological samples by ICP-MS is subject to Zr and/or Mo based oxide/hydroxide interference. This study developed a valid method for the determination of Cd by Ar aerosol dilution ICP-MS with inverse aqua regia extraction (in a water bath at 95℃ for 2h). An Agilent 7700x ICP-MS (Agilent Technologies, USA) with an aerosol dilution system was used. The extraction procedure separated most of the Zr matrix (>90%) from the analyte, and the residual Zr- hydroxides and Mo-oxides or hydroxides were successfully eliminated by adding an amount of Ar to the sample aerosol prior to the plasma. Compared to the conventional operation, the amounts of oxide and hydroxide ions formed in the plasma were reduced by up to 10 times. The relative yields of the interfering oxides and hydroxides were as low as 0.012% ((94Mo16OH++95Mo16O+)/(94Mo++95Mo+)) and 0.007% (94Zr16OH+/94Zr+). Under the optimized dilution gas flow rate (0.85 L min-1) and carrier gas flow rate (0.24 L min-1), the limit of detection (LOD, 3s) for 111Cd was 1.3 ng g-1. The accuracy of the method was assessed by using two USGS SRMs (andesite AGV-2 and basalt BCR-2). The Cd contents determined for AGV-2 and BCR-2 are 0.058±0.004μg g-1 and 0.148±0.007μg g-1 (N=10), which are in good agreement with the USGS reference values (0.061μg g-1 and 0.14μg g-1). The proposed method was also applied to determine Cd contents in 65 IGGE SRMs (28 soils, 28 sediments and 9 rocks). The measured Cd levels in these samples agree well with their certified values. The developed method shows great potential for the direct determination of trace levels of Cd in geological samples.

  17. 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

  18. 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. PMID:26212983

  19. 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.

  20. Effective LA-ICP-MS dating of common-Pb bearing accessory minerals with new data reduction schemes in Iolite

    NASA Astrophysics Data System (ADS)

    Kamber, Balz S.; Chew, David M.; Petrus, Joseph A.

    2014-05-01

    Compared to non-destructive geochemical analyses, LA-ICP-MS consumes ca. 0.1 μm of material per ablation pulse. It is therefore to be expected that the combined analyses of ca. 200 pulses will encounter geochemical and isotopic complexities in all but the most perfect minerals. Experienced LA-ICP-MS analysts spot down-hole complexities and choose signal integration areas accordingly. In U-Pb geochronology, the task of signal integration choice is complex as the analyst wants to avoid areas of common Pb and Pb-loss and separate true (concordant) age complexity. Petrus and Kamber (2012) developed VizualAge as a tool for reducing and visualising, in real time, U-Pb geochronology data obtained by LA-ICP-MS as an add-on for the freely available U-Pb geochronology data reduction scheme of Paton et al. (2010) in Iolite. The most important feature of VizualAge is its ability to display a live concordia diagram, allowing users to inspect the data of a signal on a concordia diagram as the integration area it is being adjusted, thus providing immediate visual feedback regarding discordance, uncertainty, and common lead for different regions of the signal. It can also be used to construct histograms and probability distributions, standard and Tera-Wasserburg style concordia diagrams, as well as 3D U-Th-Pb and total U-Pb concordia diagrams. More recently, Chew et al. (2014) presented a new data reduction scheme (VizualAge_UcomPbine) with much improved common Pb correction functionality. Common Pb is a problem for many U-bearing accessory minerals and an under-appreciated difficulty is the potential presence of (possibly unevenly distributed) common Pb in calibration standards, introducing systematic inaccuracy into entire datasets. One key feature of the new method is that it can correct for variable amounts of common Pb in any U-Pb accessory mineral standard as long as the standard is concordant in the U/Pb (and Th/Pb) systems after common Pb correction. Common Pb correction

  1. 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). PMID:23618175

  2. 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

  3. 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.

  4. Estimation of the lake water pollution by determination of 18 elements using ICP-MS method and their statistical analysis.

    PubMed

    Komorowicz, Izabela; Gramowska, Hanka; Barałkiewicz, Danuta

    2010-01-01

    Eighteen elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Sr and Zn) were determined in water taken from Malta Lake. All the analyses were made using the inductively coupled plasma mass spectrometry method (ICP-MS). In our investigations we focused on the variability of the element content in water from a number of sampling stations and over different seasons. The obtained results were submitted to statistical analysis. First, the results were interpreted using the analysis of variance test (ANOVA). This has revealed differences in concentration for the majority of elements with regard to seasons. Then, cluster analysis (CA) and factor analysis (FA) were applied to explore similarities between sampling stations. Neither of these have demonstrated any grouping. Finally, factor analysis and principal component analysis (PCA), applied to show the grouping of elements, revealed how different sampling stations are related to each other. PMID:20390876

  5. 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. PMID:27408828

  6. 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

  7. Measurement of 240Pu/239Pu isotopic ratios in soils from the Marshall Islands using ICP-MS.

    PubMed

    Muramatsu, Y; Hamilton, T; Uchida, S; Tagami, K; Yoshida, S; Robison, W

    2001-10-20

    Nuclear weapons tests conducted by the United States in the Marshall Islands produced significant quantities of regional or tropospheric fallout contamination. Here we report on some preliminary inductively coupled plasma-mass spectrometry (ICP-MS) measurements of plutonium isolated from seven composite soil samples collected from Bikini, Enewetak and Rongelap Atolls in the northern Marshall Islands. These data show that 240Pu/239Pu isotopic signatures in surface soils from the Marshall Island vary significantly and could potentially be used to help quantify the range and extent of fallout deposition (and associated impacts) from specific weapons tests. 137Cs and 60Co were also determined on the same set of soil samples for comparative purposes. PMID:11669263

  8. Laser ablation ICP-MS analysis of the radial distribution of lead in the femur of Alligator mississippiensis.

    PubMed

    Seltzer, Michael D; Lance, Valentine A; Elsey, Ruth M

    2006-06-15

    A laser ablation ICP-MS technique has been used to examine the radial distribution of lead in transverse sections of alligator femur. Annual bone growth in the femur results in the deposition of incremental layers of calcified tissue at the periphery of existing bone. Patterns of lead concentration within these layers provide a record of time-dependent accumulation from which exposure history can potentially be deduced. Femur specimens obtained from captive-reared alligators exhibited levels of lead accumulation that were entirely consistent with previously documented clinical signs of lead intoxication. In contrast, femurs obtained from wild alligators contained only minor amounts of lead that were likely accumulated as a result of incidental exposure. PMID:15982720

  9. Apatite U-Pb Thermochronology: A combined ID-TIMS and LA-ICP-MS study from southern Ecuador

    NASA Astrophysics Data System (ADS)

    Cochrane, R.; Spikings, R.; Chew, D.; Wotzlaw, J.

    2012-04-01

    A combination of U-Pb LA-ICP-MS and ID-TIMS analyses of apatite has been used to investigate the high temperature (>450° C) thermal history of the Ecuadorian Andean margin. The rocks of the Eastern Cordillera of Ecuador evolved via terrane collision and accretion events, and active margin magmatism since the Early Jurassic. Low temperature (0.5) reveal periods of: i) rapid cooling (~240-220 Ma) through the Pb Partial Retention Zone (PRZ) shortly after crystallization, ii) residence at temperatures lower than the PRZ throughout the Jurassic, iii) reheating during 140-90 Ma, and iv) rapid cooling starting at 80-70 Ma. These findings corroborate conclusions based on geochronological and sedimentological data. Additional in-situ age transects and age-depth profiling of apatite are scheduled to determine the concentration distribution of radiogenic lead in the apatites, which will be used to constrain further the mechanisms of lead loss.

  10. Comparative determination of methyl mercury in whole blood samples using GC-ICP-MS and GC-MS techniques.

    PubMed

    Hippler, J; Hoppe, H W; Mosel, F; Rettenmeier, A W; Hirner, A V

    2009-08-15

    Two methods for the determination of methyl mercury (MeHg) in whole blood samples based on different mass spectrometric detection techniques are compared. The methods were employed in two studies in which the internal exposure of a group of mercury-exposed workers to total mercury and MeHg was investigated. Blood samples of these workers were analysed for MeHg independently from each other in two laboratories using similar extraction procedures but different detection techniques, viz. coupled GC-EI-MS/ICP-MS and GC-MS using D(3)-MeHg as internal standard. MeHg was detected in all blood samples in concentrations ranging from 0.3 to 9.0 microg/L. Though different detection techniques were employed, the results obtained by the two laboratories were in relatively good agreement. PMID:19560985

  11. Determination of 241Am in sediments by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS).

    PubMed

    Agarande, M; Benzoubir, S; Bouisset, P; Calmet, D

    2001-08-01

    Trace levels (pg kg(-1)) of 241Am in sediments were determined by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS) using a microconcentric nebulizer. 241Am was isolated from major elements like Ca and Fe by different selective precipitations. In further steps. Am was first separated from other transuranic elements and purified by anion exchange and extraction chromatography prior to the mass spectrometric measurements. The ID HR ICP-MS results are compared with isotope dilution alpha spectrometry. PMID:11393755

  12. Limitation of secondary electron multiplier non-linearity on accurate U-Th isotopic determination by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Shen, C.; Wu, C.; Gallet, S.; Cheng, H.; Edwards, R.; Hsieh, Y.; Lin, K.

    2008-12-01

    Contemporary multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) with discrete dynode secondary electron multipliers (SEMs) can offer U-Th isotopic determinations with subpermil-permil- level precision in femtogram quantities. However, accurate isotopic measurement requires fully understanding SEM mass and intensity biases. In additional to dead-time effect, Richter et al (2001, Int. J. Mass Spectrom., 206, 105-127) reported a nonlinearity on SEMs produced by ETP and MasCom for count rates > 20 thousand counts per second (cps). We evaluated the possible biases for ion beams of 500- 1,600,000 cps on a latest MasCom SEM, SEV TE-Z/17, with more effective ion optical acceptance area (>50%) and better peak shape than previous models, used in a MC-ICP-MS, Thermo Fisher NEPTUNE. With the retarding potential quadruple lens (RPQ) turned off, ion beam intensity can be biased by only dead- time effect, which can be precisely corrected online or offline. With the RPQ on, two additional biases, an exponential-like increase of ion beam intensity from 100-100,000 s cps and an apparent dead-time effect (-2 to 2 ns) at high count rates, are observed. They are likely caused by the slightly defocused ions with a wide kinetic energy spread of ~5 eV, 10 times worse than that with thermal source, passing through the RPQ lens to the SEM, which is installed behind the focal plane. Fortunately, the two biases, which are stable during the daily measurements with the same settings of inlet system, source lenses, zoom optics, and RPQ, can be corrected effectively offline to earn accurate U-Th isotopic measurement.

  13. 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. PMID:22099643

  14. 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. PMID:21111147

  15. Application of HPLC-ICP-MS and HPLC-ESI-MS procedures for arsenic speciation in seaweeds.

    PubMed

    Hsieh, Yu-Jhe; Jiang, Shiuh-Jen

    2012-03-01

    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. PMID:22339408

  16. Coprecipitation with calcium hydroxide for determination of iron in fish otoliths by collision cell ICP-MS.

    PubMed

    Daniels, Stephanie L; Arslan, Zikri

    2007-05-01

    A method has been described for the determination of iron from fish otoliths containing high levels of calcium by collision cell technology (CCT) ICP-MS. Iron (Fe) in otolith solutions was quantitatively coprecipitated with small amounts of calcium hydroxide by adding 1.0 M sodium hydroxide solution. The performance of CCT-ICP-MS pressurized with He/H(2) cell gas was investigated on the elimination of Ca-based spectral interferences at m/z 54, 56 and 57. Molecular ion interferences at m/z 54 and 56 were reduced by 2 orders of magnitude. However, the interferences at m/z 57 increased by the same amount in the presence of Ca in solutions owing to the formation of (40)Ca(16) OH(+) through reactions with H(2) in collision cell, indicating that (57)Fe was not suitable for the determination of Fe from otoliths. Results for (56)Fe suffered significantly from interferences of Ca-based molecular ions when the Ca concentration in solution exceeded 100 microg ml(-1), for which matrix-matched calibration was required for accurate determination. CCT with the aid of He/H(2) cell gas proved to be very effective in eliminating the interferences ((40)Ar(14)N(+) and (40)Ca(14)N(+)) at m/z 54. Presence of Ca up to 300 microg ml(-1) had virtually no effect on the ion signals of (54)Fe, which with low background signals, afforded accurate determination of Fe from otoliths by using aqueous external standards. PMID:17294508

  17. 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.

  18. 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.

  19. [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. PMID:19093589

  20. Identification of Marchfeld asparagus using Sr isotope ratio measurements by MC-ICP-MS.

    PubMed

    Swoboda, S; Brunner, M; Boulyga, S F; Galler, P; Horacek, M; Prohaska, T

    2008-01-01

    This work focuses on testing and application of Sr isotope signatures for the fast and reliable authentication and traceability of Asparagus officinalis originating from Marchfeld, Austria, using multicollector inductively coupled plasma mass spectrometry after optimised Rb/Sr separation. The major sample pool comprises freeze-dried and microwave-digested asparagus samples from Hungary and Slovakia which are compared with Austrian asparagus originating from the Marchfeld region, which is a protected geographical indication. Additional samples from Peru, The Netherlands and Germany were limited in number and allowed therefore only restricted statistical evaluation. Asparagus samples from Marchfeld were harvested within two subsequent years in order to investigate the annual variation. The results show that the Sr isotope ratio is consistent within these 2 years of investigation. Moreover, the Sr isotope ratio of total Sr in soil was found to be significantly higher than in an NH4NO3 extract, reflecting the mobile (bioavailable) phase. The isotope composition in the latter extract corresponds well to the range found in the asparagus samples in Marchfeld, even though the concentration of Sr in asparagus shows no direct correlation to the concentration of Sr in the mobile phase of the soil. The major question was whether the 'Marchfelder Spargel' can be distinguished from samples from the neighbouring countries of Hungary and Slovakia. According to our findings, they can be clearly (100%) singled out from the Hungarian samples and can be distinguished from the Slovakian asparagus samples with a probability of more than 80%. PMID:17874075

  1. Arsenic-containing fatty acids and hydrocarbons in marine oils - determination using reversed-phase HPLC-ICP-MS and HPLC-qTOF-MS.

    PubMed

    Sele, Veronika; Sloth, Jens J; Holmelid, Bjarte; Valdersnes, Stig; Skov, Kasper; Amlund, Heidi

    2014-04-01

    Arsenolipids are the major arsenic species present in marine oils. Several structures of arsenolipids have been elucidated the last 5 years, demonstrating the chemical complexity of this trace element in the marine environment. Several commercial fish oils and marine oils, ranging in total arsenic concentrations from 1.6 to 12.5 mg kg(-1) oil, were analyzed for arsenolipids using reversed-phase high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The arsenolipids were quantified using three different arsenic-containing calibration standards; dimethylarsinate (DMA), triphenylarsinoxide (Ph₃AsO) and a synthesized arsenic-containing hydrocarbon (AsHC) (dimethylarsinoyl nonadecane; C₂₁H₄₃AsO). The observed variation in signal intensity for arsenic during the gradient elution profile in reversed-phase HPLC was compensated for by determining the time-resolved response factors for the arsenolipids. Isotopes of germanium ((74)Ge) and indium ((115)In) were suited as internal standards for arsenic, and were used for verification of the arsenic signal response factors during the gradient elution. Dimethylarsinate was the most suitable calibration standard for the quantification of arsenolipids, with recoveries between 91% and 104% compared to total arsenic measurements in the same extracts. A range of marine oils was investigated, including oils of several fish species, cod liver and seal, as well as three commercial fish oils. The AsHCs - C₁₇H₃₈AsO, C₁₉H₄₂AsO and C₂₃H₃₈AsO - were identified as the major arsenolipids in the extracts of all oils by HPLC coupled with quadrupole time-of-flight mass spectrometry (qTOF-MS). Minor amounts of two arsenic-containing fatty acids (AsFAs) (C₂₃H₃₈AsO₃ and C₂₄H₃₈AsO₃) were also detected in the oils. The sum of the AsHCs and the AsFAs determined in the present study accounted for 17-42% of the total arsenic in the oils. PMID

  2. 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 ...

  3. LA-ICP-MS and Textural Analyses of Impact Spherules from the 2.54 Ga Bee Gorge Spherule Layer, Western Australia

    NASA Astrophysics Data System (ADS)

    Deutsch, A.; Metzler, K.; Berndt, J.; Langenhorst, F.

    2013-08-01

    We have analyzed spherules in thin sections from the 2.54 Bee Gorge ejecta layer with special emphasize on the origin of textural features. We try to constrain the geochemical composition of the target using trace element analysis with LA-ICP-MS.

  4. Possibilities of LA-ICP-MS technique for the spatial elemental analysis of the recent fish scales: Line scan vs. depth profiling

    NASA Astrophysics Data System (ADS)

    Holá, Markéta; Kalvoda, Jiří; Nováková, Hana; Škoda, Radek; Kanický, Viktor

    2011-01-01

    LA-ICP-MS and solution based ICP-MS in combination with electron microprobe are presented as a method for the determination of the elemental spatial distribution in fish scales which represent an example of a heterogeneous layered bone structure. Two different LA-ICP-MS techniques were tested on recent common carp ( Cyprinus carpio) scales: A line scan through the whole fish scale perpendicular to the growth rings. The ablation crater of 55 μm width and 50 μm depth allowed analysis of the elemental distribution in the external layer. Suitable ablation conditions providing a deeper ablation crater gave average values from the external HAP layer and the collagen basal plate. Depth profiling using spot analysis was tested in fish scales for the first time. Spot analysis allows information to be obtained about the depth profile of the elements at the selected position on the sample. The combination of all mentioned laser ablation techniques provides complete information about the elemental distribution in the fish scale samples. The results were compared with the solution based ICP-MS and EMP analyses. The fact that the results of depth profiling are in a good agreement both with EMP and PIXE results and, with the assumed ways of incorporation of the studied elements in the HAP structure, suggests a very good potential for this method.

  5. 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

  6. Single particle ICP-MS as a tool for determining the stability of silver nanoparticles in aquatic matrixes under various environmental conditions, including treatment by ozonation.

    PubMed

    Telgmann, Lena; Nguyen, Michael Thanh Khoa; Shen, Li; Yargeau, Viviane; Hintelmann, Holger; Metcalfe, Chris D

    2016-07-01

    Silver nanoparticles (AgNPs) are used in a large number of consumer products due to their antimicrobial and antifungal properties, and these materials may be discharged into municipal wastewater. Wastewater treatment, including advanced oxidation processes (AOPs), may modify the forms of silver in wastewater before they are discharged into surface waters. In addition, little is known about the changes in AgNPs that occur in natural waters under different environmental conditions. In this project, we utilized single particle ICP-MS (spICP-MS) and dynamic light scattering (DLS) analytical techniques to evaluate changes in the number and size of AgNPs in laboratory experiments with milliQ water under different environmental conditions, as well as during ozonation. Changes in the number and size of AgNPs determined by spICP-MS were evidence of altered stability of the nanoparticles. Increased rates of dissolution occurred under extremes of pH. Lower temperature decreased the rate of dissolution of AgNP relative to the dissolution in treatments at room temperature. The addition of chloride resulted in the loss of AgNPs from suspension due to agglomeration and precipitation. Ozonation led to a rapid decline in the number and size of AgNPs, as indicated by both spICP-MS and DLS analysis. An increase in the concentration of dissolved silver in the ozone treatments was evidence that changes in particle size were a result of oxidative dissolution of AgNPs to silver ion. Graphical abstract Single particle ICP-MS is used to evaluate dissolution of silver nanoparticles under different environmental conditions, including water treatment by ozonation. PMID:27311958

  7. 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. PMID:26005744

  8. Determination of {sup 230}Th, {sup 234}U, {sup 239}Pu, and {sup 240}Pu in soils by ICP-MS using flow-injection preconcentration

    SciTech Connect

    Hollenbach, M.; Grohs, J.; Mamich, S.; Kroft, M.

    1995-12-31

    The US Department of Energy needs improved analytical methods for alpha-emitting radionuclides to support environmental restoration and waste management projects. Inductively coupled plasma-mass spectrometry (ICP-MS) has been used successfully to measure radionuclides with relatively long half-lives; however, ICP-MS used with conventional sample introduction techniques lacks the sensitivity or selectivity to measure shorter-lived radionuclides at levels important for environmental monitoring. New methods were developed for measuring {sup 230}Th, {sup 234}U, {sup 239}Pu, and {sup 240}Pu in soils. Samples are dried, ground, and dissolved by fusion. A flow injection (FI) analysis system is used to separate and concentrate the analytes by solid-phase extraction. The FI eluent is pumped directly into the nebulizer of the ICP-MS. The use of FI resulted in greater sensitivity and freedom from interferences when compared with direct aspiration. Detection limits are improved by approximately a factor of 20. The detection limits are approximately 3 Bq/kg (4 ng/kg) for {sup 230}Th, 0.6 Bq/kg (3 ng/kg) for {sup 234}U, 0.4 Bq/kg (0.2 ng/kg) for {sup 239}Pu, and 2 Bq/kg (0.3 ng/kg) for {sup 240}Pu. The FI-ICP-MS methods are faster, less labor intensive, and generate less laboratory waste than traditional radiochemical methods. The FI-ICP-MS gives individual results for {sup 239}Pu and {sup 240}Pu which cannot be resolved by the usual radiochemical method. The accuracy of the methods was verified by analyzing reference soils.

  9. 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

  10. 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

  11. 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. PMID:25404165

  12. Approach for rapid extraction and speciation of mercury using a microtip ultrasonic probe followed by LC-ICP-MS.

    PubMed

    López, Isabel; Cuello, Susana; Cámara, Carmen; Madrid, Yolanda

    2010-07-15

    A fast method for mercury extraction from biological samples based on the use of HCl leaching plus different enzymatic hydrolysis (with and without mercury complexing agents), and the use of focussed ultrasounds (2-mm microtip) is here proposed. Total mercury content in several biological samples was determined by FI-ICP-MS using a carrier solution consisting of 0.1% (v/v) HCl, 0.1% (v/v) 2-mercaptoethanol, to avoid memory effect, and 0.15% (w/v) KCl. For mercury speciation a RP18 chromatographic column coupled to ICP-MS was used. A mobile phase consisting of 0.1% (v/v) formic acid, 0.1% (v/v) HFBA, 2% (v/v) methanol, and 0.02% (w/v) mM L-cysteine at pH 2.1 was used for chromatographic separation of the mercury species in the sample extracts. Extraction procedures were validated by using 50 mg of tuna fish tissue CRM-463 (2.85+/-0.16 mg kg(-1) for methylmercury). The recoveries obtained were 99+/-3% and 93+/-1% after acid leaching (HCl 7 M) and enzymatic extraction (15 mg protease type XIV in 2.5% (v/v) 2-mercaptoethanol), respectively. The optimal sonication conditions (5 min of exposure time and 40% of ultrasound amplitude) were applied to 5 mg of CRM-463 (88+/-5%), 5 mg of mussel tissue (81+/-11%) and to 2 mg of zebra fish embryos (90+/-10%) obtaining good recoveries in all cases. Methylmecury was found to be the most abundant Hg specie in all samples. The developed method is simple and rapid (5 min sample treatment); it is suitable for very small samples and does not alter the original form of the mercury species. Thus, it is of special interest in those cases in which validation of the results may often be hampered by lack of sample availability. PMID:20602941

  13. 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

  14. 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

  15. Automated sample preparation for radiogenic and non-traditional metal isotope analysis by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Field, M. P.; Romaniello, S. J.; Gordon, G. W.; Anbar, A. D.

    2012-12-01

    High throughput analysis is becoming increasingly important for many applications of radiogenic and non-traditional metal isotopes. While MC-ICP-MS instruments offer the potential for very high sample throughout, the requirement for labor-intensive sample preparation and purification procedures remains a substantial bottleneck. Current purification protocols require manually feeding gravity-driven separation columns, a process that is both costly and time consuming. This bottleneck is eliminated with the prepFAST-MC™, an automated, low-pressure ion exchange chromatography system that can process from 1 to 60 samples in unattended operation. The syringe-driven system allows sample loading, multiple acid washes, column conditioning and elution cycles necessary to isolate elements of interest and automatically collect up to 3 discrete eluent fractions at user-defined intervals (time, volume and flow rate). Newly developed protocols for automated purification of uranium illustrates high throughput (>30 per run), multiple samples processed per column (>30), complete (>99%) matrix removal, high recovery (> 98%, n=25), and excellent precision (2 sigma =0.03 permil, n=10). The prepFAST-MC™ maximizes sample throughput and minimizes costs associated with personnel and consumables providing an opportunity to greatly expand research horizons in fields where large isotopic data sets are required, including archeology, geochemistry, and climate/environmental science

  16. Monte Carlo simulation of expert judgments on human errors in chemical analysis--a case study of ICP-MS.

    PubMed

    Kuselman, Ilya; Pennecchi, Francesca; Epstein, Malka; Fajgelj, Ales; Ellison, Stephen L R

    2014-12-01

    Monte Carlo simulation of expert judgments on human errors in a chemical analysis was used for determination of distributions of the error quantification scores (scores of likelihood and severity, and scores of effectiveness of a laboratory quality system in prevention of the errors). The simulation was based on modeling of an expert behavior: confident, reasonably doubting and irresolute expert judgments were taken into account by means of different probability mass functions (pmfs). As a case study, 36 scenarios of human errors which may occur in elemental analysis of geological samples by ICP-MS were examined. Characteristics of the score distributions for three pmfs of an expert behavior were compared. Variability of the scores, as standard deviation of the simulated score values from the distribution mean, was used for assessment of the score robustness. A range of the score values, calculated directly from elicited data and simulated by a Monte Carlo method for different pmfs, was also discussed from the robustness point of view. It was shown that robustness of the scores, obtained in the case study, can be assessed as satisfactory for the quality risk management and improvement of a laboratory quality system against human errors. PMID:25159436

  17. Simultaneous quantification of tumor uptake for targeted and non-targeted liposomes and their encapsulated contents by ICP-MS

    PubMed Central

    Cheng, Zhiliang; Zaki, Ajlan Al; Hui, James Z; Tsourkas, Andrew

    2012-01-01

    Liposomes are intensively being developed for biomedical applications including drug and gene delivery. However, targeted liposomal delivery in cancer treatment is a very complicated multi-step process. Unfavorable liposome biodistribution upon intravenous administration and membrane destabilization in blood circulation could result in only a very small fraction of cargo reaching the tumors. It would therefore be desirable to develop new quantitative strategies to track liposomal delivery systems to improve the therapeutic index and decrease systemic toxicity. Here, we developed a simple and non-radiative method to quantify the tumor uptake of targeted and non-targeted control liposomes as well as their encapsulated contents simultaneously. Specifically, four different chelated lanthanide metals were encapsulated or surface-conjugated onto tumor-targeted and non-targeted liposomes, respectively. The two liposome formulations were then injected into tumor-bearing mice simultaneously and their tumor delivery was determined quantitatively via inductively coupled plasma-mass spectroscopy (ICP-MS), allowing for direct comparisons. Tumor uptake of the liposomes themselves and their encapsulated contents were consistent with targeted and non-targeted liposome formulations that were injected individually. PMID:22882145

  18. Determination of water-soluble and insoluble elements in PM2.5 by ICP-MS.

    PubMed

    Manousakas, M; Papaefthymiou, H; Eleftheriadis, K; Katsanou, K

    2014-09-15

    The elemental composition of water-soluble and acid-soluble fractions of PM2.5 samples from two different Greek cities (Patras and Megalopolis) was investigated. Patras and Megalopolis represent different environments. Specifically, Patras is an urban environment with proximity to a large port, while Megalopolis is a small city located close to lignite power plants. Both cities can serve as a representative example of European cities with similar characteristics. The concentration of 14 elements (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Fe, Sr, Ti, V and Zn) was determined in each fraction by ICP-MS. Microwave assisted digestion was used to digest the samples using a mixture of HNO3 and HF. For the determination of the water soluble fraction, water was chosen as the simplest and most universal extraction solvent. For the validation of the extraction procedure, the recoveries were tested on two certified reference materials (NIST SRM 1648 Urban Particulate Matter and NIST 1649a Urban Dust). Results showed that Zn has the highest total concentration (273 and 186 ng/m(3)) and Co the lowest (0.48 and 0.23 ng/m(3)) for Patras and Megalopolis samples, respectively. Nickel with 65% for Patras and As with 49% for Megalopolis displayed the highest solubility, whereas Fe (10%) and Ti (2%) the lowest ones, respectively. PMID:24992462

  19. Automation of ⁹⁹Tc extraction by LOV prior ICP-MS detection: application to environmental samples.

    PubMed

    Rodríguez, Rogelio; Leal, Luz; Miranda, Silvia; Ferrer, Laura; Avivar, Jessica; García, Ariel; Cerdà, Víctor

    2015-02-01

    A new, fast, automated and inexpensive sample pre-treatment method for (99)Tc determination by inductively coupled plasma-mass spectrometry (ICP-MS) detection is presented. The miniaturized approach is based on a lab-on-valve (LOV) system, allowing automatic separation and preconcentration of (99)Tc. Selectivity is provided by the solid phase extraction system used (TEVA resin) which retains selectively pertechnetate ion in diluted nitric acid solution. The proposed system has some advantages such as minimization of sample handling, reduction of reagents volume, improvement of intermediate precision and sample throughput, offering a significant decrease of both time and cost per analysis in comparison to other flow techniques and batch methods. The proposed LOV system has been successfully applied to different samples of environmental interest (water and soil) with satisfactory recoveries, between 94% and 98%. The detection limit (LOD) of the developed method is 0.005 ng. The high durability of the resin and its low amount (32 mg), its good intermediate precision (RSD 3.8%) and repeatability (RSD 2%) and its high extraction frequency (up to 5 h(-1)) makes this method an inexpensive, high precision and fast tool for monitoring (99)Tc in environmental samples. PMID:25435232

  20. The absence of lithium isotope fractionation during basalt differentiation: New measurements by multicollector sector ICP-MS

    USGS Publications Warehouse

    Tomascak, P.B.; Tera, F.; Helz, R.T.; Walker, R.J.

    1999-01-01

    We report measurements of the isotopic composition of lithium in basalts using a multicollector magnetic sector plasma-source mass spectrometer (MC-ICP-MS). This is the first application of this analytical technique to Li isotope determination. External precision of multiple replicate and duplicate measurements for a variety of sample types averages ??1.1??? (2?? population). The method allows for the rapid (???8 min/sample) analysis of small samples (???40 ng Li) relative to commonly used thermal ionization methods. The technique has been applied to a suite of samples from Kilauea Iki lava lake, Hawaii. The samples range from olivine-rich cumulitic lava to SiO2 - and K2O-enriched differentiated liquids, and have ??7Li (per mil deviation of sample 7Li/6Li relative to the L-SVEC standard) of +3.0 to +4.8. The data indicate a lack of per mil-level Li isotope fractionation as a result of crystal-liquid fractionation at temperatures greater than 1050??C. This conclusion has been tacitly assumed but never demonstrated, and is important to the interpretation of Li isotope results from such geochemically complex environments as island arcs. Copyright ?? 1999 Elsevier Science Ltd.

  1. Mercury speciation analysis in human hair by species-specific isotope-dilution using GC-ICP-MS.

    PubMed

    Laffont, Laure; Maurice, Laurence; Amouroux, David; Navarro, Patricia; Monperrus, Mathilde; Sonke, Jeroen E; Behra, Philippe

    2013-03-01

    We optimized a mercury (Hg) speciation extraction method for human hair in combination with species-specific isotope-dilution analysis by gas chromatography-inductively coupled plasma-mass spectrometry (GC-ICP-MS). The method was validated on human hair reference material RM (IAEA-086), which is recommended for analysis of monomethylmercury (MMHg) and inorganic mercury (IHg). Three reagents, hydrochloric acid (HCl), nitric acid (HNO3), and tetramethylammonium hydroxide (TMAH), and three extraction procedures, at ambient temperature for 12 h, microwave-assisted at 75 °C for 6 min, and oven heated at 80 °C for 2 h were tested. Extraction efficiency, recovery, and potential species transformations were evaluated for each method. The most efficient procedures, with recovery of ~90 % for each species with limited demethylation (<5 %) and methylation (0 %), were HNO3 digestion, irrespective of temperature, and microwave-assisted TMAH extraction. Acidic extraction with HCl induces significant demethylation, with production of artifacts. To correct for potential demethylation artifacts we recommend spiking with isotopically enriched standards before the extraction step. PMID:22669307

  2. Analysis of arsenic, lead and cadmium in wines from the Canary Islands, Spain, by ICP/MS.

    PubMed

    Barbaste, M; Medina, B; Perez-Trujillo, J-P

    2003-02-01

    Because of their high toxicity, arsenic, lead and cadmium need to be quantified in food and beverages. For the first time, in this study the content of arsenic, lead and cadmium was investigated in 152 wine samples from the Canary Islands, Spain, belonging to eight Denominations of Origin (DO) and four islands by inductively coupled plasma mass spectrometry (ICP-MS). The ranges of concentration found were 0.58-8.45 microg l(-1) for arsenic, 0.20-1.73 microg l(-1) for cadmium and 3.89-159.5 microg l(-1) for lead, and the mean content was 3.13, 0.63 and 28.74 microg l(-1), respectively. None of the wines contained levels above the limits set by the International Office of Vine and Wine (OIV), and thus did not pose a health hazard. Significant differences in mean content of those elements between harvest, type of wine, islands and DO were observed. PMID:12623662

  3. Hair Mercury Levels Detection in Fishermen from Sicily (Italy) by ICP-MS Method after Microwave-Assisted Digestion

    PubMed Central

    Giangrosso, Giuseppe; Cammilleri, Gaetano; Macaluso, Andrea; Vella, Antonio; D'Orazio, Nicolantonio; Graci, Stefania; Lo Dico, Gianluigi Maria; Galvano, Fabio; Giangrosso, Margherita; Ferrantelli, Vincenzo

    2016-01-01

    A number of ninety-six hair samples from Sicilian fishermen were examined for total mercury detection by an Inductively Coupled Plasma Mass Spectrometry (ICP-MS) method. The mercury levels obtained were compared with mercury levels of 96 hair samples from a control group, in order to assess potential exposure to heavy metals of Sicilian fishermen due to fish consumption and closeness to industrial activities. Furthermore, the mercury levels obtained from hair samples were sorted by sampling area in order to verify the possible risks linked to the different locations. The overall mean concentration in the hair of the population of fishermen was 6.45 ± 7.03 μg g−1, with a highest value in a fisherman of Sciacca (16.48 μg g−1). Hair mercury concentration in fishermen group was significantly higher than in control group (p < 0.01). There was no significant difference in hair total mercury concentrations between sampling areas (p > 0.05). The results of this study indicate a greater risk of exposure to mercury in Sicilian fishermen, in comparison to the control population, due to the high consumption of fish and the close relationship with sources of exposure (ports, dumps, etc.). PMID:27127456

  4. Gold Nanoparticle Labeling Based ICP-MS Detection/Measurement of Bacteria, and Their Quantitative Photothermal Destruction

    PubMed Central

    Lin, Yunfeng

    2015-01-01

    Bacteria such as Salmonella and E. coli present a great challenge in public health care in today’s society. Protection of public safety against bacterial contamination and rapid diagnosis of infection require simple and fast assays for the detection and elimination of bacterial pathogens. After utilizing Salmonella DT104 as an example bacterial strain for our investigation, we report a rapid and sensitive assay for the qualitative and quantitative detection of bacteria by using antibody affinity binding, popcorn shaped gold nanoparticle (GNPOPs) labeling, surfance enchanced Raman spectroscopy (SERS), and inductively coupled plasma mass spectrometry (ICP-MS) detection. For qualitative analysis, our assay can detect Salmonella within 10 min by Raman spectroscopy; for quantitative analysis, our assay has the ability to measure as few as 100 Salmonella DT104 in a 1 mL sample (100 CFU/mL) within 40 min. Based on the quantitative detection, we investigated the quantitative destruction of Salmonella DT104, and the assay’s photothermal efficiency in order to reduce the amount of GNPOPs in the assay to ultimately to eliminate any potential side effects/toxicity to the surrounding cells in vivo. Results suggest that our assay may serve as a promising candidate for qualitative and quantitative detection and elimination of a variety of bacterial pathogens. PMID:26417447

  5. 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.

  6. Using Laser Ablation-ICP-MS to generate culture-based foraminiferal calibration relationships for Neogloboquadrina dutertrei

    NASA Astrophysics Data System (ADS)

    Fehrenbacher, J. S.; Russell, A. D.; Gagnon, A. C.; Davis, C. V.; Chu, E.; Bonnin, E. A.; Spero, H. J.

    2014-12-01

    Neogloboquadrina dutertrei is a deep-dwelling non-spinose planktic foraminifer that is abundant in tropical to mid-latitude regions. The Mg/Ca ratio and stable oxygen isotope geochemistry of this species are used to reconstruct thermocline hydrography (cf. Spero et al, 2003). Live culture experiments using this species are not common owing to the difficulty in collecting and maintaining these species in the laboratory. The existing calibration data for this species consists of two temperature points that were combined with data from live culture experiments on a related species, N. incompta (formerly N. pachyderma dextral) (Von Langen et al, 2004). We extended the temperature calibration for this species (from 16 - 19°C to 12 - 22°C) and developed a pH calibration (pH 7.85 - 8.4). Specimens were collected via plankton net from the Southern California Bight and cultured at the Wrigley Marine Science Center, Santa Catalina Island during the summer of 2013-2014. We use isotopically labeled seawater (43Ca, 87Sr, and 138Ba) to identify discrete portions of calcite that grew in culture. We use laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for trace element analysis and obtain paired stable isotope analyses on chambers that grew entirely in culture. The calcite-labeling technique we employ here can be applied to other marine calcifiers grown in culture and/or future culture work with foraminifers.

  7. Laser ablation of titanium nitride coated on silicon wafer substrate for depth profiling using ICP-MS

    NASA Astrophysics Data System (ADS)

    Lee, Jin Sook; Lim, H. B.

    2015-02-01

    Depth profiling of titanium nitride coated on silicon substrate at a thickness of 1 μm as a diffusion barrier for semiconductor application was studied using laser ablation (LA)-ICP-MS. The ablated particles and craters were characterized by SEM, TEM and a surface mapping microscope. Several unique characteristics were observed in this work. Although the laser beam had a short wavelength of 213 nm with flat energy, the ablated craters showed an inverse triangular shape, rather than a rectangular shape, with severe thermal degradation at the brink. In addition, the crater shape and depth were strongly dependent on the structure and thermal properties of the target. Since the TiN had a columnar structure with lower thermal conductivity and a higher melting point, it showed clear craters with less thermal degradation compared to Si substrate. The average rate of depth profiling was 40 nm per pulse. In addition, the repetition rate of the laser also significantly influenced the shape and depth of the craters. A low repetition rate produced deep craters due to high residual stress and providing sufficient time for energy concentration and heat dissipation, indicating that the repetition rate should be optimized for each material.

  8. Chromium localization in plant tissues of Lycopersicum esculentum Mill using ICP-MS and ion microscopy (SIMS)

    NASA Astrophysics Data System (ADS)

    Mangabeira, Pedro Antonio; Gavrilov, Konstantin L.; Almeida, Alex-Alan Furtado de; Oliveira, Arno Heeren; Severo, Maria Isabel; Rosa, Tiago Santana; Silva, Delmira da Costa; Labejof, Lise; Escaig, Françoise; Levi-Setti, Riccardo; Mielke, Marcelo Schramm; Loustalot, Florence Grenier; Galle, Pierre

    2006-03-01

    High-resolution imaging secondary ion mass spectrometry (HRI-SIMS) in combination with inductively coupled plasma mass spectrometry (ICP-MS) were utilised to determine specific sites of chromium concentration in tomato plant tissues (roots, stems and leaves). The tissues were obtained from plants grown for 2 months in hydroponic conditions with Cr added in a form chromium salt (CrCl 3·6H 2O) to concentrations of 25 and 50 mg/L. The chemical fixation procedure used permit to localize only insoluble or strongly bound Cr components in tomato plant tissue. In this work no quantitative SIMS analysis was made. HRI-SIMS analysis revealed that the transport of chromium is restricted to the vascular system of roots, stems and leaves. No Cr was detected in epidermis, palisade parenchyma and spongy parenchyma cells of the leaves. The SIMS-300 spectra obtained from the tissues confirm the HRI-SIMS observations. The roots, and especially walls of xylem vessels, were determined as the principal site of chromium accumulation in tomato plants.

  9. [Determination of elements related to reducing blood sugar (ERBS) in tea and tea polysaccharide by ICP-MS].

    PubMed

    Xie, Ming-Yong; Nie, Shao-Ping; Fu, Bo-Qiang; Wang, Xiao-Ru

    2006-09-01

    Contents of elements related to reducing blood sugar (ERBS) in several kinds of green tea of Wuyuan county, their tea infusion extracted by warm water and boiling water and tea polysaccharide (TP) were determined by ICP-MS, after the samples were digested with acids by microwave method. The relation between the amount of ERBS and tea quality and the relation between the content of ERBS in TP and the total content in tea were discussed. The results showed that the amounts of ERBS in tea and TP are different in various samples. The amount of ERBS in TP extracted from coarse tea was higher than that from fresh tea. The percentage of certain ERBS in TP accounting for the ERBS in tea ranged from 0.03% to 9.57%. As to the total ERBS in TP extracted from Mt. Zhang super grade tea and grade 5 tea, the percentages were 1.11% and 2.10% respectively. As to Mt. Gu old tea, it was 0.85%. The results could provide data for selecting tea material used to extracting tea polysaccharide and for studying the mechanism of reducing blood sugar. PMID:17112052

  10. Arsenic, Antimony, Chromium, and Thallium Speciation in Water and Sediment Samples with the LC-ICP-MS Technique

    PubMed Central

    Jabłońska-Czapla, Magdalena

    2015-01-01

    Chemical speciation is a very important subject in the environmental protection, toxicology, and chemical analytics due to the fact that toxicity, availability, and reactivity of trace elements depend on the chemical forms in which these elements occur. Research on low analyte levels, particularly in complex matrix samples, requires more and more advanced and sophisticated analytical methods and techniques. The latest trends in this field concern the so-called hyphenated techniques. Arsenic, antimony, chromium, and (underestimated) thallium attract the closest attention of toxicologists and analysts. The properties of those elements depend on the oxidation state in which they occur. The aim of the following paper is to answer the question why the speciation analytics is so important. The paper also provides numerous examples of the hyphenated technique usage (e.g., the LC-ICP-MS application in the speciation analysis of chromium, antimony, arsenic, or thallium in water and bottom sediment samples). An important issue addressed is the preparation of environmental samples for speciation analysis. PMID:25873962

  11. Evaluation of Trace Metal Content by ICP-MS Using Closed Vessel Microwave Digestion in Fresh Water Fish

    PubMed Central

    Jarapala, Sreenivasa Rao; Kandlakunta, Bhaskarachary; Thingnganing, Longvah

    2014-01-01

    The objective of the present study was to investigate trace metal levels of different varieties of fresh water fish using Inductively Coupled Plasma Mass Spectrophotometer after microwave digestion (MD-ICPMS). Fish samples were collected from the outlets of twin cities of Hyderabad and Secunderabad. The trace metal content in different varieties of analyzed fish were ranged from 0.24 to 1.68 mg/kg for Chromium in Cyprinus carpio and Masto symbollon, 0.20 to 7.52 mg/kg for Manganese in Labeo rohita and Masto symbollon, 0.006 to 0.07 mg/kg for Cobalt in Rastrelliger kanagurta and Pampus argenteus, 0.31 to 2.24 mg/kg for Copper in Labeo rohita and Penaeus monodon, 3.25 to 14.56 mg/kg for Zinc in Cyprinus carpio and Macrobrachium rosenbergii, and 0.01 to 2.05 mg/kg for Selenium in Rastrelliger kanagurta and Pampus argenteus, respectively. Proximate composition data for the different fishes were also tabulated. Since the available data for different trace elements for fish is scanty, here an effort is made to present a precise data for the same as estimated on ICP-MS. Results were in accordance with recommended daily intake allowance by WHO/FAO. PMID:24744789

  12. Retention of arsenate using genetically modified coryneform bacteria and determination of arsenic in solid samples by ICP-MS.

    PubMed

    Villadangos, A F; Ordóñez, E; Muñoz, M I; Pastrana, I M; Fiuza, M; Gil, J A; Mateos, L M; Aller, A J

    2010-01-15

    A novel method for the retention of arsenate [As(V)] combining time-controlled solid-phase extraction with living bacterial biomass is presented. As(V) retention was carried out by exposing the extractant, consisting of a living double-mutant of Corynebacterium glutamicum strain ArsC1-C2, to the sample for a retention time of 1-7min, before the arsenic distribution equilibrium between the sample solution and the extractant was established. The amount of As(V) retained in the biomass was measured by inductively coupled plasma-mass spectrometry (ICP-MS) after the sample had been treated with nitric acid. A theoretical model of the retention process was developed to describe the experimental retention-time profiles obtained with the bacterial cells. This relationship provided a feasible quantification of the retention process before steady-state was reached, providing that the agitation conditions and the retention time had been controlled. An analytical procedure for the retention/quantification of As(V) was then developed; the detection limit was 0.1 ng As(V)mL(-1) and the relative standard deviation 2.4-3.0%. The maximum effective retention capacity for As(V) was about 12.5mgAs(g biomass)(-1). The developed procedure was applied to the determination of total arsenic in coal fly ash, using a sample that had undergone oxidative pre-treatment. PMID:20006108

  13. U-Pb Dating of CA/non-CA Treated Zircons Obtained by LA-ICP-MS and CA-TIMS Techniques: Impact for their Geological Interpretation

    NASA Astrophysics Data System (ADS)

    Von Quadt, A.; Gallhofer, D.; Guillong, M.; Peytcheva, I.

    2014-12-01

    Chemical Abrasion Isotope-Dilution Thermal Ionization Mass Spectrometry (CA-ID-TIMS) is known as a high precision technique for resolving lead loss and improving the interpretation of U-Pb zircon age data. We argue that combining CA with the widely applied Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) improves the precision and accuracy of zircon dates, while removing the substantial parts with lead loss, reducing data scatter, and providing meaningful geological interpretations. The samples are magmatic rocks chosen from different geological time periods (Paleozoic, Mesozoic and Cenozoic time). All zircon separates are analysed by LA-ICP-MS before and after CA, and all age data are compared with CA-ID-TIMS 206Pb/238U dates that are considered as the most accurately age. All CA-treated zircon crystals show up to 50% less data scatter compared to the non-CA treated zircon grains and thus a reduction of the calculated uncertainties is apparent. The obtained wt average LA-ICP-MS 206Pb/238U ages of the CA-treated zircon grains are up to 4-6% higher than those of the non-CA treated crystals, exceeding the analytical uncertainties of the LA-ICP-MS dating technique of 1-2%. The damaged crystal parts, caused by U-decay, with lead loss are removed, so that we can exclude younging from the possible geological scenarios. CA-LA-ICP-MS age data are in good agreement with the CA-ID-TIMS dates and suggest advantages of using CA-LA-ICP-MS in order to define accurate ages. The use of the CA technique for very young zircons (~0.2 Ma, Kos rhyolitic tuff, Greece) seems optional; as the obtained mean 206Pb/238U ages of non-CA and CA treated zircons coincide within the uncertainty. The negligible time to produce the lattice damage (based on alpha decay or spontaneous fission) makes lead loss less important for age dating and data interpretation of very young zircons (<1 Ma). Von Quadt, A. et al., 2014, JAAS, doi: 10.1039/c4ja00102h.

  14. 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.

  15. Simultaneous Determination of 10 Ultratrace Elements in Infant Formula, Adult Nutritionals, and Milk Products by ICP/MS After Pressure Digestion: Single-Laboratory Validation.

    PubMed

    Dubascoux, Stephane; Nicolas, Marine; Rime, Celine Fragniere; Payot, Janique Richoz; Poitevin, Eric

    2015-01-01

    A single-laboratory validation (SLV) is presented for the simultaneous determination of 10 ultratrace elements (UTEs) including aluminum (Al), arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), mercury (Hg), molybdenum (Mo), lead (Pb), selenium (Se), and tin (Sn) in infant formulas, adult nutritionals, and milk based products by inductively coupled plasma (ICP)/MS after acidic pressure digestion. This robust and routine multielemental method is based on several official methods with modifications of sample preparation using either microwave digestion or high pressure ashing and of analytical conditions using ICP/MS with collision cell technology. This SLV fulfills AOAC method performance criteria in terms of linearity, specificity, sensitivity, precision, and accuracy and fully answers most international regulation limits for trace contaminants and/or recommended nutrient levels established for 10 UTEs in targeted matrixes. PMID:26268978

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

    PubMed

    Seltzer, Michaeld; Berry, Kristinh

    2005-03-01

    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. PMID:15740773

  17. 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

  18. Trace elements determination in seawater by ICP-MS with on-line pre-concentration on a Chelex-100 column using a ‘standard’ instrument setup.

    PubMed Central

    Søndergaard, Jens; Asmund, Gert; Larsen, Martin M.

    2015-01-01

    Trace element determination in seawater is analytically challenging due to the typically very low concentrations of the trace elements and the potential interference of the salt matrix. A common way to address the challenge is to pre-concentrate the trace elements on a chelating resin, then rinse the matrix elements from the resin and subsequently elute and detect the trace elements using inductively coupled plasma mass spectrometry (ICP-MS). This technique typically involves time-consuming pre-treatment of the samples for ‘off-line’ analyses or complicated sample introduction systems involving several pumps and valves for ‘on-line’ analyses. As an alternative, the following method offers a simple method for ‘on-line’ analyses of seawater by ICP-MS. As opposed to previous methods, excess seawater was pumped through the nebulizer of the ICP-MS during the pre-concentration step but the gas flow was adjusted so that the seawater was pumped out as waste without being sprayed into the instrument. Advantages of the method include: • Simple and convenient analyses of seawater requiring no changes to the ‘standard’ sample introduction system except from a resin-filled micro-column connected to the sample tube. The ‘standard’ sample introduction system refers to that used for routine digest-solution analyses of biota and sediment by ICP-MS using only one peristaltic pump; and • Accurate determination of the elements V, Mn, Co, Ni, Cu, Zn, Cd and Pb in a range of different seawater matrices verified by participation in 6 successive rounds of the international laboratory intercalibration program QUASIMEME. PMID:26258050

  19. Trace elements determination in seawater by ICP-MS with on-line pre-concentration on a Chelex-100 column using a 'standard' instrument setup.

    PubMed

    Søndergaard, Jens; Asmund, Gert; Larsen, Martin M

    2015-01-01

    Trace element determination in seawater is analytically challenging due to the typically very low concentrations of the trace elements and the potential interference of the salt matrix. A common way to address the challenge is to pre-concentrate the trace elements on a chelating resin, then rinse the matrix elements from the resin and subsequently elute and detect the trace elements using inductively coupled plasma mass spectrometry (ICP-MS). This technique typically involves time-consuming pre-treatment of the samples for 'off-line' analyses or complicated sample introduction systems involving several pumps and valves for 'on-line' analyses. As an alternative, the following method offers a simple method for 'on-line' analyses of seawater by ICP-MS. As opposed to previous methods, excess seawater was pumped through the nebulizer of the ICP-MS during the pre-concentration step but the gas flow was adjusted so that the seawater was pumped out as waste without being sprayed into the instrument. Advantages of the method include: •Simple and convenient analyses of seawater requiring no changes to the 'standard' sample introduction system except from a resin-filled micro-column connected to the sample tube. The 'standard' sample introduction system refers to that used for routine digest-solution analyses of biota and sediment by ICP-MS using only one peristaltic pump; and•Accurate determination of the elements V, Mn, Co, Ni, Cu, Zn, Cd and Pb in a range of different seawater matrices verified by participation in 6 successive rounds of the international laboratory intercalibration program QUASIMEME. PMID:26258050

  20. 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.

  1. Comparative study on macro- and micro-elements concentration in Nicotiana tabacum and Faba siliquis plants by ICP-MS

    NASA Astrophysics Data System (ADS)

    Balazs, Zoltan; Voica, Cezara; Dehelean, Adriana; Magdas, Dana Alina; Ristoiu, Dumitru

    2015-12-01

    Plants are important components of ecosystems as they transfer elements from abiotic into biotic environments. The concentration of macro and micro-elements in tobacco leaves (Nicotiana tabacum) and bean (Faba siliquis) was analyzed using ICP-MS technique. The results obtained indicated that the mean concentration of Mg, P, K and Ca in tobacco leaves was 0.965, 0.812, 4.412 and 2.694 g.kg-1, respectively, while in bean samples were 0.899, 2.024, 6.725 and 1.387 g.kg-1, respectively. Mn concentration ranged from 156.835 mg.kg-1 to 234.593 mg.kg-1 in tobacco leaves and from 116.174 mg.kg-1 to 440.423 mg.kg-1 in bean samples. The results for Cu and Zn were between 7.262 mg.kg-1 and 105.738 mg.kg-1, 68.549 mg.kg-1 and 113.720 mg.kg-1 (tobacco leaves); and 6.830 mg.kg-1 and 46.034 mg.kg-1, 50.166 mg.kg-1 and 77.242 mg.kg-1 (bean samples), respectively. In analyzed samples, Pb, Cd and As concentrations ranged between <0.001-0.717 mg.kg-1, 0.046 mg.kg-1 -6.218 mg.kg-1, <0.001-0.381 mg.kg-1. The paper discusses the transfer of metal ions (Mn, As, Cd, Cu, Pb and Zn, respectively) from soil to these plants in terms of transfer factors (TF).

  2. Detection of zinc oxide and cerium dioxide nanoparticles during drinking water treatment by rapid single particle ICP-MS methods.

    PubMed

    Donovan, Ariel R; Adams, Craig D; Ma, Yinfa; Stephan, Chady; Eichholz, Todd; Shi, Honglan

    2016-07-01

    Nanoparticles (NPs) entering water systems are an emerging concern as NPs are more frequently manufactured and used. Single particle inductively coupled plasma-mass spectrometry (SP-ICP-MS) methods were validated to detect Zn- and Ce-containing NPs in surface and drinking water using a short dwell time of 0.1 ms or lower, ensuring precision in single particle detection while eliminating the need for sample preparation. Using this technique, information regarding NP size, size distribution, particle concentration, and dissolved ion concentrations was obtained simultaneously. The fates of Zn- and Ce-NPs, including those found in river water and added engineered NPs, were evaluated by simulating a typical drinking water treatment process. Lime softening, alum coagulation, powdered activated carbon sorption, and disinfection by free chlorine were simulated sequentially using river water. Lime softening removed 38-53 % of Zn-containing and ZnO NPs and >99 % of Ce-containing and CeO2 NPs. Zn-containing and ZnO NP removal increased to 61-74 % and 77-79 % after alum coagulation and disinfection, respectively. Source and drinking water samples were collected from three large drinking water treatment facilities and analyzed for Zn- and Ce-containing NPs. Each facility had these types of NPs present. In all cases, particle concentrations were reduced by a minimum of 60 % and most were reduced by >95 % from source water to finished drinking water. This study concludes that uncoated ZnO and CeO2 NPs may be effectively removed by conventional drinking water treatments including lime softening and alum coagulation. PMID:26960902

  3. Determination of trace elements in rape honey and its corresponding rape flower and stem by ICP-MS.

    PubMed

    Chen, Hui; Wang, Zhi-Bin; Chang, Qiao-Ying; Wang, Wei; Fan, Chun-Lin; Pang, Guo-Fang

    2014-02-01

    The determination of 10 trace elements including Na, Mg, P, K, Ca, Mn, Zn, Rb, Sr and Ba, in rape honey and its corresponding rape flower and stem gathered from nine sampling sites was carried out by inductively coupled plasma mass spectrometry (ICP-MS). The contents of K, P, Ca, Mg and Na were obviously higher than Zn, Rb, Mn, Sr and Ba in rape honey, rape flower and rape stem. For the first five elements, K had the highest content, followed by P, Ca, Mg and Na. However, the order of content for latter five elements was not the same in different matrixes. The contents of K, P and Ca were all higher than 1 000 mg x kg(-1) in rape flower and rape stem, while the contents of P, Ca, Mn, Zn and Rb in rape flower were slightly higher than in rape stem. It can be concluded that rape flower showed slightly higher concentrating ability for trace elements than rape stem. Based on these results, radar chart was firstly applied to research the relationship of 10 elements in rape honey and its corresponding rape flower and stem. The aim of the present work was to study the possibility of using trace elements contents in rape flower to trace the geographical and botanical origin of honey instead of rape honey. It can be found from the radar charts that the stars of rape honey, rape flower and rape stem were similar to each other. This research not only provides the basic data of trace elements in comparative study of rape honey, but also gives scientific basis for tracing the origin of rape honey according to the trace elements in corresponding rape flower that replaces those of rape honey. PMID:24822437

  4. Simultaneous determination of organotin pesticides by HPLC-ICP-MS and their sorption, desorption, and transformation in freshwater sediments.

    PubMed

    Gui, Wenjun; Tian, Chunxia; Sun, Qianqian; Li, Shuying; Zhang, Wei; Tang, Jun; Zhu, Guonian

    2016-05-15

    In order to better assess their environmental risks, the sorption and degradation of triphenyltin hydroxide, azocyclotin and fenbutatin oxide were studied in two sediments under varying laboratory conditions in this study. An analytical method for simultaneous determination of the three organotins in environmental samples was firstly developed using high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). The limit of detection and limit of quantification for standards ranged from 0.13 to 1.46 μg/L. Fortification study showed that when spiked at 2-250 μg/kg the mass recoveries were 73.7-119.6%. Sorption isotherm experiments indicated that the organotins could be strongly adsorbed by the sediments, and organotin sorption kinetics obeyed the pseudo second-order kinetic model. The sorption affinity was inversely related to their water solubility. All isotherms fitted with the Henry mode fairly well (r(2) > 0.96) with distribution coefficients (Kd) ranging from 746.1 to 2465.2 mL/g. The three organotins could rapidly move from the upper water layer to the lower sediment layer, and they were all of moderate degradation compounds with the degradation half lives varying from 38.3 to 84.5d in anaerobic and aerobic water-sediment systems. The degradation rate seemed to be positively related to organic matter content of sediment. Result inferred that the three organotins had the low risks to pollute groundwater when applied on dry land and could moderately degrade in water-sediment system. However, more attention should still be paid to these organotins due to the wide application on agricultural field. PMID:26994697

  5. [Application of ICP-MS to determination of heavy metal content of heavy metals in two kinds of N fertilizer].

    PubMed

    Rui, Yu-kui; Shen, Jian-bo; Zhang, Fu-suo

    2008-10-01

    Environmental safety has been the focus worldwide, where involved are the pollutions of heavy metals, pesticides and persistent organic pollutants. Fertilizer has become one of the polluting sources of heavy metals, which are very deleterious to human health and environmental safety. Heavy metals are difficult to metabolize in human body and very harmful, so research on the pollution of heavy metals is considered increasingly important. The pollution sources of heavy metals include waste residue, waste water and exhaust gas from industry and automobile, and garbage from human life. The heavy metals in fertilizer can endanger the human body by the crop containing heavy metals. Two kinds of nitrogen fertilizer were analyzed in terms of the content of heavy metals by ICP-MS, and the results showed that the content of 10 kinds of heavy metals (Al, Ti, Cr, Ni, Cu, Zn, As, Cd, Hg and Pb) in (NH4)2SO4 was 1345.13, 35.12, 2539.27, 287.26, 674.05, 270.79, 42.54, 22.13, 27.20 and 123.87 ng x g(-1) respectively; and in CO(NH2)2 it is 71.59, 5.36, 1167.71, 188.60, 7.46, 64.45, 10.55, 0.00, 0.09 and 3.71 ng x g(-1) respectively. All the data showed that CO(NH2)2 contained much less heavy metals than (NH4)2SO4, so we should select CO(NH2)2 as the nitrogen fertilizer in agricultural production. PMID:19123422

  6. A method for the routine determination of methylmercury in marine tissue by GC isotope dilution-ICP-MS.

    PubMed

    Valdersnes, Stig; Maage, Amund; Fliegel, Daniel; Julshamn, Kåre

    2012-01-01

    Currently, there is no legal limit for methyl mercury (MeHg) in food; thus, no standardized method for the determination of MeHg in seafood exists within the European jurisdiction. In anticipation of a future legislative limit an inductively coupled plasma isotope dilution mass spectrometry (GC-ICP-ID-MS) method was developed in collaboration with the European Standardization Organization (CEN). The method comprises spiking the tissue sample with Me201Hg, followed by decomposition with tetramethylammonium hydroxide, pH adjustment and derivatization with sodium tetraethylborate, and finally organic extraction of the derivatized MeHg in a hexane phase. Subsequently, the sample is analyzed via GC-ICP-MS and the result calculated using the ID equation. The working range of the method was 0.0005-1.321 mg/kg MeHg in marine tissue, with an internal reproducibility (RSD) of 12-1%. The method was validated based on statistical measures, such as the z-scores, using the commercially available reference materials from National Institute of Standards and Technology Standard Reference Material (NIST SRM) 1566b, NIST SRM 2977 and National Research Council of Canada (NRCC) TORT 2, NRCC, DORM 3, NRCC DOLT 4, and European Reference Material (ERM) CE 464. Z-scores for all standard reference materials, except for NIST SRM 1566b, were better than 11.51. The wide range of marine tissues used during the validation ensures that the method will be applicable for measuring of MeHg in seafood matrixes of all kinds. PMID:22970590

  7. Arsenic speciation in environmental waters by a new specific phosphine modified polymer microsphere preconcentration and HPLC-ICP-MS determination.

    PubMed

    Jia, Xiaoyu; Gong, Dirong; Wang, Jiani; Huang, Fuyi; Duan, Taicheng; Zhang, Xian

    2016-11-01

    A new specific phosphine modified polymer microsphere (PPMs) was designed and used as the core adsorbent to comprehensively enrich both inorganic and organic arsenic species in environmental waters by on line solid-phase extraction (SPE). Avoiding any redox reagent, all the four arsenic species have been quantitatively retained on the home made mini-column with large number of positively charged adsorption groups, and then eluted rapidly (within seconds) with a mixed solution of ammonium nitrate and ammonium dihydrogen phosphate. The trace separation and determination of As(III), DMA, MMA and As(V) species have been simultaneously achieved by high performance liquid chromatography hyphenated to inductively coupled plasma spectrometry (HPLC-ICP-MS) technique. This work has developed a versatile tri-n-butylphosphine functionalized polymer microsphere for an efficient and reliable on-line of simultaneous preconcentration and detection of inorganic and organic arsenic speciation. Under the optimized experimental conditions, the enrichment factors obtained for As(III) and DMA with 25mL sample solution were 28, while for MMA and As(V) reached 30. The low detection limits of 1.2ngL(-1), 0.96ngL(-1), 0.82ngL(-1) and 0.91ngL(-1), with the relative standard deviations (RSDs) of 3.9%, 5.6%, 3.2% and 4.5% were obtained for As(III), DMA, MMA and As(V), respectively. The developed method was validated by analyzing Certified Reference Materials GSBZ 07-3171-2014, promising for routine monitoring of arsenic species in lake water, river water and seawater samples. PMID:27591635

  8. U-Th dating of vein calcite by LA-MC-ICP-MS: preliminary results from geothermal systems

    NASA Astrophysics Data System (ADS)

    McGee, L. E.; Reich, M.; Rodriguez, V.; Leisen, M.; Barra, F.

    2014-12-01

    The measurement of U-series isotopes in precipitated minerals such as calcite holds various challenges, including low U and Th concentrations (in the ppb-ppt range), and the presence of detrital 232Th which can lead to age overestimations. Additionally, as yet there does not exist a calcite standard reference material for inter-laboratory accuracy and precision comparison, with most laboratories using their own in-house standard material and focussing largely on application to paleoclimate studies (e.g. corals and speleothems). In actively deforming regions, high-pressure hydrothermal fluids play an important role in faulting and vein formation, and commonly fault rupture is followed by rapid sealing through mineral precipitation. Therefore, precise dating of vein growth is of special importance to our understanding of the complex interplay between seismic events and fluid flow in the upper crust, and opens up a new field of study using U-Th techniques. The ability to accurately date fault-filling calcite within such settings has the power to elucidate the connection between structure and fluid flow in the development of geothermal systems, and provide valuable information on the longevity of the heat/water source, in addition to regional magmatic history. We are developing U-Th measurements and ages of vein calcite from geothermal systems using a Neptune Plus MC-ICP-MS (with 5 CDDs and 3 SEMs) coupled to an excimer 193nm Photon Machines laser. We will be comparing our results with an 189ka in-house flowstone calcite standard previously dated by TIMS, as well as developing a geothermal calcite standard.

  9. The Precise Determination of Cd Isotope Ratio in Geological Samples by MC-ICP-MS with Ion Exchange Separation

    NASA Astrophysics Data System (ADS)

    Du, C.; Hu, S.; Wang, D.; Jin, L.; Guo, W.

    2014-12-01

    Cadmium (Cd) is a trace element which occurs at μg g-1 level abundances in the crust. Cd isotopes have great prospects in the study of the cosmogony, the trace of anthropogenic sources, the micronutrient cycling and the ocean productivity. This study develops an optimized technique for the precise and accurate determination of Cd isotopic compositions. Cd was separated from the matrix by elution with AG-MP-1 anionic exchange chromatographic resin. The matrix elements (K, Na, Ca, Al, Fe, and Mg etc.), polyatomic interfered elements (Ge, Ga, Zr, Nb, Ru, and Mo), and isobaric interfered elements (In, Pd and most of Sn) were eluted using HCl with gradient descent concentrations (2, 0.3, 0.06, 0.012 and 0.0012 mol L-1). The same elution procedure was repeated to eliminate the residuel Sn (Sn/Cd < 0.018). The collected Cd was analyzed using MC-ICP-MS, in which the instrumental mass fractionation was controlled by a "sample-standard bracketing" technique. The recovery of Cd larger than 96.85%, and the δ114/110Cd are in the range of -1.43~+0.20‰ for ten geological reference materials (GSD-3a, GSD-5a, GSD-7a, GSD-6, GSD-9, GSD-10, GSD-11, GSD-12, GSD-23, and GSS-1). The δ114/110Cd obtained for GSS-1 soil sample relative to the NIST SRM 3108 Cd solution was 0.20, which was coherent with the literature values (0.08±0.23). This method had a precision of 0.001~0.002% (RSD), an error range of 0.06~0.14 (δ114/110Cd, 2σ), and a long-term reproducibility of 0.12 (δ114/110Cd, 2σ).

  10. A Study of the Accuracy and Precision Among XRF, ICP-MS, and PIXE on Trace Element Analyses of Small Water Samples

    NASA Astrophysics Data System (ADS)

    Naik, Sahil; Patnaik, Ritish; Kummari, Venkata; Phinney, Lucas; Dhoubhadel, Mangal; Jesseph, Aaron; Hoffmann, William; Verbeck, Guido; Rout, Bibhudutta

    2010-10-01

    The study aimed to compare the viability, precision, and accuracy among three popular instruments - X-ray Fluorescence (XRF), Inductively Coupled Plasma Mass Spectrometer (ICP-MS), and Particle-Induced X-ray Emission (PIXE) - used to analyze the trace elemental composition of small water samples. Ten-milliliter water samples from public tap water sources in seven different localities in India (Bangalore, Kochi, Bhubaneswar, Cuttack, Puri, Hospet, and Pipili) were prepared through filtration and dilution for proper analysis. The project speculates that the ICP-MS will give the most accurate and precise trace elemental analysis, followed by PIXE and XRF. XRF will be seen as a portable and affordable instrument that can analyze samples on-site while ICP-MS is extremely accurate, and expensive option for off-site analyses. PIXE will be deemed to be too expensive and cumbersome for on-site analysis; however, laboratories with a PIXE accelerator can use the instrument to get accurate analyses.

  11. 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. PMID:27305821

  12. Preliminary evaluation of a microwave-assisted metal-labeling strategy for quantification of peptides via RPLC-ICP-MS and the method of standard additions.

    PubMed

    Christopher, Steven J; Kilpatrick, Eric L; Yu, Lee L; Davis, W Clay; Adair, Blakely M

    2012-01-15

    NIST has performed preliminary research on applying a calibration methodology based on the method of standard additions to the quantification of peptides via reverse-phase liquid chromatography coupled to inductively coupled plasma mass spectrometry (RPLC-ICP-MS). A microwave-assisted lanthanide labeling procedure was developed and applied to derivatize peptides using the macrocyclic bifunctional chemical chelator DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid), which significantly improved the lanthanide labeling yield and reduced reaction times compared to benchtop labeling procedures. Biomolecular MS technologies of matrix-assisted laser desorption ionization (MALDI)-MS and electrospray ionization (ESI)-MS/MS were used in concert with ICP-MS to confirm the results of microwave labeling, sample cleanup and standard additions experiments for several test peptides. The calibration scheme is outlined in detail and contextualized against complementary high accuracy calibration strategies currently employed for ICP-MS detection of biomolecules. Standard additions experiments using native, non-isotopic peptide calibrants confirm the simplicity of the scheme and the potential of applying a blending (recombined sample and spike) procedure, facilitating calibration via co-elution of lanthanide labeled peptides. Ways to improve and fully leverage the analytical methodology are highlighted. PMID:22265570

  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. PMID:26979648

  14. Accurate and Precise in Situ Zircon U-Pb age Dating With High Sample Throughput by Automated LA-SF-ICP-MS

    NASA Astrophysics Data System (ADS)

    Frei, D.; Gerdes, A.; Schersten, A.; Hollis, J. A.; Martina, F.; Knudsen, C.

    2006-12-01

    Zircon is an ubiquitous mineral in most crystalline rocks as well as clastic sediments. The high resistance to thermal resetting and physical erosion makes zircon an exceptionally useful mineral for precise and accurate dating of thermal geological events. For example, the analysis of the U-Pb ages of detrital zircon grains in clastic sediments is a powerful tool in sedimentary provenance studies. Accurate and precise U-Pb ages of > 100 zircon grains in a sample usually allow to detect all major sedimentary source age components with statistical confidence. U-Pb age dating of detrital zircons is generally the domain of high resolution ion microprobe techniques (high resolution SIMS), where relatively rapid in situ analysis can be achieved. The major limitations of these techniques are sample throughput (about 75 zircon age dates per 24 hours), the very high purchasing and operating costs of the equipment and the need for highly specialised personnel, resulting in high cost. These high costs usually impose uncomfortable restrictions on the number of samples that can be analysed in a provenance study. Here, we present a high sample throughput technique for highly accurate and precise U-Pb dating of zircons by laser ablation magnetic sectorfield inductively coupled plasma mass spectrometry (LA-SF-ICP-MS). This technique takes advantage of recent progress in laser technology and the introduction of magnetic sectorfield ICP-MS instruments. Based on a ThermoFinnigan Element2 magnetic sctorfield ICP-MS and a New Wave UP 213 laser ablation system, this techniques allows U-Pb dating of zircon grains with precision, accuray and spatial resolution comparable to high resolution SIMS. Because an individual analysis is carried out in less than two minutes and all data is acquired automated in pre-set mode with only minimal operator presence, the sample throughput is an order of magnitude higher compared to high resolution SIMS. Furthermore, the purchasing and operating costs of

  15. 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

  16. Accidental potassium dichromate poisoning. Toxicokinetics of chromium by ICP-MS-CRC in biological fluids and in hair.

    PubMed

    Goullé, J P; Saussereau, E; Grosjean, J; Doche, C; Mahieu, L; Thouret, J M; Guerbet, M; Lacroix, C

    2012-04-10

    Intoxications by chromium (Cr) compounds are very life threatening and often lethal. After oral ingestion of 2 or 3g of hexavalent Cr (Cr(VI)), gastrointestinal injury, but also hepatic and renal failure, often occurs which each leads to a fatal outcome in most patients. Cellular toxicity is associated with mitochondrial and lysosomal injury by biologically Cr(VI) reactive intermediates and reactive oxygen species. After Cr(VI) has been absorbed, there is not much that can be done except to control the main complications as the treatment is only symptomatic. The biotransformation of Cr(VI) to Cr(III) reduces the toxicity because the trivalent form does not cross cellular membranes as rapidly. In fact, more than 80% of Cr(VI) is cleared in urine as Cr(III). We report the case of a 58-year-old male patient who was admitted to hospital after accidental oral ingestion of a 30 g/L potassium dichromate (the estimated amount of ingested Cr is about 3g). ICP-MS equipped with a collision/reaction cell (CRC) and validated methods were used to monitor plasma (P), red blood cells (RBCs), urine (U) and hair chromium. For urine the results were expressed per gram of creatinine. After 7 days in the intensive care unit, the patient was discharged without renal or liver failure. P, RBC and U were monitored during 49 days. During this period Cr decreased respectively from 2088 μg/L to 5 μg/L, 631 μg/L to 129 μg/L and 3512 μg/g to 10 μg/g. The half-life was much shorter in P than in RBC as the poison was more quickly cleared from the P than from the RBC, suggesting a cellular trapping of the metal. Hair was collected 2 months after the intoxication. We report a very rare case of survival after accidental Cr poisoning which has an extremely poor prognosis and usually leads to rapid death. For the first time, this toxicokinetic study highlights a sequestration of chromium in the RBC and probably in all the cells. PMID:22024652

  17. 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

  18. An HPLC-ICP-MS technique for determination of cadmium-phytochelatins in genetically modified Arabidopsis thaliana.

    PubMed

    Sadi, Baki B M; Vonderheide, Anne P; Gong, Ji-Ming; Schroeder, Julian I; Shann, Jodi R; Caruso, Joseph A

    2008-01-01

    A reversed-phase high-performance liquid chromatographic technique was developed to separate cadmium-phytochelatin complexes (Cd-PC2, Cd-PC3, and Cd-PC4) of interest in the plant Arapidopsis thaliana. High-performance liquid chromatography (HPLC) was coupled to an inductively coupled plasma mass spectrometric (ICP-MS) system with some modification to the interface. This was done in order to sustain the plasma with optimum sensitivity for cadmium detection in the presence of the high methanol loads used in the gradient elution of the reversed-phase separation. The detection limits were found to be 91.8 ngl(-1), 77.2 ngl(-1) and 49.2 ngl(-1) for Cd-PC2, Cd-PC3, and Cd-PC4 respectively. The regression coefficients (r2) for Cd-PC2 to Cd-PC4 detection ranged from 0.998 to 0.999. The method was then used to investigate the occurrence and effect of cadmium-phytochelatin complexes in wild-type Arabidopsis and a phytochelatin-deficient mutant cad1-3 that had been genetically modified to ectopically express the wheat TaPCS1 phytochelatin synthase enzyme. The primary complex found in both wild-type and transgenic plants was Cd-PC2. In both lines, higher levels of Cd-PC2 were found in shoots than in roots, showing that phytochelatin synthases contribute to the accumulation of cadmium in shoots, in the Cd-PC2 form. Genetic modification did, however, impact the overall accumulation of Cd. Transgenic plants contained almost two times more cadmium in the form of Cd-PC2 in their roots than did the corresponding wild-type plants. Similarly, the shoot samples of the modified species also contained more (by 1.6 times) cadmium in the form of Cd-PC2 than the wild type. The enhanced role of PC2 in the transgenic Arabidopsis correlates with data showing long-distance transport of Cd in transgenic plants. Targeted transgenic expression of non-native phytochelatin synthases may contribute to improving the efficiency of plants for phytoremediation. PMID:18065298

  19. An HPLC-ICP-MS technique for determination of cadmium–phytochelatins in genetically modified Arabidopsis thaliana

    PubMed Central

    Sadi, Baki B.M.; Vonderheide, Anne P.; Gong, Ji-Ming; Schroeder, Julian I.; Shann, Jodi R.; Caruso, Joseph A.

    2010-01-01

    A reversed-phase high-performance liquid chromatographic technique was developed to separate cadmium–phytochelatin complexes (Cd-PC2, Cd-PC3, and Cd-PC4) of interest in the plant Arapidopsis thaliana. High-performance liquid chromatography (HPLC) was coupled to an inductively coupled plasma mass spectrometric (ICP-MS) system with some modification to the interface. This was done in order to sustain the plasma with optimum sensitivity for cadmium detection in the presence of the high methanol loads used in the gradient elution of the reversed-phase separation. The detection limits were found to be 91.8 ng l−1, 77.2 ng l−1 and 49.2 ng l−1 for Cd-PC2, Cd-PC3, and Cd-PC4 respectively. The regression coefficients (r2) for Cd-PC2 to Cd-PC4 detection ranged from 0.998 to 0.999. The method was then used to investigate the occurrence and effect of cadmium–phytochelatin complexes in wild-type Arabidopsis and a phytochelatin-deficient mutant cad1-3 that had been genetically modified to ectopically express the wheat TaPCS1 phytochelatin synthase enzyme. The primary complex found in both wild-type and transgenic plants was Cd-PC2. In both lines, higher levels of Cd-PC2 were found in shoots than in roots, showing that phytochelatin synthases contribute to the accumulation of cadmium in shoots, in the Cd-PC2 form. Genetic modification did, however, impact the overall accumulation of Cd. Transgenic plants contained almost two times more cadmium in the form of Cd-PC2 in their roots than did the corresponding wild-type plants. Similarly, the shoot samples of the modified species also contained more (by 1.6 times) cadmium in the form of Cd-PC2 than the wild type. The enhanced role of PC2 in the transgenic Arabidopsis correlates with data showing long-distance transport of Cd in transgenic plants. Targeted transgenic expression of non-native phytochelatin synthases may contribute to improving the efficiency of plants for phytoremediation. PMID:18065298

  20. 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

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

    PubMed Central

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

    2012-01-01

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

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

    PubMed

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

    2012-05-15

    A method based on cold vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS) has been developed for determination of inorganic mercury, Hg(II), and total mercury in fish otoliths. Sodium borohydride (NaBH(4)) was used as the only reducing agent and its concentration was optimized across an acidity gradient to selectively reduce Hg(II) without affecting methylmercury, CH(3)Hg(I). Inorganic Hg was quantitatively reduced to elemental mercury (Hg(0)) with 1 × 10(-4)% (m/v) NaBH(4). CH(3)Hg(I) required a minimum of 0.5% (m/v) NaBH(4) for complete reduction. Increasing the HCl concentration of solution to 5% (v/v) improved the selectivity toward Hg(II) as it decreased the signals from CH(3)Hg(I) to baseline levels. Potassium ferricyanide solution was the most effective in eliminating the memory effects of Hg compared with a number of chelating and oxidizing agents, including EDTA, gold chloride, thiourea, cerium ammonium nitrate and 2-mercaptoethylamine chloride. The relative standard deviation (RSD) was less than 5% for 1.0 μg L(-1) Hg(II) solution. The detection limits were 4.2 and 6.4 ng L(-1) (ppt) for Hg(II) and total Hg, respectively. Sample dissolution conditions and recoveries were examined with ultra-pure CaCO(3) (99.99%) spiked with Hg(II) and CH(3)HgCl. Methylmercury was stable when dissolution was performed with up to 20% (v/v) HCl at 100°C. Recoveries from spiked solutions were higher than 95% for both Hg(II) and CH(3)Hg(I). The method was applied to the determination of Hg(II) and total Hg concentrations in the otoliths of red emperor (CRM 22) and Pacific halibut. Total Hg concentration in the otoliths was 0.038 ± 0.004 μg g(-1) for the red emperor and 0.021 ± 0.003 μg g(-1) for the Pacific halibut. Inorganic Hg accounted for about 25% of total Hg indicating that Hg in the otoliths was predominantly organic mercury (e.g., methylmercury). However, as opposed to the bioaccumulation in tissues, methylmercury levels in otoliths was

  3. 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

  4. 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

  5. Selected problems with boron determination in water treatment processes. Part I: comparison of the reference methods for ICP-MS and ICP-OES determinations.

    PubMed

    Kmiecik, Ewa; Tomaszewska, Barbara; Wątor, Katarzyna; Bodzek, Michał

    2016-06-01

    The aim of the study was to compare the two reference methods for the determination of boron in water samples and further assess the impact of the method of preparation of samples for analysis on the results obtained. Samples were collected during different desalination processes, ultrafiltration and the double reverse osmosis system, connected in series. From each point, samples were prepared in four different ways: the first was filtered (through a membrane filter of 0.45 μm) and acidified (using 1 mL ultrapure nitric acid for each 100 mL of samples) (FA), the second was unfiltered and not acidified (UFNA), the third was filtered but not acidified (FNA), and finally, the fourth was unfiltered but acidified (UFA). All samples were analysed using two analytical methods: inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES). The results obtained were compared and correlated, and the differences between them were studied. The results show that there are statistically significant differences between the concentrations obtained using the ICP-MS and ICP-OES techniques regardless of the methods of sampling preparation (sample filtration and preservation). Finally, both the ICP-MS and ICP-OES methods can be used for determination of the boron concentration in water. The differences in the boron concentrations obtained using these two methods can be caused by several high-level concentrations in selected whole-water digestates and some matrix effects. Higher concentrations of iron (from 1 to 20 mg/L) than chromium (0.02-1 mg/L) in the samples analysed can influence boron determination. When iron concentrations are high, we can observe the emission spectrum as a double joined and overlapping peak. PMID:26939686

  6. Extravasation of Pt-based chemotherapeutics - bioimaging of their distribution in resectates using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS).

    PubMed

    Egger, Alexander E; Kornauth, Christoph; Haslik, Werner; Hann, Stephan; Theiner, Sarah; Bayer, Günther; Hartinger, Christian G; Keppler, Bernhard K; Pluschnig, Ursula; Mader, Robert M

    2015-03-01

    Platinum-based drugs (cisplatin, carboplatin and oxaliplatin) are widely used in cancer treatment. They are administered intravenously, thus accidental extravasations of infusions can occur. This may cause severe complications for the patient as the toxic platinum compounds likely persist in subcutaneous tissue. At high concentrations, platinum toxicity in combination with local thrombosis may result in tissue necrosis, eventually requiring surgical intervention. To describe tissue distribution at the anatomic level, we quantified drug extravasation in cryosections of various tissues (muscle, nerve tissue, connective tissue, fat tissue) by means of quantitative laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and compared the resulting data with bulk analysis of microwave-assisted digestion of tissue samples followed by ICP-MS analysis. Samples of three patients receiving systemic chemotherapy either via peripheral venous access or central access via port-a-cath® were analyzed. Pt was enriched up to 50-times in connective tissue when compared with muscle tissue or drain samples collected over five days. The large areas of subcutaneous fat tissue showed areactive necrosis and average Pt concentrations (determined upon sample digestion) ranged from 0.2 μg g(-1) (therapy with 25 mg m(-2) cisplatin, four weeks after peripheral extravasation) to 10 μg g(-1) (therapy with 50 mg m(-2) oxaliplatin: four weeks after port-a-cath® extravasation). A peripheral nerve subjected to bioimaging by LA-ICP-MS showed a 5-times lower Pt concentration (0.2 μg g(-1)) than the surrounding connective tissue (1.0 μg g(-1)). This is in accordance with the patient showing no signs of neurotoxicity during recovery from extravasation side-effects. Thus, bioimaging of cutaneous nerve tissue may contribute to understand the risk of peripheral neurotoxic events. PMID:25659827

  7. Determination of δ11B by HR-ICP-MS from mass limited samples: Application to natural carbonates and water samples

    NASA Astrophysics Data System (ADS)

    Misra, Sambuddha; Owen, Robert; Kerr, Joanna; Greaves, Mervyn; Elderfield, Henry

    2014-09-01

    We present an improved method for accurate and precise determination of the boron isotopic composition (11B/10B) of carbonate and water samples using a mineral acid matrix and HR-ICP-MS. Our method for δ11B determination utilizes a micro-distillation based boron purification technique for both carbonate and seawater matrices. The micro-distillation method is characterized by low blank (⩽0.01 ng-B) and 99.8 ± 5.7% boron recovery. We also report a new ICP-MS method, performed in a hydrofluoric acid matrix, using a jet interface fitted Thermo® Element XR that consumes <3.0 ng-B per quintuplicate analyses (±0.5‰, 2σ, n = 5). A comparatively high matrix tolerance limit of ⩽50 ppb Na/K/Mg/Ca characterizes our ICP-MS method. With an extremely low procedural blank (⩽0.05 ± 0.01 ng-B) the present isotope method is optimized for rapid (∼25 samples per session) analysis of small masses of carbonates (foraminifera, corals) with low boron abundance and small volume water samples (seawater, porewater, river water). Our δ11B estimates of seawater (39.8 ± 0.5‰, 2σ, n = 30); SRM AE-120 (-20.2 ± 0.5‰, 2s, n = 33); SRM AE-121 (19.8 ± 0.4‰, 2s, n = 16); SRM AE-122 (39.6 ± 0.5‰, 2s, n = 16) are within analytical uncertainty of published values. We apply this new method to assess the impacts of laboratory handling induced sample contamination and seawater physio-chemical parameters (temperature, pH, and salinity) on marine carbonate bound δ11B by analyzing core-top planktonic foraminifera samples.

  8. Study and determination of elemental impurities by ICP-MS in active pharmaceutical ingredients using single reaction chamber digestion in compliance with USP requirements.

    PubMed

    Muller, Aline L H; Oliveira, Jussiane S S; Mello, Paola A; Muller, Edson I; Flores, Erico M M

    2015-05-01

    In this work a method for active pharmaceutical ingredients (APIs) digestion using the single reaction chamber (SRC-UltraWave™) system was proposed following the new recommendations of United States Pharmacopeia (USP). Levodope (LEVO), primaquine diphosphate (PRIM), propranolol hydrochloride (PROP) and sulfamethoxazole (SULF) were used to evaluate the digestion efficiency of the proposed method. A comparison of digestion efficiency was performed by measuring the carbon content and residual acidity in digests obtained using SRC and in digests obtained using conventional microwave-assisted digestion system (Multiwave(TM)). Three digestion solutions (concentrated HNO3, aqua regia or inverse aqua regia) were evaluated for digestion of APIs. The determination of Cd, Ir, Mn, Mo, Ni, Os, Pb, Pd, Pt, Rh, Ru was performed using inductively coupled plasma mass spectrometry (ICP-MS) in standard mode. Dynamic reaction cell (DRC) mode was used for the determination of (51)V, (52)Cr, (53)Cr, (63)Cu and (65)Cu in order to solve polyatomic ion interferences. Arsenic and Hg were determined using chemical vapor generation coupled to ICP-MS (FI-CVG-ICP-MS). Masses of 500mg of APIs were efficiently digested in a SRC-UltraWave™ system using only HNO3 and allowing a carbon content lower than 250mg L(-1) in final digests. Inverse aqua regia was suitable for digestion of sample masses up to 250mg allowing the determination of Ir, Pd, Pt, Rh and Ru. By using HNO3 or inverse aqua regia, suitable recoveries were obtained (between 91 and 109%) for all analytes (exception for Os). Limits of quantification were in agreement with USP requirements and they ranged from 0.001 to 0.015µg g(-1) for all elemental impurities (exception for Os). The proposed method was suitable for elemental impurities determination in APIs and it can be used in routine analysis for quality control in pharmaceutical industries. PMID:25702998

  9. A novel quantification strategy of transferrin and albumin in human serum by species-unspecific isotope dilution laser ablation inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Feng, Liuxing; Zhang, Dan; Wang, Jun; Shen, Dairui; Li, Hongmei

    2015-07-16

    Species-specific (SS) isotope dilution analysis with gel electrophoresis (GE)-laser ablation (LA)-ICP-MS is a promising technique for the quantification of particular metal-binding proteins in biological samples. However, unavailable isotopically enriched spike and metal losses in GE separation are main limitations for SS-isotope dilution PAGE-LA-ICP-MS. In this study, we report for the first time the absolute quantification of transferrin (Tf) and albumin (Alb) in human serum by non-denaturing (native) GE combined with species-unspecific isotope dilution mass spectrometry (IDMS). In order to achieve a homogeneous distribution of both protein and isotope-enriched spike (simulated isotope equilibration), immersing the protein strips with (34)S spike solution after gel electrophoresis was demonstrated to be an effective way of spike addition. Furthermore, effects of immersion time and (34)S spike concentration were investigated to obtain optimal conditions of the post-electrophoresis isotope dilution method. The relative mass of spike and ablated sample (m(sp)/m(sam)) in IDMS equation was calculated by standard Tf and Alb proteins, which could be applied to the quantification of Tf and Alb in ERM-DA470k/IFCC for method confirmation. The results were in agreement with the certified value with good precision and small uncertainty (1.5-3%). In this method, species-specific spike protein is not necessary and the integrity of the heteroatom-protein could be maintained in sample preparation process. Moreover, the application of species-unspecific isotope dilution GE-LA-ICP-MS has the potential to offer reliable, direct and simultaneous quantification of proteins after conventional 1D and 2D gel electrophoretic separations. PMID:26073803

  10. 234U/238U isotope ratios in groundwater from Southern Nevada: a comparison of alpha counting and magnetic sector ICP-MS.

    PubMed

    Cizdziel, James; Farmer, Dennis; Hodge, Vernon; Lindley, Kazumasa; Stetzenbach, Klaus

    2005-11-01

    The 234U/238U activity ratio (AR) is extensively used as a geochemical tool to investigate movement and flow relationships in major hydrological units, information that is particularly important when considering nuclear waste disposal. It is usually determined by radiochemical separation and concentration of U, followed by energy-specific alpha particle counting. Alternatively, sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) can be used to measure U isotopic signatures directly in groundwater samples. Here, we compare the two methods for samples of spring and groundwater from southern Nevada. Results for samples stripped from stainless steel disks, previously used for alpha counting, and for splits of groundwater samples show good agreement between the methods. However, SF-ICP-MS is faster, requires much less sample, and produces essentially no waste. We demonstrate applicability of the SF-ICP-MS method for groundwater collected from over 25 wells on and near the Nevada Test Site during 2003. Uranium concentrations ranged from 0.17 to 9.87 ppb with a mean of 2.9 ppb, while 234U/238U AR values ranged from 1.9 to 11.5 with a mean of 4.3. Groundwater collected from deep wells in the northern part of the study area tended to have moderate to high U concentrations and AR values, possibly representative of older volcanic-type waters, whereas groundwater from wells in the Fortymile Wash area had relatively low AR and U concentrations, suggesting younger waters with a possible local recharge component. PMID:16227084

  11. Feasibility of ultra-trace determination of bromine and iodine in honey by ICP-MS using high sample mass in microwave-induced combustion.

    PubMed

    Costa, Vanize C; Picoloto, Rochele S; Hartwig, Carla A; Mello, Paola A; Flores, Erico M M; Mesko, Marcia F

    2015-10-01

    This work demonstrates the feasibility of ultra-trace determination of halogens in biological samples by inductively coupled plasma mass spectrometry (ICP-MS) after decomposition by microwave-induced combustion (MIC). The conventional MIC method was improved to allow the combustion of samples with mass higher than that used in previous works in order to achieve better limits of detection (LODs). The applicability of the proposed method for ultra-trace determination of bromine and iodine in organic samples was demonstrated here using honey. It was possible to decompose up to 1000 mg of honey using microcrystalline cellulose as a combustion aid and polyethylene film for sample wrapping. After combustion, analytes were absorbed using 50 mmol L(-1) NH4OH and recoveries for Br and I were between 99 and 104 %, and relative standard deviations were lower than 5 %. Microwave-assisted alkaline dissolution (MA-AD) was also evaluated for honey sample preparation using NH4OH or tetramethylammonium hydroxide solutions. However, the LODs for the MA-AD method were unsuitable because the high carbon content in digests required a dilution step prior to the analysis by ICP-MS. The LODs obtained by MIC were improved from 1143 to 34 ng g(-1) for Br and from 571 to 6.0 ng g(-1) for I, when compared to the MA-AD method. Furthermore, it was possible to decompose up to eight samples simultaneously in 30 min (including the cooling step) with very low reagent consumption and consequently lower generation of effluents, making MIC method well suited for routine ultra-trace determination of Br and I in honey. Graphical Abstract A high mass of honey was efficiently digested by MIC for subsequent Br and I determination by ICP-MS. PMID:26310846

  12. 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. PMID:19892565

  13. Rapid screening of copper intermediates in Cu(i)-catalyzed azide-alkyne cycloaddition using a modified ICP-MS/MS platform.

    PubMed

    He, Qian; Xing, Zhi; Wei, Chao; Fang, Xiang; Zhang, Sichun; Zhang, Xinrong

    2016-08-18

    Rapid screening of Cu(+)-intermediates by using (63)Cu(+) or (65)Cu(+) ions as catalysts with or without ligand protection in Cu(i)-catalyzed azide-alkyne cycloaddition was realized using an on-line modified ICP-MS/MS platform in this work, while the Cu(+)-intermediates without ligand protection are very active, which are extremely difficult to be observed using other existing techniques. This universal platform was suitable to study the mechanism of organic reactions catalyzed by unstable metal(i) ions as well as to discover new candidates for metal(i) catalysts. PMID:27487942

  14. Determination of cadmium and lead species and phytochelatins in pea (Pisum sativum) by HPLC-ICP-MS and HPLC-ESI-MSn.

    PubMed

    Barałkiewicz, Danuta; Kózka, Małgorzata; Piechalak, Aneta; Tomaszewska, Barbara; Sobczak, Paweł

    2009-07-15

    An analytical approach based on hyphenated techniques was used for studying the speciation of cadmium and lead in Pisum sativum. Proper preservation conditions were employed to avoid the oxidation of -SH groups and corresponding decomposition of metal-binding complexes. SEC column was washed with 5 mM beta-mercaptoethanol and then samples were analysed using ICP-MS as a detector. Results showed that cadmium is the inhibitor of lead uptake. HPLC-ESI-MS(n) assays revealed fragmentation pathways of phytochelatins. PMID:19559910

  15. Estimation of the formation rates of polyatomic species of heavy metals in plutonium analyses using a multicollector ICP-MS with a desolvating nebulizer

    SciTech Connect

    Mitroshkov, Alexandre V.; Olsen, Khris B.; Thomas, Linda M.

    2015-01-01

    The analyses of IAEA and environmental samples for Plutonium isotopic content are conducted normally at very low concentrations of Pu–usually in the range of part per trillion level and even more often at the parts per quadrillion level. To analyze such low concentrations, the interferences in the analytical solution must be reduced as much as possible. Polyatomic interferences (PIs), formed by the heavy metals (HMs) from Hf to Bi are known to create the problems for Pu isotopic analyses, because even the relatively high resolution of a modern multicollector ICP-MS is not enough to separate Pu isotopes from this PIs in most of the cases. Desolvating nebulizers (DSN) (e.g. APEX and AridusII) reduce significantly the formation of PIs compare to the use of wet plasma. The purpose of this work was to investigate the rate of formation of PIs, produced by HMs, when high resolution MC ICP-MS with desolvating nebulizer was used for Pu isotopic analyses and to estimate the influence of the metals present in the sample on the results of analyses. The NU Plasma HR Multicollector and AridusII desolvating nebulizer were used in this investigation. This investigation was done for all Pu isotopes normally analyzed by ICP-MS, including ²⁴⁴Pu, with the exception of ²³⁸Pu, which most of the time can’t be analyzed by ICP-MS, because of the overwhelming presence of ²³⁸U in the solutions. The PI formation rates were determined and reported for all 12 HMs from Hf to Bi. Selected IAEA samples were scanned for the presence of HMs and the influence of HMs on the results of Pu isotopic analyses was evaluated. It was found that the implemented separation procedure provides sufficient separation of HM from Pu, although the effect of PIs on the measurement of low level isotopes like ²⁴¹Pu and ²⁴²Pu in some cases can still be observed.

  16. 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

  17. 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

  18. Optimisation of sample preparation protocols for measurement of PGE and Re-Os in organic-rich shales by isotope dilution ICP-MS

    NASA Astrophysics Data System (ADS)

    Rammensee, Philipp; Aulbach, Sonja; Gudelius, Dominik; Brey, Gerhard

    2013-04-01

    Platinum-group elements (PGE) and Re-Os isotopes, which are variably redox-sensitive and fluid-soluble, have potential as proxies for the oxygenation of the atmosphere and oceans (e.g. [1]). However, analysis of these elements in organic rich shales (ORS) is challenging due to abundances of <1 ng/g and the presence of interfering isotopes or molecules of matrix elements. Furthermore, PGE-ReOs systematics in detrital and hydrogenous components may vary, and the choice of digestion parameters (reagents, temperature and pressure) during decomposition of rock powder affects the ratio of digested components [2,3]. Additional treatment to remove the matrix and pre-concentrate PGE-Re by column chromatography is necessary to minimise the effects of interfering elements, but presents its own challenges. We are in the process of conducting variations of acid digestion and column chromatographic protocols on reference sample SDO-1 (Devonian Ohio Shale, USGS). We aim to identify the optimum protocol to investigate PGE-Re-Os systematics of ORS that were sampled as part of the Barberton Drilling Project BARB5 drill core, in order to constrain the changes in detrital and hydrogenous contributions to the sediment with time, to assess the extent of euxinity in the sedimentary basin and to look for evidence of transient "whiffs of oxygen" [1]. The following digestion methods were tested: (1) 4h acid digestion in High Pressure Asher (HPA) apparatus with reverse aqua regia at 300°C and 130 bar (only this digestion allows extraction of volatilised Os in CHCl3 followed by HBr); (2) 3h reverse aqua regia digestion in centrifuge vials on hotplate at 80°C; (3) 48h reverse aqua regia digestion in closed Teflon beakers on hotplate at 140°C followed by a HF/HNO3 digestion step; (4) 48h HF/HNO3 digestion of ashed sample powder in closed Teflon beaker at 140°C on hotplate followed by an aqua regia digestion step. Column chromatographic approaches to decrease the concentrations of interfering elements (Y, Zr, Mo, Cd, Hf, Hg) include the use of cation- and anion resins, and variations of the molarity and composition of the eluent. Preliminary results show that digestion method (1) leaves behind small amounts of presumably PGE-free silica gel; (2) yields consistently higher Re concentrations with an expectedly large amount of solid residue; (3) produces an insoluble sludge; (4) allows complete digestion, but precludes the collection of Os. Column calibrations show the best recovery of PGE-Re in cation resin using 0.2 mol/l HCl as eluent, but intolerably high ratios of interfering over elements of interest, whereas the best matrix separation is achieved using 0.05 mol/l HCl as eluent, but is accompanied by low PGE-Re yields presumably due to the instability of Cl complexes in this medium. They also show that U elutes separately from PGE-Re in 6 mol/l HCl and could be collected with a view to analysing U isotopes as an additional redox proxy. Further tests will be carried out using alternative high-pressure digestion systems. [1] Anbar, et al. (2007) Science 317:1903-1906; [2] Meisel et al. (2003) JAAS 18:720-726; [3] Xu et al. (2012) CG 324:132-147

  19. 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.

  20. Direct ICP-MS determination of trace and ultratrace elements in geological materials after decomposition in a microwave oven. I. Quantitation of Y, Th, U and the lanthanides.

    PubMed

    Gupta, J G; Bertrand, N B

    1995-11-01

    A microwave digestion technique using a mixture of HF + HNO(3) + HCl + H(3)BO(3) was found to be effective for the rapid dissolution of various silicate rock and sediment reference samples. From the solutions thus prepared, it was possible to determine quantitatively trace and ultratrace amounts of yttrium, thorium, uranium and the lanthanides by inductively coupled plasma-mass spectrometry (ICP-MS) without any separation of matrix elements or preconcentration. In the ICP-MS determinations, oxide and non-spectral interferences on individual masses of the rare earth element ions were corrected by the method of algebraic approach of elimination and dilution, respectively, and measurement drift was controlled by ruthenium and rhenium internal standards. The method yielded excellent results comparable with "recommended", "consensus" and "working" values of the literature for the specified elements on various well-known international reference materials such as andesite (AGV-1), basalts (BCR-1, BHVO-1, BIR-1 and BE-N), granites (G-2 and NIM-G), syenite (SY-2), gabbro (MRG-1), diabase (W-2 and DNC-1), marine mud (MAG-1), river sediment (NBS 1645), lake sediments (LKSD-1-LKSD-4) and stream sediment (GSD-1, GSD-5, GSD-6 and STSD-1-STSD-4)). New values for Er, Gd, Ho, Pr and Tm in LKSD-1-LKSD-4 and STSD-1-STSD-4, and Er, Ho, Lu, Nd, Pr, Tb, Tm and Yb in NBS 1645 are first reported in this work. PMID:18966393

  1. Simplified method for the determination of Ru, Pd, Re, Os, Ir and Pt in chromitites and other geological materials by isotope dilution ICP-MS and acid digestion.

    PubMed

    Meisel, T; Moser, J; Fellner, N; Wegscheider, W; Schoenberg, R

    2001-03-01

    A method for the determination of low Ru, Pd, Re, Os, Ir and Pt abundances in geological reference materials by isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion in a high pressure asher (HPA-S) is presented. The digestion technique is similar to that using Carius tubes but easier to handle and reaches higher temperatures. Osmium can be determined as OsO4 with ICP-MS directly after digestion through a sparging technique. The remaining elements are preconcentrated by means of anion column chromatography. The resin is digested directly without elution leading to high yields but this causes problems if Zr is present at higher levels in the silicate rich materials. The analytical results for international platinum group element (PGE) reference materials, chromitite CHR-Bkg, basalt TDB-1 and gabbro WGB-1, are presented and compared with literature data, demonstrating the validity of the described method. Although higher in concentration, PGEs determined for reference material WGB-1 were worse than for TDB-1 indicating a more inhomogeneous distribution of the platinum group mineral phases. The low PGE abundance chromitite standard, CHR-Bkg, is likely to be homogeneous for Ru, Re, Os and Ir and is recommended as a reference material for the study of chromitites. Detection limits (3s x total procedure blank) range from 0.012 ng (Re and Os) to 0.77 ng (Pt), which could be further improved by applying higher quality acids. PMID:11284333

  2. Comparison of MP AES and ICP-MS for analysis of principal and selected trace elements in nitric acid digests of sunflower (Helianthus annuus).

    PubMed

    Karlsson, Stefan; Sjöberg, Viktor; Ogar, Anna

    2015-04-01

    The use of nitrogen as plasma gas for microwave plasma atomic emission spectroscopy (MP AES) is an interesting development in analytical science since the running cost can be significantly reduced in comparison to the inductively coupled argon plasma. Here, we evaluate the performance of the Agilent 4100 MP AES instrument for the analysis of principal metals (Ca, K, Mg, and Na), lithogenic metals (Al, Fe, and Mn) and selected trace metals (As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn) in nitric acid plant digests. The digests were prepared by microwave-assisted dissolution of dry plant material from sunflower (Helianthus annuus) in concentrated nitric acid. Comparisons are made with analysis of the same solutions with ICP-MS (Agilent 7500cx) using the octopole reaction system (ORS) in the collision mode for As, Fe, and V. The limits of detection were usually in the low µg L(-1) range and all principal and lithogenic metals were successfully determined with the MP AES and provided almost identical results with the ICP-MS. The same applies for the selected trace metals except for As, Co and Mo where the concentrations were below the detection limit with the MP AES. For successful analysis we recommend that (i) only atom lines are used, (ii) ionization is minimized (e.g. addition of CsNO3) and (iii) the use of internal standards should be considered to resolve spectral interferences. PMID:25640135

  3. Speciation of nickel, copper, zinc, and manganese in different edible nuts: a comparative study of molecular size distribution by SEC-UV-ICP-MS.

    PubMed

    Wuilloud, Rodolfo G; Kannamkumarath, Sasi S; Caruso, Joseph A

    2004-06-01

    Molecular size distribution patterns of Cu, Mn, Ni, and Zn were determined in several nut species by size-exclusion liquid chromatography (SEC) coupled on-line to UV and inductively coupled plasma mass spectrometry (ICP-MS) for detection. The molecular weight (MW) fractionation of the different metals was performed with a Superdex Peptide column, injecting 100 microL of the extracted solutions. The association of the elements with different MW fractions was observed with sequential detection by UV and ICP-MS. Various separation conditions were evaluated to obtain proper resolution and reproducible results with the size-exclusion column. Complete MW information of the elemental fractions in the nut samples was obtained within a retention time of 30 min. Fractionation of the above mentioned elements was done in nine different nut species commonly found in commercial markets. Variability of the fractionation patterns for two different extraction media, 0.05 mol L(-1) NaOH and 0.05 mol L(-1) HCl, was evaluated for every nut sample. Differences in the elemental fractionation patterns were found depending on the extraction procedure, nut species, and the type of element studied. It was also observed that the elements studied showed predominant association with high MW fractions when extracted with basic solution whereas with acidic extraction media only low MW fractions were obtained. PMID:15048546

  4. Study of the effect of sample preparation and cooking on the selenium speciation of selenized potatoes by HPLC with ICP-MS and electrospray ionization MS/MS.

    PubMed

    Infante, Heidi Goenaga; Borrego, Ana Arias; Peachey, Emma; Hearn, Ruth; O'Connor, Gavin; Barrera, Tamara García; Ariza, José Luis Gómez

    2009-01-14

    The efficiency of enzymatic hydrolysis and leaching with water using accelerated solvent extraction (ASE) or boiling was investigated for quantitative Se speciation in selenized potatoes using reversed phase HPLC coupled to ICP-MS. Preliminary identification of selenomethionine (SeMet), Se-methylselenocysteine (SeMeCys), and selenate in extracts of potato skin and flesh was achieved using complementary reversed phase and anion-exchange HPLC-ICP-MS and retention time matching with standards. The quantitative speciation data revealed a higher percentage of selenomethionine (73% of the total Se) found in the flesh in comparison with skin (containing 21% of the total Se as SeMet). ASE and boiling in water were found to be similar in terms of Se extraction efficiency and profiles. However, ASE was found to be more efficient than boiling with respect to sample cleanup and reduced sample handling. The presence of SeMet at parts per billion levels in selenized potatoes was confirmed by reversed phase HPLC with online ESI MS/MS. PMID:19093878

  5. Comparitive study of the sample decomposition procedures in the determination of trace and rare earth elements in anorthosites and related rocks by ICP-MS.

    PubMed

    Balaram, V; Ramesh, S L; Anjaiah, K V

    1995-09-01

    ICP-MS has been used for the determination of over 30 geochemically significant trace elements (Sc, V, Cr, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th, U and REEs) in anorthosites and related rock reference samples. Open acid digestion, pressure decomposition using HF, HNO(3) and HClO(4), and a fusion method using lithium metaborate and subsequent dissolution in dil. HNO(3) were adopted for the decomposition of these rock samples before analysis. The dissolution problems and interference effects are discussed. Rh and Bi were used as internal standards. The first set of data on several rare earths and other trace elements in the Russian anorthosite reference sample, MO-6 are presented along with data on other samples. The data are compared with the available data. The results obtained with different dissolution methods were found to be in good agreement for the majority of the trace elements. The accuracy and precision achieved (better than 6% RSD in most cases) suggested that the data obtained by ICP-MS for such samples are best suited for geochemical interpretations. PMID:15048536

  6. 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.

  7. Isotope dilution quantification of ultratrace gamma-glutamyl-Se-methylselenocysteine species using HPLC with enhanced ICP-MS detection by ultrasonic nebulisation or carbon-loaded plasma.

    PubMed

    Goenaga Infante, Heidi; Ovejero Bendito, María del Carmen; Cámara, Carmen; Evans, Linda; Hearn, Ruth; Moesgaard, Sven

    2008-04-01

    A method for the accurate determination of ultratrace selenium species of relevance to cancer research, such as gamma-glutamyl-Se-methylselenocysteine (gamma-glutamyl-SeMC), using species-specific double isotope dilution analysis (IDA) with HPLC-ICP-MS is reported for the first time. The (77)Se-enriched gamma-glutamyl-SeMC spike was produced in-house by collecting the fraction at the retention time of the gamma-glutamyl-SeMC peak from a chromatographed aqueous extract of (77)Se-enriched yeast, pooling the collected fractions and freeze-drying the homogenate. The Se content of this spike was characterised using reverse isotope dilution mass spectrometry (IDMS) and the isotopic composition of this spike was checked prior to quantification of the natural abundance dipeptide species in garlic using speciated IDA. The extraction of the gamma-glutamyl-SeMC species in water was performed in a sonication bath for 2 h after adding an appropriate quantity of (77)Se-enriched gamma-glutamyl-SeMC to 50 mg of garlic to give optimal (78)Se/(77)Se and (82)Se/(77)Se ratios of 1.5 and 0.6, respectively. The effect of ultrasonic nebulisation, in comparison with the loading of the ICP with carbon (through the addition of methane gas on-line), on the detection of Se associated with gamma-glutamyl-SeMC using collision/reaction cell ICP-MS with hydrogen as collision gas was investigated. Sensitivity enhancements of approximately fourfold and twofold were achieved using USN and methane mixed plasma, respectively, in comparison with conventional nebulisation and conventional Ar ICP-MS. However, an approximately twofold improvement in the detection limit was achieved using both approaches (42 ng kg(-1) for (78)Se using peak height measurements). The use of species-specific IDMS enabled quantification of the dipeptide species at ng g(-1) levels (603 ng g(-1) Se) in the complex food matrix with a relative standard deviation (RSD, n = 4) of 4.5%, which was approximately half that obtained

  8. Determining the isotopic compositions of uranium and fission products in radioactive environmental microsamples using laser ablation ICP-MS with multiple ion counters.

    PubMed

    Boulyga, Sergei F; Prohaska, Thomas

    2008-01-01

    This paper presents the application of a multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS)--a Nu Plasma HR--equipped with three ion-counting multipliers and coupled to a laser ablation system (LA) for the rapid and sensitive determination of the 235U/238U, 236U/238U, 145Nd/143Nd, 146Nd/143Nd, 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios in microsamples collected in the vicinity of Chernobyl. Microsamples with dimensions ranging from a hundred mum to about 1 mm and with surface alpha activities of 3-38 mBq were first identified using nuclear track radiography. U, Nd and Ru isotope systems were then measured sequentially for the same microsample by LA-MC-ICP-MS. The application of a zoom ion optic for aligning the ion beams into the ion counters allows fast switching between different isotope systems, which enables all of the abovementioned isotope ratios to be measured for the same microsample within a total analysis time of 15-20 min (excluding MC-ICP-MS optimization and calibration). The 101Ru/(99Ru+99Tc) and 102Ru/(99Ru+99Tc) isotope ratios were measured for four microsamples and were found to be significantly lower than the natural ratios, indicating that the microsamples were contaminated with the corresponding fission products (Ru and Tc). A slight depletion in 146Nd of about 3-5% was observed in the contaminated samples, but the Nd isotopic ratios measured in the contaminated samples coincided with natural isotopic composition within the measurement uncertainty, as most of the Nd in the analyzed samples originates from the natural soil load of this element. The 235U/238U and 236U/238U isotope ratios were the most sensitive indicators of irradiated uranium. The present work yielded a significant variation in uranium isotope ratios in microsamples, in contrast with previously published results from the bulk analysis of contaminated samples originating from the vicinity of Chernobyl. Thus, the 235U/238U ratios measured in ten

  9. Operationally defined species characterization and bioaccessibility evaluation of cobalt, copper and selenium in Cape gooseberry (Physalis Peruviana L.) by SEC-ICP MS.

    PubMed

    Wojcieszek, Justyna; Ruzik, Lena

    2016-03-01

    Physalis peruviana could attract great interest because of its nutritional and industrial properties. It is an excellent source of vitamins, minerals, essential fatty acids and carotenoids. Physalis Peruviana is also known to have a positive impact on human health. Unfortunately, still little is known about trace elements present in Physalis Peruviana and their forms available for the human body. Thus, the aim of this study was to estimate bioaccessibility and characterization of species of cobalt, copper and selenium in Physalis Peruviana fruits. Total and extractable contents of elements were determined by mass spectrometer with inductively coupled plasma (ICP MS). In order to separate the different types of metal complexes Physalis peruviana fruits were treated with the following solvents: Tris-HCl (pH 7.4), sodium dodecyl sulfate (SDS) (pH 7.4) and ammonium acetate (pH 5.5). The best efficiency of extraction of: cobalt was obtained for ammonium acetate (56%) and Tris-HCl (60%); for copper was obtained for SDS (66%), for selenium the best extraction efficiency was obtained after extraction with SDS (48%). To obtain information about bioaccessibility of investigated elements, enzymatic extraction based on in vitro simulation of gastric (pepsin) and intestinal (pancreatin) digestion was performed. For copper and selenium the simulation of gastric digestion leads to the extraction yield above 90%, while both steps of digestion method were necessary to obtain satisfactory extraction yield in the case of cobalt. Size exclusion chromatography (SEC) coupled to on-line ICP MS detection was used to investigate collected metal species. The main fraction of metal compounds was found in the 17 kDa region. Cobalt and copper create complexes mostly with compounds extracted by means of ammonium acetate and SDS, respectively. Cobalt, copper and selenium were found to be highly bioaccessible from Physalis Peruviana. Investigation of available standards of cobalt and selenium

  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. Dispersive liquid-liquid microextraction based on the solidification of floating organic drop followed by ICP-MS for the simultaneous determination of heavy metals in wastewaters

    NASA Astrophysics Data System (ADS)

    Li, Yong; Peng, Guilong; He, Qiang; Zhu, Hui; Al-Hamadani, Sulala M. Z. F.

    2015-04-01

    In the present work, a dispersive liquid-liquid microextraction based on the solidification of floating organic drop (DLLME-SFO) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of Pb, Co, Cu, Ni, Zn. The influences of analytical parameters, including pH, extraction solvent volume, disperser solvent volume, concentration of chelating agent on the quantitative recoveries of Pb, Co, Cu, Ni, Zn were investigated. The effect of the interfering ions on the analytes recovery was also investigated. Under the optimized conditions, the limits of detection were 0.97-2.18 ng L-1. The relative standard deviations (RSDs) were 2.62-4.51% (n = 7, C = 20 ng L-1). The proposed method was successfully applied for the analysis of ultra trace metals in wastewater samples.

  12. Quality control considerations for size exclusion chromatography with online ICP-MS: a powerful tool for evaluating the size dependence of metal-organic matter complexation

    PubMed Central

    McKenzie, Erica R.; Young, Thomas M.

    2013-01-01

    Size exclusion chromatography (SEC), which separates molecules based on molecular volume, can be coupled with online inductively coupled plasma mass spectrometry (ICP-MS) to explore size-dependent metal-natural organic matter (NOM) complexation. To make effective use of this analytical dual detector system, the operator should be mindful of quality control measures. Al, Cr, Fe, Se, and Sn all exhibited columnless attenuation, which indicated unintended interactions with system components. Based on signal-to-noise ratio and peak reproducibility between duplicate analyses of environmental samples, consistent peak time and height were observed for Mg, Cl, Mn, Cu, Br, and Pb. Al, V, Fe, Co, Ni, Zn, Se, Cd, Sn, and Sb were less consistent overall, but produced consistent measurements in select samples. Ultrafiltering and centrifuging produced similar peak distributions, but glass fiber filtration produced more high molecular weight peaks. Storage in glass also produced more high molecular weight peaks than did plastic bottles. PMID:23416600

  13. Measurement of haem and total iron in fish, shrimp and prawn using ICP-MS: Implications for dietary iron intake calculations.

    PubMed

    Wheal, Matthew S; DeCourcy-Ireland, Emma; Bogard, Jessica R; Thilsted, Shakuntala H; Stangoulis, James C R

    2016-06-15

    Twenty-five species of fish, shrimp and prawn from local markets in Bangladesh were analysed for concentrations of total Fe, haem Fe and non-haem Fe by ICP-MS. Total Fe and non-haem Fe concentrations were measured in nitric acid-digested samples and haem Fe was extracted using acidified 80% acetone for 60 min. Total Fe concentrations ranged from 0.55-14.43 mg/100 g FW, and haem Fe% ranged from 18%-93% of total Fe. Repeat extractions with 80% acetone recovered additional haem Fe, suggesting that previous measurement by this technique may have underestimated haem Fe content. Calculation of Fe balance (summing Fe in acetone extracts and Fe in the residue after haem Fe extraction) was not significantly different from total Fe, indicating the two processes recovered the different forms of Fe with similar effectiveness. PMID:26868569

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

    NASA Astrophysics Data System (ADS)

    Voica, C.; Dehelean, A.; Kovacs, M. H.

    2012-02-01

    Food is the primary source of essential elements for humans and it is an important source of exposure to toxic elements. In this context, levels of essential and toxic elements must be determined routinely in consumed food products. The content of trace elements (As, Pb, Cu, Cd, Zn, Sn, Hg) in different types of food samples (e.g. rice, bread, sugar, cheese, milk, butter, wheat, coffee, chocolate, biscuits pasta, etc.) was determined, using inductively coupled plasma mass spectrometry (ICP-MS). Trace element contents in some foods were higher than maximum permissible levels of toxic metals in human food (Cd in bread, Zn in cheese, Cu in coffee, Hg in carrots and peppers).

  15. 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.

  16. LA-ICP-MS imaging in multicellular tumor spheroids - a novel tool in the preclinical development of metal-based anticancer drugs.

    PubMed

    Theiner, Sarah; Schreiber-Brynzak, Ekaterina; Jakupec, Michael A; Galanski, Markus; Koellensperger, Gunda; Keppler, Bernhard K

    2016-04-01

    A novel application of advanced elemental imaging offers cutting edge in vitro assays with more predictive power on the efficacy of anticancer drugs in preclinical development compared to two dimensional cell culture models. We propose LA-ICP-MS analysis of multicellular spheroids, which are increasingly being used as three dimensional (3D) models of tumors, for improving the in vitro evaluation of anticancer metallodrugs. The presented strategy is very well suited for screening drug-tumor penetration, a key issue for drug efficacy. A major advantage of tumor spheroid models is that they enable us to create a tissue-like structure and function. With respect to 2D culture on the one hand and in vivo models on the other, multicellular spheroids thus show intermediate complexity, still allowing high repeatability and adequate through-put for drug research. This strongly argues for the use of spheroids as bridging models in preclinical anticancer drug development. Probing the lateral platinum distribution within these tumor models allows visualizing the penetration depth and targeting of platinum-based complexes. In the present study, we show for the first time that spatially-resolved metal accumulation in tumor spheroids upon treatment with platinum compounds can be appropriately assessed. The optimized LA-ICP-MS setup allowed discerning the platinum localization in different regions of the tumor spheroids upon compound treatment at biologically relevant (low micromolar) concentrations. Predominant platinum accumulation was observed at the periphery as well as in the center of the spheroids. This corresponds to the proliferating outermost layers of cells and the necrotic core, respectively, indicating enhanced platinum sequestration in these regions. PMID:26806253

  17. Development of an analytical procedure for the determination of polybrominated diphenyl ethers in environmental water samples by GC-ICP-MS.

    PubMed

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

    2014-05-27

    Polybrominated diphenyl ethers (PBDEs) are flame retardants, which due to their widespread use are frequently present as pollutants in the environment. In the EU Water Framework Directive (WFD) six PBDE congeners (BDE 28, BDE47, BDE 99, BDE 100, BDE 153 and BDE 154) are listed as priority substances. The uncertainty of the analytical method used for their determination in water samples at environmental quality standard (EQS) level (0.5 ng L(-1) for the ΣPBDEs) should be equal or less than 50% and the limit of quantification (LOQ) for ΣPBDEs below 0.15 ng L(-1). To meet these requirements, an analytical procedure for the determination of these six PBDEs in environmental water samples by gas chromatography-inductively coupled plasma mass spectrometry (GC-ICP-MS) was developed. The acidification of water samples to pH 2 maintained the stability of PBDEs for at least 20 days. The use of Tris-citrate buffer enabled efficient desorption of PBDEs from suspended particulate matter (SPM) and humic acids (HA), and their further quantitative solvent extraction into 2 mL of iso-octane. When 300 mL of water sample was used for analysis and the organic phase concentrated to 25 μL, the expanded uncertainty for determination of PBDEs at EQS level was found to be around 40% (a coverage factor for a confidence level of 95%, k=2), and the LOQ for the ΣPBDEs 0.109 ng L(-1). Finally, to demonstrate the applicability of the newly developed GC-ICP-MS procedure, PBDEs were determined in river and sea water samples. PMID:24832996

  18. Tubular textures in pillow lavas from a Caledonian west Norwegian ophiolite: A combined TEM, LA-ICP-MS, and STXM study

    NASA Astrophysics Data System (ADS)

    Fliegel, Daniel; Wirth, Richard; Simonetti, Antonio; Schreiber, Anja; Furnes, Harald; Muehlenbachs, Karlis

    2011-02-01

    Tubular alteration textures, mineralized by titanite, in glassy rims of pillow lavas from a Norwegian ophiolite (Solund-Stavfjord ophiolite complex (SSOC)) are described and characterized by a multimethod approach. Tubular alteration textures, mineralized by titanite, have been previously proposed to result from bioalteration. The microstructure of the titanite and the tubes is investigated using focused ion beam milling in combination with transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM). These indicate an assemblage of submicrometer-sized (about 500 nm) titanite single crystals with no organic film or residue in between the grains. In situ U-Pb radiometric dating of the titanite, using laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS), yielded a metamorphic age of 442 ± 13 Ma. An isotope dilution-thermal ionization mass spectrometric age obtained previously for zircons from the SSOC plutonic rocks yielded a magmatic age of 443 ± 3 Ma. The overlap in ages indicates that subseafloor metamorphism, responsible for titanite formation, occurred during seafloor or subseafloor formation of the tubular alteration textures. The rare earth element contents of the titanite were determined using LA-ICP-MS and chondrite-normalized patterns are similar to those of the SSOC volcanics; hence these do not reflect hydrothermal or seawater influence. The Y/Ho ratio of ˜20-30 in the titanite is also consistent with an upper mantle-derived origin. The sum of all of the spatial resolved data reported here neither supports nor refutes a biogenic origin for the tubular textures.

  19. Determination of reduced homocysteine in human serum by elemental labelling and liquid chromatography with ICP-MS and ESI-MS detection.

    PubMed

    Espina, Juan Gómez; Montes-Bayón, Maria; Blanco-González, Elisa; Sanz-Medel, Alfredo

    2015-10-01

    Analytical methods allowing sensitive determination of reduced homocysteine (rHcy), one of the so-called biothiols, in human serum is a topic of growing interest due to its close relation to several human disorders, mainly cardiovascular diseases. Although most widely used analytical strategies to determine total Hcy involve derivatization by means of fluorescent labels, this work proposes the use of ebselen, a Se-containing labelling agent to derivatize the reactive sulfhydryl group of the Hcy molecule in its "free" reduced form, which is more likely to play different roles in disease pathogenesis. Optimization of the derivatization and separation conditions by high-performance liquid chromatography (HPLC) to isolate the excess of derivatizing reagent is carried out here using UV/VIS detection. Further, the study of the Se labelling reaction by electrospray ionization tandem mass spectrometry (ESI-MS/MS) provides a stoichiometry of the derivative of 1:1. The main advantage of using ebselen as a labelling agent is the presence of the Se atom in the molecule that allows the use of inductively coupled plasma mass spectrometry (ICP-MS) as a sensitive and selective Se detector. The coupling of HPLC with ICP-MS provided excellent features for the determination of Se-derivatized rHcy (detection limit of 9.6 nM) in real samples. Quantification was accomplished by using post-column isotope dilution (ID) of Se in serum samples, after precipitation of the main serum proteins. Quantitative results for "free" rHcy turned out to be around 0.18-0.22 μM in serum samples from healthy individuals that could be directly analyzed without sample preconcentration. PMID:26362154

  20. ICP-MS analysis of lanthanide-doped nanoparticles: A quantitative and multiplexing approach to investigate biodistribution, blood clearance, and targeting

    NASA Astrophysics Data System (ADS)

    Crayton, Samuel

    The rapidly progressing field of nanotechnology promises to revolutionize healthcare in the 21st century, with applications in the prevention, diagnosis, and treatment of a wide range of diseases. However, before nanoparticulate agents can be brought into clinical use, they must first be developed, optimized, and evaluated in animal models. In the typical pre-clinical paradigm, almost all of the optimization is done at the in vitro level, with only a few select agents reaching the level of animal studies. Since only one experimental nanoparticle formulation can be investigated in a single animal, and in vivo experiments have relatively higher complexity, cost, and time requirements, it is not feasible to evaluate a very large number of agents at the in vivo stage. A major drawback of this approach, however, is that in vitro assays do not always accurately predict how a nanoparticle will perform in animal studies. Therefore, a method that allows many agents to be evaluated in a single animal subject would allow for much more efficient and predictive optimization of nanoparticles. We have found that by incorporating lanthanide tracer metals into nanoparticle formulations, we are successfully able to use inductively coupled plasma mass spectrometry (ICP-MS) to quantitatively determine a nanoparticle's blood clearance kinetics, biodistribution, and tumor delivery. This approach was applied to evaluate both passive and active tumor targeting, as well as metabolically directed targeting of nanoparticles to low pH tumor microenvironments. Importantly, we found that these in vivo measurements could be made for many nanoparticle formulations simultaneously, in single animals, due to the high-order multiplexing capability of mass spectrometry. This approach allowed for efficient and reproducible comparison of performance between different nanoparticle formulations, by eliminating the effects of subject-to-subject variability. In the future, we envision that this "higher

  1. Panafrican basement and Mesozoic gabbro in the Zagros orogenic belt in the Dorud-Azna region (NW Iran): Laser-ablation ICP-MS zircon ages and geochemistry

    NASA Astrophysics Data System (ADS)

    Shakerardakani, Farzaneh; Neubauer, Franz; Masoudi, Fariborz; Mehrabi, Behzad; Liu, Xiaoming; Dong, Yunpeng; Mohajjel, Mohammad; Monfaredi, Behzad; Friedl, Gertrude

    2015-04-01

    The Dorud-Azna region of the Sanandaj-Sirjan metamorphic zone (SSMZ) in NW Iran is part of the Zagros orogenic belt and exposes an amphibolite-grade metamorphic succession of mixed continental (e.g., the granitic Galeh-Doz orthogneiss) and oceanic or rift (e.g., various amphibolites) origin, which is intruded by the Darijune gabbro. Laser-ablation ICP-MS U-Pb zircon ages of 608 ± 18 Ma and 588 ± 41 Ma of the granitic Galeh-Doz orthogneiss indicate a Panafrican basement similar to that of the Yazd block of Central Iran. We therefore interpret this part of the SSMZ to represent a previously subducted part of the Panafrican basement of the Iranian microcontinent. Based on geochemistry, amphibolites and metagabbros from the Amphibolite unit representially potentially the cover on the Panafrican Galeh-Doz orthogneiss are interpreted to have their origin in a likely Upper Paleozoic to Mesozoic rift or E-MORB ophiolite succession. One of the metagabbros, here termed Dare-Hedavand metagabbro yield a 206Pb/238U mean age of 314.6 ± 3.7 Ma. Talc-bearing greenschists to epidote amphibolites of the Triassic June complex formed in a similar, but younger environment. Furthermore, the metamorphic complex is intruded by the Darijune gabbro, which yields a mean ICP-MS U-Pb zircon age of 170.2 ± 3.1 Ma. The final stage of likely Jurassic greenschist facies-grade metamorphism postdates the gabbro intrusion. We interpret the Darijune gabbro to have resulted from the initial subduction of Neotethyan oceanic lithosphere in a continental arc setting. The new data combined with data from literature indicate that the SSMZ represents a tectonic element of a mixed continental and oceanic origin, likely accreted to Central Iran during a Jurassic tectonic process. The new data also constrains thick-skinned nappe stacking within the Sanandaj-Sirjan zone.

  2. Direct spectral analysis of tea samples using 266 nm UV pulsed laser-induced breakdown spectroscopy and cross validation of LIBS results with ICP-MS.

    PubMed

    Gondal, M A; Habibullah, Y B; Baig, Umair; Oloore, L E

    2016-05-15

    Tea is one of the most common and popular beverages spanning vast array of cultures all over the world. The main nutritional benefits of drinking tea are its anti-oxidant properties, presumed protection against certain cancers, inhibition of inflammation and possible protective effects against diabetes. Laser induced breakdown spectrometer (LIBS) was assembled as a powerful tool for qualitative and quantitative analysis of various brands of tea samples using 266 nm pulsed UV laser. LIBS spectra for six brands of tea samples in the wavelength range of 200-900 nm was recorded and all elements present in our tea samples were identified. The major toxic elements detected in several brands of tea samples were bromine, chromium and minerals like iron, calcium, potassium and silicon. The spectral assignment was conducted prior to the determination of concentration of each element. For quantitative analysis, calibration curves were drawn for each element using standard samples prepared in known concentration in the tea matrix. The plasma parameters (electron temperature and electron density) were also determined prior to the tea samples spectroscopic analysis. The concentration of iron, chromium, potassium, bromine, copper, silicon and calcium detected in all tea samples was between 378-656, 96-124, 1421-6785, 99-1476, 17-36, 2-11 and 92-130 mg L(-1) respectively. The limits of detection estimated for Fe, Cr, K, Br, Cu, Si, Ca in tea samples were 22, 12, 14, 11, 6, 1 and 12 mg L(-1) respectively. To further confirm the accuracy of our LIBS results, we determined the concentration of each element present in tea samples by using standard analytical technique like ICP-MS. The concentrations detected with our LIBS system are in excellent agreement with ICP-MS results. The system assembled for spectral analysis in this work could be highly applicable for testing the quality and purity of food and also pharmaceuticals products. PMID:26992530

  3. 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.

  4. Evaluating the capabilities of aerosol-to-liquid particle extraction system (ALPXS)/ICP-MS for monitoring trace metals in indoor air.

    PubMed

    Jayawardene, Innocent; Rasmussen, Pat E; Chenier, Marc; Gardner, H David

    2014-09-01

    This study investigates the application of the Aerosol-to-Liquid Particle Extraction System (ALPXS), which uses wet electrostatic precipitation to collect airborne particles, for multi-element indoor stationary monitoring. Optimum conditions are determined for capturing airborne particles for metal determination by inductively coupled plasma-mass spectrometry (ICP-MS), for measuring field blanks, and for calculating limits of detection (LOD) and quantification (LOQ). Due to the relatively high flow rate (300 L min(-1)), a sampling duration of 1 hr to 2 hr was adequate to capture airborne particle-bound metals under the investigated experimental conditions. The performance of the ALPXS during a building renovation demonstrated signal-to-noise ratios appropriate for sampling airborne particles in environments with elevated metal concentrations, such as workplace settings. The ALPXS shows promise as a research tool for providing useful information on short-term variations (transient signals) and for trapping particles into aqueous solutions where needed for subsequent characterization. As the ALPXS does not provide size-specific samples, and its efficiency at different flow rates has yet to be quantified, the ALPXS would not replace standard filter-based protocols accepted for regulatory applications (e.g., exposure measurements), but rather would provide additional information if used in conjunction with filter based methods. Implications: This study investigates the capability of the Aerosol-to-Liquid Particle Extraction System (ALPXS) for stationary sampling of airborne metals in indoor workplace environments, with subsequent analysis by ICP-MS. The high flow rate (300 L/min) permits a short sampling duration (< 2 hr). Results indicated that the ALPXS was capable of monitoring short-term changes in metal emissions during a renovation activity. This portable instrument may prove to be advantageous in occupational settings as a qualitative indicator of elevated

  5. 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.

  6. COMPLEMENTARY MOLECULAR AND ELEMENTAL DETECTION OF SPECIATED THIOARSENICALS USING ESI-MS IN COMBINATION WITH A XENON-BASED COLLISION-CELL ICP-MS WITH APPLICATION TO FORTIFIED NIST FREEZE-DRIED URINE

    EPA Science Inventory

    The simultaneous detection of arsenic and sulfur in thio-arsenicals was achieved using xenonbased collision cell ICP-MS in combination with HPLC. In an attempt to minimize the 16O16O+ interference at m/z 32, both sample introduction and collision cell experimental parameters were...

  7. DETECTION AND QUANTIFICATION OF THIO-ARSENOSUGAR IN MARINE MOLLUSKS BY IC-ICP-MS WITH AN EMPHASIS ON THE INTERACTION OF ARSENOSUGARS WITH SULFIDE AS A FUNCTION OF PH

    EPA Science Inventory

    The sulfar analog of As(328)(2,3-dihydroxypropyl-5-deoxy-5-dimethylarsinoyl-ß-D-riboside), abbreviated (As(328-S), was detected and quantified in five species of marine shellfish using IC-ICP-MS with structural verification via IC-ESI-MS/MS. The CAD spectra produced from the par...

  8. APPLICATION OF SAMPLE PRE-OXIDATION OF ARSENITE IN HUMAN URINE PRIOR TO SPECIATON VIA ON-LINE PHOTO-OXIDATION WITH MEMBRANE HYDRIDE GENRATION AND ICP-MS DETECTION

    EPA Science Inventory

    A pre-oxidation procedure which converts arsenite (AS(III)) to arsenate (As(VVV)) was investigated in urinary arsenic speciation prior to on-line photo-oxidation hydride-generation with ICP-MS detection. This sample pre-oxidation method eliminates As(III) and As(V) preservation c...

  9. A systematic approach to the accurate quantification of selenium in serum selenoalbumin by HPLC-ICP-MS.

    PubMed

    Jitaru, Petru; Goenaga-Infante, Heidi; Vaslin-Reimann, Sophie; Fisicaro, Paola

    2010-01-11

    In this paper, two different methods are for the first time systematically compared for the determination of selenium in human serum selenoalbumin (SeAlb). Firstly, SeAlb was enzymatically hydrolyzed and the resulting selenomethionine (SeMet) was quantified using species-specific isotope dilution (SSID) with reversed phase-HPLC (RP-HPLC) hyphenated to (collision/reaction cell) inductively coupled plasma-quadrupole mass spectrometry (CRC ICP-QMS). In order to assess the enzymatic hydrolysis yield, SeAlb was determined as an intact protein by affinity-HPLC (AF-HPLC) coupled to CRC ICP-QMS. Using this approach, glutathione peroxidase (GPx) and selenoprotein P (SelP) (the two selenoproteins present in serum) were also determined within the same chromatographic run. The levels of selenium associated with SeAlb in three serum materials, namely BCR-637, Seronorm level 1 and Seronorm level 2, obtained using both methods were in a good agreement. Verification of the absence of free SeMet, which interferes with the SeAlb determination (down to the amino acid level), in such materials was addressed by analyzing the fraction of GPx, partially purified by AF-HPLC, using RP-HPLC (GPx only) and size exclusion-HPLC (SE-HPLC) coupled to CRC ICP-QMS. The latter methodology was also used for the investigation of the presence of selenium species other than the selenoproteins in the (AF-HPLC) SelP and SeAlb fractions; the same selenium peaks were detected in both control and BCR-637 serum with a difference in age of ca. 12 years. It is also for the first time that the concentrations of selenium associated with SeAlb, GPx and SelP species in such commercially available serums (only certified or having indicative levels of total selenium content) are reported. Such indicative values can be used for reference purposes in future validation of speciation methods for selenium in human serum and/or inter-laboratory comparisons. PMID:20005320

  10. "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

  11. Determination of arsenic species in fish, crustacean and sediment samples from Thailand using high performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Rattanachongkiat, S; Millward, G E; Foulkes, M E

    2004-04-01

    Suitable techniques have been developed for the extraction of arsenic species in a variety of biological and environmental samples from the Pak Pa-Nang Estuary and catchment, located in Southern Thailand, and for their determination using HPLC directly coupled with ICP-MS. The estuary catchment comprises a tin mining area and inhabitants of the region can suffer from various stages of arsenic poisoning. The important arsenic species, AsB, DMA, MMA, and inorganic arsenic (As III and V) have been determined in fish and crustacean samples to provide toxicological information on those fauna which contribute to the local diet. A Hamilton PRP-X100 anion-exchange HPLC system employing a step elution has been used successfully to achieve separation of the arsenic species. A nitric acid microwave digestion procedure, followed by carrier gas nitrogen addition- (N2)-ICP-MS analysis was used to measure total arsenic in sample digests and extracts. The arsenic speciation of the biological samples was preserved using a Trypsin enzymatic extraction procedure. Extraction efficiencies were high, with values of 82-102%(As) for fish and crustacean samples. Validation for these procedures was carried out using certified reference materials. Fish and crustacean samples from the Pak Pa-Nang Estuary showed a range for total arsenic concentration, up to 17 microg g(-1) dry mass. The major species of arsenic in all fauna samples taken was AsB, together with smaller quantities of DMA and, more importantly, inorganic As. For sediment samples, arsenic species were determined following phosphoric acid (1 M H3PO4) extraction in an open focused microwave system. A phosphate-based eluant, pH 6-7.5, with anion exchange HPLC coupled with ICP-MS was used for separation and detection of AsIII, AsV, MMA and DMA. The optimum conditions, identified using an estuarine sediment reference material (LGC), were achieved using 45 W power and a 20 minute heating period for extraction of 0.5 g sediment. The

  12. U-Pb dating of calcite-aragonite layers in speleothems from hominin sites in South Africa by MC-ICP-MS

    NASA Astrophysics Data System (ADS)

    Pickering, Robyn; Kramers, Jan

    2010-05-01

    Speleothems are found in association with early human (hominin) fossil-bearing cave deposits in South Africa and can be used to provide valuable chronological constraints. Such material is generally too old for U-Th dating and, although U-Pb geochronology presents a suitable alternative, bulk U concentrations are typically too low (< 0.05 μg/g) to provide useful ages. Very small amounts of radiogenic Pb accumulated in young samples, especially those with low U contents and a dominance of common Pb, even in Pb poor material, further complicates dating. U-Pb isochron age estimates can, however, be obtained by taking a number of sub-samples very close to each other (cm-scale) from growth layers. The close spacing makes it more likely that common Pb in the samples is homogeneous and minimizing scatter in isochron diagrams. Multi-collector ICP-MS is highly suitable for measuring isotope ratios of small (˜ng) quantities of Pb from such samples. Strong heterogeneity in U concentrations is frequent, rendering layers with sufficient U concentrations (≥ 1 μg/g) rare and difficult to locate. For this reason, a pre-screening step is necessary: we used simple non-invasive beta-scanner imaging to identify U-rich (≥ 1 μg/g) domains that could be analyzed with MC-ICP-MS techniques to provide U-Pb ages. Laser ablation scans for U and other trace elements is an alternative. A set of flowstone samples from the hominin bearing cave sediments at Sterkfontein Cave exhibit infrequent < 1 cm-thick layers with U concentrations ≥ 1 μg/g. These layers were thoroughly investigated using thin section petrography, scanning electron microscopy (SEM) and laser ablation ICP-MS. Relict aragonite needles are found exclusively in these U-rich layers. Apart from U, they are also enriched in Sr and Ba, due to the compatibility of large ions in the aragonite structure. They are also lower in common Pb than calcite layers above and below them. The layers occur in all cases in the lowermost few

  13. Construction of high-resolution trace element time-series in slow growth speleothems by LA-ICP-MS: Importance of parameter optimization and oriented band fabric imagery

    NASA Astrophysics Data System (ADS)

    Miller, N. R.; Griffiths, R. E.; Banner, J. L.

    2012-12-01

    Establishing high-resolution trace element time series in speleothems requires analytical techniques capable of representative sampling at sub-annual spatial resolution, but also possessing sufficient signal-to-noise to reliably discern potential season-to-season concentration variations. Growth rate is a major factor affecting both of these analytical challenges. To date, LA-ICP-MS, LA-MC-ICP-MS, SIMS, and μXRF techniques have been successfully applied to speleothem records, but nearly all studies have focused on speleothems with relatively fast growth rates of ≥ 100 μm/yr and which display well-defined banding. U-series dating of central Texas speleothems of the Edwards aquifer karst system demonstrate that calcite growth followed glacial-interglacial climate transitions spanning the past 70 ky. In contrast to previous high-resolution studies, central Texas speleothem growth rates seldom exceeded 25-50μm/yr and thus reside within a "slow-growth" (< 100 μm/yr) regime. Furthermore, seasonal banding is seldom revealed by conventional petrographic methods, thus complicating temporal/spatial sampling. To meet the analytical challenges posed by slow growth speleothems, we present an approach using LA-ICP-MS that integrates ablation and ionization parameters customized for speleothem calcite with oriented UV-fluorescence imagery. Ablation aerosol generation, transport, and ionization efficiency in the ICP are major interrelated factors affecting resolution of micro-scale, chemically-banded materials. To enhance chemical variations in finely banded materials, the aperture diameter must: (1) not exceed the critical sampling limit defined by the Nyquist frequency of the effective chemical waveform, whether sinusoidal or otherwise skewed with a higher frequency limb; and (2) must be capable of generating signals in excess of natural lateral heterogeneity and analytical noise components of measurement. Fabric-oriented, slow line scans, using narrow (5μm) rectangular

  14. [Application of ICP-MS and ICP-AES for Studying on Source Apportionment of PM2.5 during Haze Weather in Urban Beijing].

    PubMed

    Chen, Xi; Du, Peng; Guan, Qing; Feng, Xu; Xu, Dong-qun; Lin, Shao-bin

    2015-06-01

    To investigate the characteristics of chemical constitute and pollution sources of aerosol fine particulate matter during haze-fog day in Beijing in winter 2013. The samples of PM2.5 were collected in Beijing from January to February, 2013. The technique of ICP-MS and ICP-AES coupled with procedure of bathing-ultrasonic extraction was applied to determine the concentration of 40 elements in the aerosol samples to analyze the characteristics of elements distribution statistically. The absolute principal factor method was used to apportion the pollution sources of PM2.5 during the haze weather in Beijing city in winter 2013. The results showed that during the period of sampling, the volume concentration of Li, Mn, Pb, S etc. obeyed normal distribution approximately, and according to National Ambient Air Quality Standard issued by Ministry of Environmental Protection of the People's Republic of China, the geometric mean concentration of As was twice the annual limit of standard reference, while Pb of some aerosol samples beyond the annual limit of standard reference respectively. The mass fraction of Fe, Zn, Pb, Ti accounted for over 0.1%, while that of Mn, Cu, As, Se etc. 0.01%. These elements were primary inorganic pollutants, and especially the hazards and sources of As and Pb should be concerned. There were 6 main pollution sources were chosen by the factor analysis method, including industrial dust and human beings activities, biomass combustion and building dust, soil and sand dusts, fossil fuel, electronic waste and metal smelting, with the variance contribution rate of 40.3%, 27.0%, 9.1%, 4.9%, 4.8% and 4.6% respectively. ICP-MS and ICP-AES can be applied to analyzing multi-elements in PM2.5 accurately and quickly to facilitate source apportionment, and it indicated that the relevant pollution sources should be considered and the effect of regional transferring of haze pollution sources should be taken into account, and specific measures should be taken for

  15. MC ICP-MS δ(34)S(VCDT) measurement of dissolved sulfate in environmental aqueous samples after matrix separation by means of an anion exchange membrane.

    PubMed

    Hanousek, Ondrej; Berger, Torsten W; Prohaska, Thomas

    2016-01-01

    Analysis of (34)S/(32)S of sulfate in rainwater and soil solutions can be seen as a powerful tool for the study of the sulfur cycle. Therefore, it is considered as a useful means, e.g., for amelioration and calibration of ecological or biogeochemical models. Due to several analytical limitations, mainly caused by low sulfate concentration in rainwater, complex matrix of soil solutions, limited sample volume, and high number of samples in ecosystem studies, a straightforward analytical protocol is required to provide accurate S isotopic data on a large set of diverse samples. Therefore, sulfate separation by anion exchange membrane was combined with precise isotopic measurement by multicollector inductively coupled plasma mass spectrometry (MC ICP-MS). The separation method proved to be able to remove quantitatively sulfate from matrix cations (Ca, K, Na, or Li) which is a precondition in order to avoid a matrix-induced analytical bias in the mass spectrometer. Moreover, sulfate exchange on the resin is capable of preconcentrating sulfate from low concentrated solutions (to factor 3 in our protocol). No significant sulfur isotope fractionation was observed during separation and preconcentration. MC ICP-MS operated at edge mass resolution has enabled the direct (34)S/(32)S analysis of sulfate eluted from the membrane, with an expanded uncertainty U (k = 2) down to 0.3 ‰ (a single measurement). The protocol was optimized and validated using different sulfate solutions and different matrix compositions. The optimized method was applied in a study on solute samples retrieved in a beech (Fagus sylvatica) forest in the Vienna Woods. Both rainwater (precipitation and tree throughfall) and soil solution δ (34)SVCDT ranged between 4 and 6 ‰, the ratio in soil solution being slightly lower. The lower ratio indicates that a considerable portion of the atmospherically deposited sulfate is cycled through the organic S pool before being released to the soil solution

  16. Comparison of LA-ICP-MS analyses of melt inclusions and their host olivine from the 1959 eruption of Kilauea Iki, Hawaii: Insights into picrite formation

    NASA Astrophysics Data System (ADS)

    Bradshaw, R. W.; Kent, A. J.

    2013-12-01

    Picrites represent some of the most mafic magmas known, and as such are often assumed to represent relatively near-primary magma compositions and to provide important information about mantle sources. However most picrites also consist of a relatively evolved liquid (MgO ~8-9 wt.%) together with abundant olivine. Understanding the origin of picrites therefore requires techniques capable of identifying different sources of olivine, which may be either phenocrysts derived from fractional crystallization of the host magma, antecrysts or accumulated xenocrysts. These distinctions are usually made based on grain textures with the common interpretation being that grains with dislocation textures or 'kink bands' are xenocrysts and undeformed grains are related phenocrysts. However, due to the simple major element chemistry of olivine and rapid major element interdiffusion rates, chemical distinctions are difficult to relate to textures. Trace elements offer an alternative approach, and we present the results of laser ablation ICP-MS trace element analyses of olivine grains from the 1959 eruption of Kilauea Iki. A suite of elements (Li, Na, Mg, Al, Si, P, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, Zr, Y, Mo, Ba, Ce, Dy, Er, and Yb) were analyzed in olivine grains and compared to trace element analyses of melt inclusions, and associated glass from the same samples. Olivine grains were analyzed adjacent to the analyzed melt inclusions. Several elements (Ca, Ni, Cu, Zn, and Y) and ratios of these and other elements correlate well with melt inclusions and glass and suggest that olivine composition and melt inclusions exhibit similar compositional features. This suggests that trace elements in olivine may be used to predict the composition of the melts from which they are derived, and, potentially, to distinguish olivine crystals with different origins.. In addition, olivine from both Hawaii and the Snake River Plain, Idaho were analyzed by both electron microprobe

  17. A rapid and accurate method for the determination of plutonium in food using magnetic sector ICP-MS with an ultra-sonic nebuliser and ion chromatography.

    PubMed

    Evans, P; Elahi, S; Lee, K; Fairman, B

    2003-02-01

    In the event of a nuclear incident it is essential that analytical information on the distribution and level of contamination is available. An ICP-MS method is described which can provide data on plutonium contamination in food within 3 h of sample receipt without compromising detection limits or accuracy relative to traditional counting methods. The method can also provide simultaneous determinations of americium and neptunium. Samples were prepared by HNO3 closed-vessel microwave digestion, evaporated to dryness and diluted into a mobile phase comprising 1.5 M HNO3 and 0.1 mM 2,6-pyridinedicarboxylic acid. A commercially available polystyrene-divinylbenzene ion chromatography column provides on-line separation of 239Pu and 238U reducing the impact of the 238U1H interference. Oxidation of the sample using H2O2 ensures all Pu is in the Pu(+4) state. The oxidation also displaces Np away from the solvent front by changing the oxidation state from Np(+3) to Np(+4) and produces the insoluble Am(+4) ion. Simultaneous Pu, Am and Np analyses therefore require omission of the oxidation stage and some loss of Pu data quality. Analyses were performed using a magnetic sector ICP-MS (Finnigan MAT Element). The sample is introduced to the plasma via an ultrasonic nebuliser-desolvation unit (Cetac USN 6000AT+). This combination achieves an instrumental sensitivity of 238U > 2 x 10(7) cps/ppb and removes hydrogen from the sample gas, which also inhibits the formation of 238U1H. The net effect of the improved sample introduction conditions is to achieve detection levels for Pu of 0.020 pg g(-1) (4.6 x 10(-2) Bq kg(-1)) which is significantly below 1/10th of the most stringent EU (European Union) legislation, currently 0.436 pg g(-1) (1 Bq kg(-1)) set for baby food. The new method was evaluated with a range of biological samples ranging from cabbage to milk and meat. Recovery of Pu agrees with published values (100% +/- 20%). PMID:12619774

  18. NanoSIMS mapping and LA-ICP-MS chemical and U-Th-Pb data in monazite from a xenolith enclosed in andesite (Central Slovakia Volcanic Field)

    NASA Astrophysics Data System (ADS)

    Didier, A.; Bosse, V.; Bouloton, J.; Mostefaoui, S.; Viala, M.; Paquette, J. L.; Devidal, J. L.; Duhamel, R.

    2015-12-01

    In this study, we use NanoSIMS element and isotope ratio mapping and LA-ICP-MS trace element measurements to elucidate the origins of monazites from a restitic xenolith enclosed in a 13.5 ± 0.3 Ma andesitic lava (Slovakia). The xenolith/lava interaction is mainly characterized by the growth of a plagioclase-bearing corona around the xenolith and magmatic garnet overgrowths on primary metamorphic garnets within the xenolith. NanoSIMS images (89Y, 139La, 208Pb, 232Th and 238U) and trace element analyses indicate that variations of HREE, Y and Eu contents in the monazite are correlated with the resorption and the following overgrowth of garnet and plagioclase in the xenolith. Three domains are distinguished in the monazite grains: the inherited Variscan core at ca. 310 Ma (M1 domain) characterized by low Y and HREE contents and a weak negative Eu anomaly; the inner rim (M2 domain) crystallized during the growth of the plagioclase magmatic corona (large negative Eu anomaly) and the resorption of metamorphic garnet (high HREE and Y contents); and the external rim (M3 domain) crystallized during the growth of the plagioclase corona (large negative Eu anomaly) and during the crystallization of magmatic garnet (low Y, HREE contents) at ~13 Ma, i.e. the age of the andesitic lava. The age and chemical zonation of the monazites attest to the preservation of primary monazite in the xenolith despite the interaction with the andesite lava. NanoSIMS imaging provides high-quality sub-µm scale images of the monazite that reveals chemical domains that were not distinguishable on WDS X-ray maps, especially for depleted elements such as U and Pb. Owing to its small size, the M2 domain could not be accurately dated by the LA-ICP-MS method. However, NanoSIMS isotopic maps reveal that the M2 domain has similar 208Pb/232Th isotope ratios to the M3 domain and thus similar ages. These results support the hypothesis that melt-assisted partial dissolution-precipitation in monazite

  19. Study of Infra Red femtosecond laser induced aerosols using Transmission Electron Microscopy and Low Pressure Impactor: implications for LA-ICP-MS measurements

    NASA Astrophysics Data System (ADS)

    D'Abzac, F.; Seydoux-Guillaume, A.; Poitrasson, F.; Freydier, R.; Datas, L.

    2009-12-01

    Processes linked to the creation of laser induced aerosols are not yet fully understood, especially in the Infra Red femtosecond regime. It is of great interest to understand these mechanisms in order to better constrain chemical fractionation observed on LA-ICP-MS signals. A meticulous study of particles produced by IR-fs laser ablation (λ=800nm, τ=60fs, E=0,1-1mJ/pulse, f=5Hz) has been conducted on a wide variety of samples (phosphate, silicates, oxides, glass and metals), using transmission electron microscopy (Bright field TEM and EDS). Afterwards, observations using TEM coupled with focused ion beam (FIB) preparation have been performed on craters, to study the laser induced redeposition structure and chemistry and bring comparison with related aerosols. Finally, quantitative data have been collected using a low pressure impactor (LPI) device. Observed aerosols always consist in amorphous dark beads (30-150nm diameter) and more or less developed clusters (>100nm) of smaller particles (10-15 nm diameter). Their composition differs from each other and from the initial sample. Counting reveals a decreasing density of particle over 10min of ablation, while size distribution appears Gaussian, monomodal and remains centered on 90-100nm. Craters in monazite (phosphate, Moacir, Itembe, Brazil) show two different domains. Strained areas, induced by very high pressure resulting from matter removal, and, on the top, a thin layer (~250nm in the single shot crater for E=0,1mJ/pulse) probably melted then annealed. Qualitative EDS data from the latter shows the same composition as unshocked sample. Data allows an advanced reconstruction of events driving matter from crater digging through plasma and finally into metastable particles. Numerous theoretical[1] and experimental[2,3] reports, focused on each successive stage, help putting forward the hypothesis of a single complex process of condensation/coalescence. Direct qualitative and quantitative measurements on aerosols

  20. A simple method based on ICP-MS for estimation of background levels of arsenic, cadmium, copper, manganese, nickel, lead, and selenium in blood of the Brazilian population.

    PubMed

    Nunes, Juliana A; Batista, Bruno L; Rodrigues, Jairo L; Caldas, Naise M; Neto, Jose A G; Barbosa, Fernando

    2010-01-01

    Throughout the world, biomonitoring has become the standard for assessing exposure of individuals to toxic elements as well as for responding to serious environmental public health problems. However, extensive biomonitoring surveys require rapid and simple analytical methods. Thus, a simple and high-throughput method is proposed for the determination of arsenic (As), cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se) in blood samples by using inductively coupled plasma-mass spectrometry (ICP-MS). Prior to analysis, 200 microl of blood samples was mixed with 500 microl of 10% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 10 min, and subsequently diluted to 10 ml with a solution containing 0.05% w/v ethylenediamine tetraacetic acid (EDTA) + 0.005% v/v Triton X-100. After that, samples were directly analyzed by ICP-MS (ELAN DRC II). Rhodium was selected as an internal standard with matrix-matching calibration. Method detection limits were 0.08, 0.04, 0.5, 0.09, 0.12, 0.04, and 0.1 microg//L for As, Cd, Cu, Mn, Ni, Pb, and Se, respectively. Validation data are provided based on the analysis of blood samples from the trace elements inter-\\comparison program operated by the Institut National de Sante Publique du Quebec, Canada. Additional validation was provided by the analysis of human blood samples by the proposed method and by using electrothermal atomic absorption spectrometry (ETAAS). The method was subsequently applied for the estimation of background metal blood values in the Brazilian population. In general, the mean concentrations of As, Cd, Cu, Mn, Ni, Pb, and Se in blood were 1.1, 0.4, 890, 9.6, 2.1, 65.4, and 89.3 microg/L, respectively, and are in agreement with other global populations. Influences of age, gender, smoking habits, alcohol consumption, and geographical variation on the values were also considered. Smoking habits influenced the levels of Cd in blood. The levels of Cu, Mn, and Pb were

  1. Application of high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) for determination of chromium compounds in the air at the workplace.

    PubMed

    Stanislawska, Magdalena; Janasik, Beata; Wasowicz, Wojciech

    2013-12-15

    The toxicity and bioavailability of chromium species are highly dependable on the form or species, therefore determination of total chromium is insufficient for a complete toxicological evaluation and risk assessment. An analytical method for determination of soluble and insoluble Cr (III) and Cr (VI) compounds in welding fume at workplace air has been developed. The total chromium (Cr) was determined by using quadruple inductively coupled plasma mass spectrometry (ICP-MS) equipped with a dynamic reaction cell (DRC(®)). Soluble trivalent and hexavalent chromium compounds were determined by high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A high-speed, reversed-phase CR C8 column (PerkinElmer, Inc., Shelton, CT, USA) was used for the speciation of soluble Cr (III) and soluble Cr (VI). The separation was accomplished by interaction of the chromium species with the different components of the mobile phase. Cr (III) formed a complex with EDTA, i.e. retained on the column, while Cr (VI) existed in the solutions as dichromate. Alkaline extraction (2% KOH and 3% Na2CO3) and anion exchange column (PRP-X100, PEEK, Hamilton) were used for the separation of the total Cr (VI). The results of the determination of Cr (VI) were confirmed by the analysis of the certified reference material BCR CRM 545 (Cr (VI) in welding dust). The results obtained for the certified material (40.2±0.6 g kg(-1)) and the values recorded in the examined samples (40.7±0.6 g kg(-1)) were highly consistent. This analytical method was applied for the determination of chromium in the samples in the workplace air collected onto glass (Whatman, Ø 37 mm) and membrane filters (Sartorius, 0.8 μm, Ø 37 mm). High performance liquid chromatography with inductively coupled plasma mass spectrometry is a remarkably powerful and versatile technique for determination of chromium species in welding fume at workplace air. PMID:24209303

  2. Mass Spectrometric Investigation of Silicon Extremely Enriched in (28)Si: From (28)SiF4 (Gas Phase IRMS) to (28)Si Crystals (MC-ICP-MS).

    PubMed

    Pramann, Axel; Rienitz, Olaf

    2016-06-01

    A new generation of silicon crystals even further enriched in (28)Si (x((28)Si) > 0.999 98 mol/mol), recently produced by companies and institutes in Russia within the framework of a project initiated by PTB, were investigated with respect to their isotopic composition and molar mass M(Si). A modified isotope dilution mass spectrometric (IDMS) method treating the silicon as the matrix containing a so-called virtual element (VE) existing of the isotopes (29)Si and (30)Si solely and high resolution multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) were applied in combination. This method succeeds also when examining the new materials holding merely trace amounts of (29)Si (x((29)Si) ≈ 5 × 10(-6) mol/mol) and (30)Si (x((30)Si) ≈ 7 × 10(-7) mol/mol) extremely difficult to detect with lowest uncertainty. However, there is a need for validating the enrichment in (28)Si already in the precursor material of the final crystals, silicon tetrafluoride (SiF4) gas prior to crystal production. For that purpose, the isotopic composition of selected SiF4 samples was determined using a multicollector magnetic sector field gas-phase isotope ratio mass spectrometer. Contaminations of SiF4 by natural silicon due to storing and during the isotope ratio mass spectrometry (IRMS) measurements were observed and quantified. The respective MC-ICP-MS measurements of the corresponding crystal samples show-in contrast-several advantages compared to gas phase IRMS. M(Si) of the new crystals were determined to some extent with uncertainties urel(M) < 1 × 10(-9). This study presents a clear dependence of the uncertainty urel(M(Si)) on the degree of enrichment in (28)Si. This leads to a reduction of urel(M(Si)) during the past decade by almost 3 orders of magnitude and thus further reduces the uncertainty of the Avogadro constant NA which is one of the preconditions for the redefinition of the SI unit kilogram. PMID:27173726

  3. Melting and Metasomatism in the Mantle Lithosphere beneath the Pribilof Islands: Petrology and ICP-MS Analyses of Spinel Peridotite Xenoliths from St. George Island, Bering Sea, Alaska

    NASA Astrophysics Data System (ADS)

    Feeley, T. C.; Ulianov, A.; Underwood, S. J.

    2006-12-01

    A suite of protogranular spinel lherzolite xenoliths from an alkali basalt lava flow on St. George Island, Alaska, have been analyzed by for their bulk compositions by XRF and ICP-MS and for mineral compositions by electron microprobe and laser ablation ICP-MS. Bulk compositions of the peridotites range from relatively fertile (15-19% modal diopside) to depleted (10-8% modal diopside) and are consistent with variable degrees of melt extraction (7-18%) from a primitive mantle source. No hydrous minerals (e.g., mica or amphibole) were observed in any of the studied xenoliths. However, all xenoliths show melt-reaction textures characterized by glass-bearing, sieved textured rims on clinopyroxene and spinel. In several samples, complete clinopyroxene grains show sieve texture and are associated with melt pockets composed of coexisting silicic glass (Na- ± K-rich) and quench-textured olivine, spinel, clinopyroxene, and feldspar. In general, clinopyroxene and whole-rock chondrite-normalized REE patterns are similar, indicating that the whole-rock compositions reliably record the pre-entrainment REE patterns of the xenoliths. Whole-rock and clinopyroxene REE patterns show a considerable range from LREE-depleted to LREE-enriched, with most samples having flat to MREE-enriched patterns. The REE systematics suggest that most St. George lherzolites experienced little metasomatic overprinting of highly incompatible trace elements following melt extraction. In this regard, only the most refractory sample studied shows clear compositional evidence for metasomatism, as reflected in high whole-rock and clinopyroxene LREE/HREE ratios and abundances of other highly incompatible trace elements (e.g., Th, Ta, Nb, Rb, Sr). Based on the pervasive homogenization of this metasomatic signature, it is likely that it does not reflect a recent event related to the magmatism that brought the xenoliths to the surface. In spite of this evidence, the melt-reaction textures clearly demonstrate

  4. Cobalt Biogeochemistry in the South Atlantic: A Full-Depth Zonal Ocean Section of Total Dissolved Cobalt, and Development of a High Throughput Cobalt ICP-MS Method

    NASA Astrophysics Data System (ADS)

    Noble, A. E.; Saito, M. A.; Goepfert, T. J.

    2008-12-01

    This study presents the first high-resolution full-depth zonal section of total dissolved cobalt from a recent cruise transecting the South Atlantic Ocean along approximately 11S. This section demonstrates that current electrochemical analytical techniques are capable of producing the high precision and high resolution datasets for total dissolved cobalt expected to be generated as a part of the international GEOTRACES Program. The micronutritive role of cobalt may affect community structure in different regions of the oceans, a compelling reason to include cobalt in the trace element analyses planned for the GEOTRACES Program. This cobalt section reveals an advective source of cobalt from the African coast near Namibia, which we propose to be due to the Benguela Current interacting with reducing shelf sediments. These high concentrations of cobalt were also observed within the oxygen minimum zone that extends across much of the South Atlantic basin in this section, and are likely indicative of redox cycling of cobalt in the water column. Nutrient-like vertical structure of cobalt was observed in the surface waters across the majority of the basin due to biological utilization, and the expected hybrid-type trend is observed at depth, with scavenging of cobalt below the nutricline. Deepwater concentrations of cobalt were around 50pM across the basin below 3000m. Analysis of the shelf-life of refrigerated filtered samples stored without acidification for electrochemical cobalt analysis demonstrated that those samples which were collected specifically within oxygen minimum zones may underestimate cobalt if not analyzed within a few weeks of collection. These results motivate our on-going development of a method to measure cobalt in acidified samples via inductively coupled plasma mass spectrometry (ICP-MS). The benefit of this technique would be twofold: acidification would extend the shelf-life of the samples significantly, and samples would be preserved identically

  5. Single particle ICP-MS method development for the determination of plant uptake and accumulation of CeO2 nanoparticles.

    PubMed

    Dan, Yongbo; Ma, Xingmao; Zhang, Weilan; Liu, Kun; Stephan, Chady; Shi, Honglan

    2016-07-01

    Cerium dioxide nanoparticles (CeO2NPs) are among the most broadly used engineered nanoparticles that will be increasingly released into the environment. Thus, understanding their uptake, transportation, and transformation in plants, especially food crops, is critical because it represents a potential pathway for human consumption. One of the primary challenges for the endeavor is the inadequacy of current analytical methodologies to characterize and quantify the nanomaterial in complex biological samples at environmentally relevant concentrations. Herein, a method was developed using single particle-inductively coupled plasma-mass spectrometry (SP-ICP-MS) technology to simultaneously detect the size and size distribution of particulate Ce, particle concentration, and dissolved cerium in the shoots of four plant species including cucumber, tomato, soybean, and pumpkin. An enzymatic digestion method with Macerozyme R-10 enzyme previously used for gold nanoparticle extraction from the tomato plant was adapted successfully for CeO2NP extraction from all four plant species. This study is the first to report and demonstrate the presence of dissolved cerium in plant seedling shoots exposed to CeO2NPs hydroponically. The extent of plant uptake and accumulation appears to be dependent on the plant species, requiring further systematic investigation of the mechanisms. PMID:27129977

  6. 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.

  7. The CETAC ADX-500 Autodiluter System: A Study of Dilution Performance with the ELAN 6000 ICP-MS and ELAN Software

    USGS Publications Warehouse

    May, T.W.; Wiedmeyer, R.H.

    1998-01-01

    The CETAC ADX-500 autodiluter system was tested with ELAN?? v 2.1 software and the ELAN 6000 ICP-MS instrument to determine on-line automated dilution performance during analysis of standard solutions containing nine analytes representative of the mass spectral range (mass 9 to mass 238). Two or more dilution schemes were tested for each of 5 test tube designs. Dilution performance was determined by comparison of analyte concentration means of diluted and non-diluted standards. Accurate dilutions resulted with one syringe pump addition of diluent in small diameter round-bottomed (13 mm OD) or conical-tipped (18 mm OD) tubes and one or more syringe pump additions in large diameter (28 mm OD) conical-tipped tubes. Inadequate dilution mixing which produced high analyte concentration means was observed for all dilutions conducted in flat-bottomed tubes, and for dilutions requiring multiple syringe additions of diluent in small diameter round-bottomed and conical tipped tubes. Effective mixing of diluted solutions was found to depend largely upon tube diameter and liquid depth: smaller tube diameters and greater liquid depth resulted in ineffective mixing, whereas greater tube diameter and shallower liquid depth facilitated effective mixing. Two design changes for the autodiluter were suggested that would allow effective mixing to occur using any dilution scheme and tube design.

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

    PubMed

    Brittain, S R; Cox, A G; Tomos, A D; Paterson, E; Siripinyanond, A; McLeod, C W

    2012-03-01

    Flow field flow fractionation (FlFFF) in combination with inductively coupled plasma mass spectrometry (ICP-MS) was used to study the chemical speciation of U and trace metals in depleted uranium (DU) contaminated soils. A chemical extraction procedure using sodium pyrophosphate, followed by isolation of humic and fulvic substances was applied to two dissimilar DU contaminated sample types (a sandy soil and a clay-rich soil), in addition to a control soil. The sodium pyrophosphate fractions of the firing range soils (Eskmeals and Kirkcudbright) were found to contain over 50% of the total U (measured after aqua regia digestion), compared to approximately 10% for the control soil. This implies that the soils from the contaminated sites contained a large proportion of the U within more easily mobile soil fractions. Humic and fulvic acid fractions each gave characteristic peak maxima for analytes of interest (Mn, Fe, Cu, Zn, Pb and U), with the fulvic acid fraction eluting at a smaller diameter (approximately 2.1 nm on average) than the humic fraction (approximately 2.4 nm on average). DU in the fulvic acid fraction gave a bimodal peak, not apparent for other trace elements investigated, including natural U. This implies that DU interacts with the fulvic acid fraction in a different way to all other elements studied. PMID:22237634

  9. [Study on microwave digestion of coal for the determination of multi-element by ICP-OES and ICP-MS].

    PubMed

    Wang, Hui; Song, Qiang; Yao, Qiang; Chen, Chang-He; Yu, Fei-Lu

    2012-06-01

    Effects of temperature and four acids (HNO3, HNO3/H2O2, HNO3/HF and HNO3/HF+H3BO3) on the coal decomposition by microwave digestion and the multi-element analysis were studied. SARM20 was used as a coal standard reference material. The contents of 10 mineral elements (Al, Ca, Fe, Mg, K, Na, S, Si, Sr and Ti) in the coal SARM20 were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES). And the contents of 20 heavy metals (Li, Be, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se, Zr, Sn, Cs, Ba, Ce, Eu and Pb) were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The results showed that the coal was completely decomposed by microwave digestion with HNO3/HF+ H3BO3 at 210 degrees C. Good recoveries for all elements in the coal SARM20 were obtained by this two-step microwave digestion method. The recoveries of the 10 mineral elements were from 87.5% to 98.8%, and the recoveries of the 20 heavy metals were from 85% to 112.5%. All RSDs of tests were below 3%. PMID:22870661

  10. Concurrent determination of 237Np and Pu isotopes using ICP-MS: analysis of NIST environmental matrix standard reference materials 4357, 1646a, and 2702.

    PubMed

    Matteson, Brent S; Hanson, Susan K; Miller, Jeffrey L; Oldham, Warren J

    2015-04-01

    An optimized method was developed to analyze environmental soil and sediment samples for (237)Np, (239)Pu, and (240)Pu by ICP-MS using a (242)Pu isotope dilution standard. The high yield, short time frame required for analysis, and the commercial availability of the (242)Pu tracer are significant advantages of the method. Control experiments designed to assess method uncertainty, including variation in inter-element fractionation that occurs during the purification protocol, suggest that the overall precision for measurements of (237)Np is typically on the order of ± 5%. Measurements of the (237)Np concentration in a Peruvian Soil blank (NIST SRM 4355) spiked with a known concentration of (237)Np tracer confirmed the accuracy of the method, agreeing well with the expected value. The method has been used to determine neptunium and plutonium concentrations in several environmental matrix standard reference materials available from NIST: SRM 4357 (Radioactivity Standard), SRM 1646a (Estuarine Sediment) and SRM 2702 (Inorganics in Marine Sediment). PMID:25644752

  11. A study of Cu turnover in proteins of the visceral complex of Littorina littorea by stable isotopic analysis using coupled HPLC-ICP-MS.

    PubMed

    Mason, A Z; Borja, M R

    2002-01-01

    A two-dimensional HPLC system, tandemly coupled to an ICP-MS, has been used to study copper accumulation and turnover in the visceral complex cytosol of the gastropod, Littorina littorea. Animals were exposed for 8 weeks to NTA-buffered seawater containing stable isotopic 65Cu and then transferred to media containing stable isotopic 63Cu. The free ion activity of each isotope was maintained at 10(-11) M. Size exclusion (SE) HPLC showed Cu associated with haemocyanin (HC) and metallothionein-like (MT) proteins in two ligand pools with apparent molecular weights of >300 kDa and approximately 17 kDa, respectively. The MT pool was inducible by Cu, could assimilate the metal from both intrinsic and extrinsic sources and showed a higher rate of Cu accumulation and turnover than the HC pool. The induction of this pool also caused the sequestration and cytosolic redistribution of Zn, Cd, Pb, Mn and Co. Further fractionation of the MT pool by ion-exchange (IE) HPLC revealed that the Cu was associated with a single, major isoform of the protein that was Cu inducible and also bound trace quantities of Zn and Pb. A number of additional metal containing proteins were also resolved by IE. the most prominent of which also bound Pb, Mn and minor quantities of Zn. The significance of these findings in metal homeostasis and detoxification is discussed. PMID:12408587

  12. Uranium comparison by means of AMS and ICP-MS and Pu and 137Cs results around an Italian Nuclear Power Plant

    NASA Astrophysics Data System (ADS)

    De Cesare, M.; Tims, S. G.; Fifield, L. K.

    2015-04-01

    Italy built and commissioned 4 nuclear power plants between 1958-1978, which delivered a total of 1500 MW. All four were closed down after the Chernobyl accident following a referendum in 1987. One of the plants was Garigliano, commissioned in 1959. This plant used a 160 MW BWR1 (SEU of 2.3 %) and was operational from 1964 to 1979, when it was switched off for maintenance. It was definitively stopped in 1982, and is presently being decommissioned. We report here details on the chemistry procedure and on the measurements for soil samples, collected up to 4.5 km from the Nuclear Plant. A comparison between uranium (238U) concentration as determined by means of AMS (Accelerator Mass Spectrometry) and by ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) techniques respectively at the ANU (Australian National University) and at the Ecowise company in Canberra, Australia, is reported, as well as 236U and 239;240Pu concentration results detected by AMS. 236U/238U and 240Pu/239Pu isotopic ratios by means of AMS are also provided. A contamination from Chernobyl is visible in the 137Cs/239+240Pu activity ratio measurements.

  13. 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.

  14. Rapid determination of technetium-99 in large volume seawater samples using sequential injection extraction chromatographic separation and ICP-MS measurement.

    PubMed

    Shi, Keliang; Qiao, Jixin; Wu, Wangsuo; Roos, Per; Hou, Xiaolin

    2012-08-01

    An automated method was developed for rapid determination of (99)Tc in large volume seawater samples. The analytical procedure involves preconcentration of technetium with coprecipitation, online separation using extraction chromatography (two TEVA columns) implemented in a sequential injection setup, and measurement of (99)Tc by inductively coupled plasma mass spectrometry (ICP-MS). Chromatographic behaviors of technetium, molybdenum, and ruthenium were investigated, and the mechanism of adsorption and elution of TcO(4)(-) on a TEVA column using HNO(3) was explored. The results show that not only NO(3)(-) but also acidity (or concentration of H(+)) of the loading or eluting solution affect the adsorption and desorption of TcO(4)(-) on TEVA resin. Decontamination factors of more than 1 × 10(6) for ruthenium and 5 × 10(5) for molybdenum are achieved. Chemical yields of technetium in the overall procedure range from 60% to 75% depending on the sample volumes, and a detection limit of 7.5 mBq/m(3) (or 11.5 pg/m(3)) for 200 L of seawater was obtained. Compared with the conventional analytical procedure, the developed method significantly reduces analytical time. A batch of samples (n > 4) can be analyzed within 24 h. The method has been successfully applied for rapid and automated determination of low level (99)Tc in large volume seawater samples. The analytical results of seawater samples collected in Denmark show a good agreement with the values obtained using the conventional method. PMID:22783983

  15. [Determination of 235U/238U isotope ratios in camphor tree bark samples by MC-ICP-MS after separation of uranium from matrix elements].

    PubMed

    Wang, Xiao-Ping; Zhang, Ji-Long

    2007-07-01

    Twelve camphor (cinnamomum camphora) tree bark samples were collected from Hiroshima and Kyoto, and the matrix element composition and morphology of the outer surface of these camphor tree bark samples were studied by EDXS and SEM respectively. After a dry decomposition, DOWEX 1-X8 anion exchange resin was used to separate uranium from matrix elements in these camphor tree bark samples. Finally, 235U/238 U isotope ratios in purified uranium solutions were determined by MC-ICP-MS. It was demonstrated that the outer surface of these camphor tree bark samples is porous and rough, with Al, Ca, Fe, K, Mg, Si, C, O and S as its matrix element composition. Uranium in these camphor tree bark samples can be efficiently separated and quantitatively recovered from the matrix element composition. Compared with those collected from Kyoto, the camphor tree bark samples collected from Hiroshima have significantly higher uranium contents, which may be due to the increased aerosol mass concentration during the city reconstruction. Moreover, the 235 U/23.U isotope ratios in a few camphor tree bark samples collected from Hiroshima are slightly higher than 0.007 25. PMID:17944430

  16. ICP-MS Analysis of Lanthanide-Doped Nanoparticles as a Non-Radiative, Multiplex Approach to Quantify Biodistribution and Blood Clearance

    PubMed Central

    Crayton, Samuel H.; Elias, Andrew; Al-Zaki, Ajlan; Cheng, Zhiliang; Tsourkas, Andrew

    2011-01-01

    Recent advances in material science and chemistry have led to the development of nanoparticles with diverse physicochemical properties, e.g. size, charge, shape, and surface chemistry. Evaluating which physicochemical properties are best for imaging and therapeutic studies is challenging not only because of the multitude of samples to evaluate, but also because of the large experimental variability associated with in vivo studies (e.g. differences in tumor size, injected dose, subject weight, etc.). To address this issue, we have developed a lanthanide-doped nanoparticle system and analytical method that allows for the quantitative comparison of multiple nanoparticle compositions simultaneously. Specifically, superparamagnetic iron oxide (SPIO) with a range of different sizes and charges were synthesized, each with a unique lanthanide dopant. Following the simultaneous injection of the various SPIO compositions into tumor-bearing mice, inductively coupled plasma mass spectroscopy (ICP-MS) was used to quantitatively and orthogonally assess the concentration of each SPIO composition in serial blood samples and the resected tumor and organs. The method proved generalizable to other nanoparticle platforms, including dendrimers, liposomes, and polymersomes. This approach provides a simple, cost-effective, and non-radiative method to quantitatively compare tumor localization, biodistribution, and blood clearance of more than 10 nanoparticle compositions simultaneously, removing subject-to-subject variability. PMID:22100983

  17. Hydrolysis of proteins with methanesulfonic acid for improved HPLC-ICP-MS determination of seleno-methionine in yeast and nuts.

    PubMed

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

    2003-01-01

    In this work, the use of methanesulfonic acid for protein hydrolysis is proposed for evaluation of Se-methionine in yeast, Brazil nuts, and possibly other selenium-rich biological samples. The hydrolysis was carried out by heating the sample with 4 mol L(-1) acid at reflux for 8 h. Two chromatographic techniques (size-exclusion and ion-pairing) coupled with ICP-MS detection were used to compare the release of Se-methionine from proteins by enzymatic (proteinase K, protease XIV) and acid hydrolyses. A more efficient liberation of Se-methionine was observed by acid hydrolysis. For quantification, the sample extracts were introduced onto a C8 Alltima column, and the separation was achieved with a mobile phase containing 5 mmol L(-1) hexanesulfonic acid in citrate buffer (pH 4.5)/methanol (95:5). The results obtained by standard addition showed 816+/-17 micro g g(-1) and 36.2+/-1.5 micro g g(-1) of selenium in the form of Se-methionine in yeast and nuts, respectively (65% and 75% of total selenium). PMID:12520449

  18. 234U and 230Th determination by FIA-ICP-MS and application to uranium-series disequilibrium in marine samples.

    PubMed

    Godoy, Maria Luiza D P; Godoy, José Marcus; Kowsmann, Renato; Dos Santos, Guaciara M; Petinatti da Cruz, Rosana

    2006-01-01

    A 234U and 230Th determination method based on an extraction chromatographic separation on a flow injection system coupled to a quadruple ICP-MS was developed. Two-milliliter UTEVA (Eichrom Co.) cartridges were applied as separation tool and 236U and 229Th as spikes. Loading and washing steps were carried out in 3 M HNO3 solution and 0.05 M ammonium oxalate applied to elute both uranium and thorium. The method was applied initially to the IAEA-327 soil reference sample and NIST SRM 4357 ocean sediment reference material, with the obtained 234U and 230Th concentrations in agreement with the reference levels. Samples from a deep-sea sediment core (2450 m water depth) were analyzed and based on 230Th/234U dating, a mean sedimentation rate of 3.3 cm ky(-1) was calculated. Samples from two sediment layers were also dated by 14C-AMS and the observed ages agree with the 230Th/234U results. PMID:16545893

  19. Disequilibrium effects in metal speciation by capillary electrophoresis inductively coupled plasma mass spectrometry (CE-ICP-MS); theory, simulations and experiments.

    PubMed

    Sonke, Jeroen E; Salters, Vincent J M

    2004-08-01

    A theoretical-experimental approach to evaluate disequilibrium effects in capillary electrophoresis inductively coupled plasma mass spectrometry (CE-ICP-MS) is presented. Electrophoresis requires metal ligand (ML) complexes to be stable on the time scale of separation and detection. By expressing ML complex stability in terms of half-life during a CE separation, an evaluation of separation artifacts can be made. Kinetically slow metals like Cr, Al or Fe form complexes that are stable on the time scale of electrophoretic separations. Kinetically fast metals, like Pb, Hg, Cu, Cd and REE, however tend to form labile complexes which unless complexed by strong chelators will dissociate during CE separations. A reactive transport simulation model of CE separations involving ML complexes allows a more detailed prediction of disequilibrium bias and identifies kinetically limited from mobility-limited types of dissociation. Complementary experimental results are given for kinetic and equilibrium binding experiments of Sm with humic acid. The equilibrium logK for Sm-Leonardite humic acid (HA) binding at pH 7 and 0.01 mol L(-1) ionic strength was determined to be 13.04. Kinetic rates of formation and dissociation for SmHA were 5.9 10(8) and 5.3 10(-5) mol s(-1). PMID:15284917

  20. Antioxidant Potential and In Situ Analysis of Major and Trace Element Determination of Ood-saleeb, a Known Unani Herbal Medicine by ICP-MS.

    PubMed

    Raish, Mohammad; Ahmad, Ajaz; Alkharfy, Khalid M; Al-Jenoobi, Fahad I; Al-Mohizea, Abdullah M; Mohsin, Kazi; Ahamad, Syed Rizwan; Ali, Naushad; Shakeel, Faiyaz

    2016-08-01

    The intention of the present research work was to investigate the antioxidant activity and trace element analysis of Ood-saleeb, a known herbal medicine. Preliminary screening of phytochemicals showed that the extract of Ood-saleeb had flavonoids and phenolics. The significant activities in all antioxidant assays were observed in the extract of Ood-saleeb in comparison with the standard antioxidant with respect to dose of Ood-saleeb. Incredible activities to scavenge reactive oxygen species were also observed by the extract of Ood-saleeb. The IC50 values of all factors were determined using ascorbic acid as a standard. The inductive coupled plasma-mass spectroscopy (ICP-MS) was employed for the estimation of trace elements in Ood-saleeb extract. The concentrations of up to 18 elements were detected successfully. Silicon was found in high concentration (85.3 μg/g) while lithium was in low concentration (3 ng/g). The trace elements in the sample were found at different percentage levels which play a key role in the treatment of diseases. PMID:26758866

  1. Trace elements in e-liquids - Development and validation of an ICP-MS method for the analysis of electronic cigarette refills.

    PubMed

    Beauval, N; Howsam, M; Antherieu, S; Allorge, D; Soyez, M; Garçon, G; Goossens, J F; Lo-Guidice, J M; Garat, A

    2016-08-01

    Electronic cigarette use has rapidly increased in recent years. In assessing their safety, and in view of coming regulations, trace elements (TE) are among the potentially toxic compounds required to be evaluated in electronic cigarette refill fluids ("e-liquids"). An analytical method using inductively coupled plasma with mass spectrometric detection (ICP-MS) was developed and rigorously validated in order to determine concentrations of 15 TE in 54 e-liquids from a French brand. Despite a significant matrix effect from the main e-liquid constituents, and difficulties related to the current lack of reference materials, our method demonstrated satisfactory linearity, precision and robustness, and permitted the quantification of low concentrations of these 15 elements: lower limits of quantification (LLQ) obtained were ≤4 ppb for all elements except for Ni, Cu and Zn (16 ppb, 20 ppb and 200 ppb, respectively). All TE concentrations in all tested samples were <510 ppb, mostly near or below the LLQs. This method is transposable and is timely for laboratories seeking to meet a prospective demand in light of current or future regulations. PMID:27058761

  2. Breakdown of orthopyroxene contributing to melt pockets in mantle peridotite xenoliths from the Western Qinling, central China: constraints from in situ LA-ICP-MS mineral analyses

    NASA Astrophysics Data System (ADS)

    Su, Ben-Xun; Zhang, Hong-Fu; Yang, Yue-Heng; Sakyi, Patrick Asamoah; Ying, Ji-Feng; Tang, Yan-Jie

    2012-03-01

    Major and trace element compositions of constituent minerals, partly decomposed rims of orthopyroxenes (DRO), `closed' melt pockets (CMP) and open melt pockets (OMP) in some Western Qinling peridotite xenoliths were obtained by LA-ICP-MS. Systematic core-to-rim compositional variations of garnet, clinopyroxene and orthopyroxene demonstrate that these minerals underwent variable degrees of subsolidus breakdown or partial melting. Both DROs and CMPs consist of similar mineral assemblages and are characterized by high TiO2, CaO + Na2O and low MgO contents; they are enriched in LREE and LILE compositions, have positive anomalies in Pb, Sr and particularly Ti, negative Th and U, and variable Zr and Hf anomalies. These chemical features are distinct and reflect reactions involving the orthopyroxenes. Compared to the CMPs, the OMPs, which are composed of a complex assemblage of minerals, display lower FeO and MgO contents, larger ranges in SiO2 and Na2O, higher TiO2, Al2O3, CaO and trace element concentrations, slightly negative Zr and Hf anomalies, and apparently negative Ti anomalies. Modeling calculations of partial fusion of orthopyroxenes and clinopyroxenes suggest that the CMPs most likely originated from the breakdown of orthopyroxenes with variably minor contribution of external melts from the melting of clinopyroxenes, whereas the OMPs were probably formed from the modification of the CMPs through the interaction with large amount of external melts.

  3. Sequential digestion for measuring leachable and total lead in the same sample of dust or paint chips by ICP-MS.

    PubMed

    Le Bot, Barbara; Arcelin, Claire; Briand, Emmanuel; Glorennec, Philippe

    2011-01-01

    House lead exposure is generally assessed using total lead, except in France, where acid-leachable lead is used for routine regulatory purposes. In order to allow an international comparison of French lead dust contamination, a sequential digestion protocol is developed to determine both leachable and total lead on the same sample with a two-step digestion stage: firstly, hydrochloric acid is added to the sample at 37°C to solubilize leachable lead; then nitric acid is added to an aliquot at 95°C to solubilize residual (i.e., non-leachable) lead. Both sample fractions are analyzed with inductively coupled plasma mass spectrometry (ICP-MS). The sum of the two fractions allows to determine total lead. This new protocol has been tested with wiped dust (n = 111) and paint chip (n = 46) samples collected in houses (n = 16). The leachability of lead ranged from 63 to 100% in dust and from 4 to 100% in paint. These findings confirm the strong variability of lead leachability in houses samples and thus the importance of considering it for lead poisoning prevention. This double determination of leachable and total lead for each wiped dust or paint sample appears to be a reproducible, simple, low-cost protocol and thus a useful tool for international comparison of house dust lead contamination. PMID:21104496

  4. Determination of the platinum - Group elements (PGE) and gold (Au) in manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with ICP-MS

    USGS Publications Warehouse

    Balaram, V.; Mathur, R.; Banakar, V.K.; Hein, J.R.; Rao, C.R.M.; Gnaneswara, Rao T.; Dasaram, B.

    2006-01-01

    Platinum group elements (PGE) and Au data in polymetallic oceanic ferromanganese nodule reference samples and crust samples obtained by inductively coupled plasma mass spectrometry (ICP-MS), after separation and pre-concentration by nickel sulfide fire-assay and Te coprecipitation, are presented. By optimizing several critical parameters such as flux composition, matrix matching calibration, etc., best experimental conditions were established to develop a method suitable for routine analysis of manganese nodule samples for PGE and Au. Calibrations were performed using international PGE reference materials, WMG-1 and WMS-1. This improved procedure offers extremely low detection limits in the range of 0.004 to 0.016 ng/g. The results obtained in this study for the reference materials compare well with previously published data wherever available. New PGE data arc also provided on some international manganese nodule reference materials. The analytical methodology described here can be used for the routine analysis of manganese nodule and crust samples in marine geochemical studies.

  5. Use of Electrodeposition for Sample Preparation and Rejection Rate Prediction for Assay of Electroformed Ultra High Purity Copper for 232Th and 238U Prior to Inductively Coupled Plasma Mass Spectrometry (ICP/MS)

    SciTech Connect

    Hoppe, Eric W.; Aalseth, Craig E.; Brodzinski, Ronald L.; Day, Anthony R.; Farmer, Orville T.; Hossbach, Todd W.; McIntyre, Justin I.; Miley, Harry S.; Mintzer, Esther E.; Seifert, Allen; Smart, John E.; Warren, Glen A.

    2008-07-01

    The search for neutrinoless double beta decay in 76Ge has driven the need for ultra-low background Ge detectors shielded by electroformed copper of ultra-high radiopurity (<0.1µBq/kg). Although electrodeposition processes are almost sophisticated enough to produce copper of this purity, to date there are no methods sensitive enough to assay it. Inductively-coupled plasma mass spectrometry (ICP/MS) can detect thorium and uranium at femtogram levels, but in the past, this assay has been hindered by high copper concentrations in the sample. Electrodeposition of copper samples removes copper from the solution while selectively concentrating thorium and uranium contaminants to be assayed by ICP/MS. Spiking 232Th and 238U into the plating bath simulates low purity copper and allows for the calculation of the electrochemical rejection rate of thorium and uranium in the electroplating system. This rejection value will help to model plating bath chemistry.

  6. Inductively coupled plasma - Tandem mass spectrometry (ICP-MS/MS): A powerful and universal tool for the interference-free determination of (ultra)trace elements – A tutorial review.

    PubMed

    Balcaen, Lieve; Bolea-Fernandez, Eduardo; Resano, Martín; Vanhaecke, Frank

    2015-09-24

    This paper is intended as a tutorial review on the use of inductively coupled plasma - tandem mass spectrometry (ICP-MS/MS) for the interference-free quantitative determination and isotope ratio analysis of metals and metalloids in different sample types. Attention is devoted both to the instrumentation and to some specific tools and procedures available for advanced method development. Next to the more typical reaction gases, e.g., H2, O2 and NH3, also the use of promising alternative gases, such as CH3F, is covered, and the possible reaction pathways with those reactive gases are discussed. A variety of published applications relying on the use of ICP-MS/MS are described, to illustrate the added value of tandem mass spectrometry in (ultra)trace analysis. PMID:26423624

  7. 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

  8. 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

  9. Determination of rare earth elements, uranium and thorium in geological samples by ICP-MS, using an automatic fusion machine as an alkaline digestion tool.

    NASA Astrophysics Data System (ADS)

    Granda, Luis; Rivera, Maria; Velasquez, Colon; Barona, Diego; Carpintero, Natalia

    2014-05-01

    nitric acid solution . After an incorporation time, a fraction of this sample was then diluted 20 times in ultrapure deionized water ( resistivity greater 18.2 megohms / cm ). The diluted sample was analized in the ICP- MS, which was setted in high sensitivity mode. The results were compared through cross samples (the same samples tested in the laboratory were sent to another international laboratory, which works under accreditation ISO 17025 ) and no major deviations (5%) was obtained by making comparisons between the two laboratories. When comparing the results and evaluated the development of the art, it is concluded that this is an alternative that allows performing samples up to 50 alkaline fusions per day with great accuracy, saving resources and time. References: (1) British Geological Survey, Natural Environment Research Council, , Minerals UK Centre of Sustainable mineral development: Rare Earth Elements, p18-22, 2011 (2) Germain Bayon, Jean Alix Barrat, Joel Etoubleau, Mathieu Benoit ,Claire Bollinger, and Sidonie Revillon: Determination of Rare Earth Elements, Sc, Y, Zr, Ba, Hf and Th in Geological Samples by ICP-MS after Tm Addition and Alkaline Fusion, Geostandards and Geoanalytical Research, vol 33-N1, p51-62, 2008

  10. Examination of correlation between histidine and nickel absorption by Morus L., Robinia pseudoacacia L. and Populus nigra L. using HPLC-MS and ICP-MS.

    PubMed

    Ozen, Sukran Akkus; Yaman, Mehmet

    2016-08-01

    In this study, HPLC-MS and ICP-MS methods were used for the determination of histidine and nickel in Morus L., Robinia pseudoacacia L., and Populus nigra L. leaves taken from industrial areas including Gaziantep and Bursa cities. In the determination of histidine by HPLC-MS, all of the system parameters such as flow rate of mobile phase, fragmentor potential, injection volume and column temperature were optimized and found to be 0.2 mL min(-1), 70 V, 15 µL, and 20°C, respectively. Under the optimum conditions, histidine was extracted from plant sample by distilled water at 90°C for 30 min. Concentrations of histidine as mg kg(-1) were found to be between 2-9 for Morus L., 6-13 for Robinia pseudoacacia L., and 2-10 for Populus nigra L. Concentrations of nickel were in the ranges of 5-10 mg kg(-1) for Morus L., 3-10 mg kg(-1) for Robinia pseudoacacia L., and 0.6-4 mg kg(-1) for Populus nigra L. A significant linear correlation (r = 0.78) between histidine and Ni was observed for Populus nigra L., whereas insignificant linear correlation for Robinia pseudoacacia L. (r = 0.22) were seen. Limits of detection (LOD) and quantitation (LOQ) were found to be 0.025 mg Ni L(-1) and 0.075 mg Ni L(-1), respectively. PMID:26709863

  11. Flow injection combined with ICP-MS for accurate high throughput analysis of elemental impurities in pharmaceutical products according to USP <232>/<233>.

    PubMed

    Fischer, Lisa; Zipfel, Barbara; Koellensperger, Gunda; Kovac, Jessica; Bilz, Susanne; Kunkel, Andrea; Venzago, Cornel; Hann, Stephan

    2014-07-01

    New guidelines of the United States Pharmacopeia (USP), European Pharmacopeia (EP) and international organization (ICH, International Conference on Harmonization) regulating elemental impurity limits in pharmaceuticals seal the end of unspecific analysis of metal(oid)s as outlined in USP <231> and EP 2.4.8. Chapter USP <232> and EP 5.20 as well as drafts from ICH Q3D specify both daily doses and concentration limits of metallic impurities in pharmaceutical final products and in active pharmaceutical ingredients (API) and excipients. In chapters USP <233> and EP 2.4.20 method implementation, validation and quality control during the analytical process are described. By contrast with the--by now--applied methods, substance specific quantitative analysis features new basic requirements, further, significantly lower detection limits ask for the necessity of a general changeover of the methodology toward sensitive multi element analysis by ICP-AES and ICP-MS, respectively. A novel methodological approach based on flow injection analysis and ICP-SFMS/ICP-QMS for the quick and accurate analysis of Cd, Pb, As, Hg, Ir, Os, Pd, Pt, Rh, Ru, Cr, Mo, Ni, V, Cu, Mn, Fe and Zn in drug products by prior dilution, dissolution or microwave assisted closed vessel digestion according to the regulations is presented. In comparison to the acquisition of continuous signals, this method is advantageous with respect to the unprecedented high sample throughput due to a total analysis time of approximately 30s and the low sample consumption of below 50 μL, while meeting the strict USP demands on detection/quantification limits, precision and accuracy. PMID:24667566

  12. 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.

  13. Validation of a method to quantify titanium, vanadium and zirconium in oral mucosa cells by inductively coupled plasma-mass spectrometry (ICP-MS).

    PubMed

    Martín-Cameán, Ana; Jos, Angeles; Calleja, Ana; Gil, Fernando; Iglesias, Alejandro; Solano, Enrique; Cameán, Ana M

    2014-01-01

    The release of metal ions from fixed orthodontic appliances is a source of major concern. Various studies have evaluated the discharge of metals from these appliances in biological fluids, such as saliva or blood, overlooking the cells with prolonged contact with fixed appliances. The aim of this work is to develop and optimize an analytical procedure to determine Ti, V and Zr in oral mucosa cells in patients with and without orthodontic appliances by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The analytical procedure is based on an extraction and digestion of the samples and quantification of the elements. A suitable and practical procedure for assessing the trueness and precision of the proposed method has been applied by using validation standards. The method has been suitably validated: the regression equation was calculated from standards prepared in the same matrix without oral mucosa cells and the linear range was 0.5-50.0 ng/mL for Zr and 5.0-50.0 ng/mL for Ti and V. Limits of detection were 0.9, 2.8 and 0.4 ng/mL and limits of quantification 1.8, 3.4 and 0.7 ng/mL for Ti, V and Zr, respectively. The recovery percentages (%) obtained oscillated between 101 and 108 for Ti, 98 and 111 for V, and 92 and 104 for Zr. Intermediate precision (RSD%) data obtained were also adequate. The present method showed to be robust for the three factors considered: heating time, volume of the deionized water, and volume of PlasmaPure 65% HNO₃ used to dilute the samples, which permits its validation and application to oral mucosa cells from orthodontic patients. PMID:24274294

  14. Lead isotopic composition from data of high-precession MC-ICP-MS and sources of matter in the large-scale Sukhoi Log noble metal deposit, Russia

    NASA Astrophysics Data System (ADS)

    Chernyshev, I. V.; Chugaev, A. V.; Safonov, Yu. G.; Saroyan, M. R.; Yudovskaya, M. A.; Eremina, A. V.

    2009-12-01

    The lead isotopic composition of 33 sulfide samples from orebodies of the Sukhoi Log deposit was studied by high-precession MC-ICP-MS with a precision of ±0.02% (±2SD from 120 analyses of the SRM 981 standard sample). The deposit is located in the Bodaibo gold mining district in the northern Baikal-Patom Highland. Gold mineralization is hosted in Neoproterosoic black slates. Variations of lead isotope ratios of the Sukhoi Log sulfides are generally typical of Phanerozoic deposits and ore fields. They are significant for 206Pb/204Pb (17.903-18.674), moderate for 208Pb/204Pb (37.822-38.457), and relatively narrow for 207Pb/204Pb (15.555-15.679). In the Pb-Pb isotope diagrams, the data points of pyrite and galena constitute a linear trend. The points corresponding to pyrite from metasomatic ore occupy the left lower part of the trend. Galena from late gold-quartz veins shows more radiogenic Pb, and corresponding data points are located in the upper part of the trend. According to the Stacey-Kramers model, the end points of the trend, which is regarded as a mixing line, have μ2 = 9.6 and μ2 = 13.2 and model Pb-Pb ages 455 and 130 Ma, respectively. The isotope characteristics of ore lead, their relationships in pyrite and galena, and the mixing trend of Pb isotopic compositions are clearly tied to two Paleozoic stages in the formation of the Sukhoi Log deposit (447 ± 6 and 321 ± 14Ma) and testify to the leading role of crustal sources, which are suggested as being the Neoproterozoic black-shale terrigenous-carbonate rocks.

  15. 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. PMID:25476301

  16. Investigating Pu and U isotopic compositions in sediments: a case study in Lake Obuchi, Rokkasho Village, Japan using sector-field ICP-MS and ICP-QMS.

    PubMed

    Zheng, Jian; Yamada, Masatoshi

    2005-08-01

    The objectives of the present work were to study isotope ratios and the inventory of plutonium and uranium isotope compositions in sediments from Lake Obuchi, which is in the vicinity of several nuclear fuel facilities in Rokkasho, Japan. Pu and its isotopes were determined using sector-field ICP-MS and U and its isotopes were determined with ICP-QMS after separation and purification with a combination of ion-exchange and extraction chromatography. The observed (240)Pu/(239)Pu atom ratio (0.186 +/- 0.016) was similar to that of global fallout, indicating that the possible early tropospheric fallout Pu did not deliver Pu from the Pacific Proving Ground to areas above 40 degrees N. The previously reported higher Pu inventory in the deep water area of Lake Obuchi could be attributed to the lateral transportation of Pu deposited in the shallow area which resulted from the migration of deposited global fallout Pu from the land into the lake by river runoff and from the Pacific Ocean by tide movement and sea water scavenging, as well as from direct soil input by winds. The (235)U/(238)U atom ratios ranged from 0.00723 to 0.00732, indicating the natural origin of U in the sediments. The average (234)U/(238)U activity ratio of 1.11 in a sediment core indicated a significant sea water U contribution. No evidence was found for the release of U containing wastes from the nearby nuclear facilities. These results will serve as a reference baseline on the levels of Pu and U in the studied site so that any further contamination from the spent nuclear fuel reprocessing plants, the radioactive waste disposal and storage facilities, and the uranium enrichment plant can be identified, and the impact of future release can be rapidly assessed. PMID:16049580

  17. Quantitative analysis of some important metals and metalloids in tobacco products by inductively coupled plasma-mass spectrometry (ICP-MS)

    PubMed Central

    2012-01-01

    Background Large scale usage of tobacco causes a lot of health troubles in human. Various formulations of tobacco are extensively used by the people particularly in developing world. Besides several toxic tobacco constituents some metals and metalloids are also believed to pose health risks. This paper describes inductively coupled plasma-mass spectrometric (ICP-MS) quantification of some important metals and metalloids in various brands of smoked, sniffed, dipped and chewed tobacco products. Results A microwave-assisted digestion method was used for sample preparation. The method was validated by analyzing a certified reference material. Percentage relative standard deviation (% R.S.D.) between recovered and certified values was < 5.8. Linearity value for calibration curve of each metal was 1 > r > 0.999. Improved limits of detection (LODs) were in range of ng/L for all elements. Fe, Al and Mn were found to be in the highest concentration in all types of tobacco products, while Zn, Cu, Ni and Cr were below the average concentration of 40 μg/g, and Pb, Co, As, Se and Cd were below 5 μg/g. All elements, apart from Pb, were high in concentration in dipping tobacco in comparison to other tobacco products. Generally, the order of all elemental concentration can be expressed in different tobacco products as chewing < smoked < sniffing < dipping. However, smoked and sniffing will interchange their position in the case of Mn, Cu, Se and Cd. Multivariate statistical analyses were also performed to evaluate the correlation and variations among tobacco products. Conclusions The present study highlights the quantification of some important metals and metalloids in a wide spectrum of tobacco formulations. The outcome of this study would be beneficial for health authorities and individuals. PMID:22709464

  18. 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.

  19. High resolution micromill sampling for analysis of fish otoliths by ICP-MS: effects of sampling and specimen preparation on trace element fingerprints.

    PubMed

    Arslan, Zikri; Secor, David H

    2008-09-01

    Otoliths are calcified structures in the head of fish that record environmental information about fish's life history. Gathering the elemental information from the core of an otolith corresponding to the juvenile period of fish's life is critical to discriminate the adult fish to their natal habitats reliably. A high resolution micromill has been used to isolate the otolith core from a whole otolith for elemental analysis. The effects of micromilling procedures (e.g., sectioning, embedding and drilling) on contamination to otolith trace element levels were examined using paired blackfin tuna (Thunnus atlanticus) otoliths. Otoliths were decontaminated by dilute hydrogen peroxide and nitric acid throughout to remove surface contamination. A preconcentration procedure was used to determine the trace elements from the small core material by ICP-MS. It was found that micromilling procedures introduce significant contamination to otoliths, especially for Al, Cu, Pb and Zn. The sectioning procedure caused significant contamination for Co and Cu, while the embedding procedure resulted in contamination for nearly all trace elements (Al, Cd, Co, Cu, Ga, Mn, Ni, Pb, V and Zn). The combined sectioning, embedding and drilling procedure also resulted in contamination for most trace elements. Despite the contamination across all procedural steps, the decontamination procedure effectively removed the surface contamination with the exception of Pb and Zn. Bias (e.g., residual contamination) on Pb was small in comparison to overall concentration of Pb expected to occur in fish otoliths, therefore, its effect may be minor in discriminating individuals. Bias on Zn was larger that could limit its application in discriminating individuals. PMID:18640714

  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. 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.

  2. Quantitative analyse of trace elements with HR-ICP-MS Element2 : an example of application in calcite shell of the Great Scallop Pecten Maximus.

    NASA Astrophysics Data System (ADS)

    Richard, M.; Chauvaud, L.; Benoit, M.; Thebault, J.; L'Helguen, S.; Hemond, C.; Maguer, J.; Sinquin, G.

    2008-12-01

    Carbonate minerals are abundant on the Earth's surface, and they are produced by a number of processes, including precipitation from hydrothermal fluids or synthesis by organisms like coral, foraminifera, molluscs, or bacteria. Consequently, they are found in a large variety of environments. Their isotopic compositions (Sr, C, or O ) and trace element concentrations are widely used to understand or reconstruct biological, geological or biogeochimical processes. A large scientific community define the elemental composition of bivalve shells a promising tool as a recorder of environmental parameters like sea surface temperature, salinity and primary productivity. But we have compile evidences that trace elements variation within shells can be species dependant or change in a complex network of environmental interactions. In this context, a better understanding of the incorporation of elements from seawater into biogenic carbonate is necessary to generalize the use of these proxies. Daily shell growth in the calcitic bivalve Pecten maximus has been extensively measured and these daily growth marks can be used to date each subsequent sample of calcium carbonate. In this study, micro- sampling of carbonate powder along the shell was carried out with a high-resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS, Finnigan Element2). This method led to a quantitative detection of trace element in biocaronates and to the accurate reconstruction of ontogenetic profiles of elemental ratios with a 3-day temporal resolution. Repeated analyses of different growth layers sections on the same valve showed that the trace elements are homogeneously distributed along the shell. Mo concentration was reproducible for several scallop individuals from a same location over different years and from different coastal temperate environments. Each profile was characterised by a background level punctuated by sharp episodic peaks occurring in spring (may). Some hypotheses will be

  3. Antimony, Arsenic and Chromium Speciation Studies in Biała Przemsza River (Upper Silesia, Poland) Water by HPLC-ICP-MS

    PubMed Central

    Jabłońska-Czapla, Magdalena

    2015-01-01

    In this paper the total concentration of As, Cr, Sb, pH and the red-ox potential of water and sediment samples of the Biała Przemsza River were determined. The arsenic (AB, MMA, DMA, As(III), As(V)), chromium (Cr(III), Cr(VI)) and antimony (Sb(III), Sb(V)) forms were studied by HPLC-ICP-MS. Ions were successfully separated on Hamilton PRP-X100: (AB, MMA, DMA, As(III), As(V)), Dionex Ion Pac AS-7 (Sb(III), Sb(V)) and Dionex IonPac AG7 columns: Cr(III), Cr(VI) with LOD 0.16 μg/L, 0.08 μg/L, 0.09 μg/L, 0.012 μg/L, 0.08 μg/L, 0.12 μg/L, 0.009 μg/L, 0.012 μg/L, 0.19 μg/L, 0.37 μg/L, respectively. The simplified BCR three-step sequential chemical extraction was performed on the bottom sediment samples. The samples were collected monthly, between April and December 2014, at five sampling points. Large contents of manganese, lead, cadmium and zinc were found in the Biała Przemsza River water. In December 2014, the lead content in the bottom sediment in Sławków was nearly 6000 mg/kg. In the river water, only the inorganic arsenic speciation forms were found. Sb(V), As(V) and Cr(III) were dominant. Studies have shown that arsenic, antimony and chromium were mainly bound to oxides, organic matter and sulphides in the bottom sediments. PMID:25941843

  4. Determination of size-dependent metal distribution in dissolved organic matter by SEC-UV/VIS-ICP-MS with special focus on changes in seawater.

    PubMed

    Rathgeb, Anna; Causon, Tim; Krachler, Regina; Hann, Stephan

    2016-04-01

    Iron is an essential micronutrient for all marine organisms, but it is also a growth limiting factor as the iron concentrations in the open ocean are below 1 nmol/L in sea water iron is almost entirely bound to organic ligands of the dissolved organic matter fraction, which are mostly of unknown structure. The input from rivers was traditionally considered as less important due to estuarine sedimentation processes of the mainly colloidal iron particles. However, recent studies have shown that this removal is not complete and riverine input may represent an important iron source in the open ocean. In this context, iron transport by land-derived natural organic matter (NOM), and dissolved organic matter (DOM) have been identified as carrier mechanisms for riverine iron. The aim of this work is to characterize complexes containing iron and other metals in waters simulating estuarine conditions in order to help understand which role iron-DOM compounds play in the open ocean. A method based on size-exclusion chromatography (SEC) with sequential UV/VIS and ICP-MS detection was developed for investigation of DOM size distribution and for assessment of the size-dependent metal distribution in NOM-rich surface water. Furthermore, sample matrix experiments were also performed revealing a dependence of DOM size distribution upon seawater concentration and different compounds present in seawater. Finally, efforts toward determination of DOM size with standardization with typical SEC standards indicate that only relative comparisons are possible with this approach, and that the sample matrix composition strongly influences obtained results. PMID:26814136

  5. Liquid immiscibility between arsenide and sulfide melts: evidence from a LA-ICP-MS study in magmatic deposits at Serranía de Ronda (Spain)

    NASA Astrophysics Data System (ADS)

    Piña, R.; Gervilla, F.; Barnes, S.-J.; Ortega, L.; Lunar, R.

    2015-03-01

    The chromite-Ni arsenide (Cr-Ni-As) and sulfide-graphite (S-G) deposits from the Serranía de Ronda (Málaga, South Spain) contain an arsenide assemblage (nickeline, maucherite and nickeliferous löllingite) that has been interpreted to represent an arsenide melt and a sulfide-graphite assemblage (pyrrhotite, pentlandite, chalcopyrite and graphite) that has been interpreted to represent a sulfide melt, both of which have been interpreted to have segregated as immiscible liquids from an arsenic-rich sulfide melt. We have determined the platinum-group element (PGE), Au, Ag, Se, Sb, Bi and Te contents of the arsenide and sulfide assemblages using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to establish their partitioning behaviour during the immiscibility of an arsenide melt from a sulfide melt. Previous experimental work has shown that PGE partition more strongly into arsenide melts than into sulfide melts and our results fit with this observation. Arsenide minerals are enriched in all PGE, but especially in elements with the strongest affinity for the arsenide melt, including Ir, Rh and Pt. In contrast and also in agreement with previous studies, Se and Ag partition preferentially into the sulfide assemblage. The PGE-depleted nature of sulfides in the S-G deposits along with the discordant morphologies of the bodies suggest that these sulfides are not mantle sulfides, but that they represent the crystallization product of a PGE-depleted sulfide melt due to the sequestering of PGE by an arsenide melt.

  6. Differentiating the Bishop ash bed and related tephra layers by elemental-based similarity coefficients of volcanic glass shards using solution inductively coupled plasma-mass spectrometry (S-ICP-MS)

    USGS Publications Warehouse

    Knott, J.R.; Sarna-Wojcicki, A. M.; Montanez, I.P.; Wan, E.

    2007-01-01

    Volcanic glass samples from the same volcanic center (intra-source) often have a similar major-element composition. Thus, it can be difficult to distinguish between individual tephra layers, particularly when using similarity coefficients calculated from electron microprobe major-element measurements. Minor/trace element concentrations in glass can be determined by solution inductively coupled plasma mass spectrometry (S-ICP-MS), but have not been shown as suitable for use in large tephrochronologic databases. Here, we present minor/trace-element concentrations measured by S-ICP-MS and compare these data by similarity coefficients, the method commonly used in large databases. Trial samples from the Bishop Tuff, the upper and lower tuffs of Glass Mountain and the tuffs of Mesquite Spring suites from eastern California, USA, which have an indistinguishable major-element composition, were analyzed using S-ICP-MS. The resulting minor/trace element similarity coefficients clearly separated the suites of tephra layers and, in most cases, individual tephra layers within each suite. Comparisons with previous instrumental neutron activation analysis (INAA) elemental measurements were marginally successful. This is important step toward quantitative correlation in large tephrochronologic databases to achieve definitive identification of volcanic glass samples and for high-resolution age determinations. ?? 2007 Elsevier Ltd and INQUA.

  7. Destructive versus non-destructive methods for geochemical analyses of ceramic artifacts: comparison of portable XRF and ICP-MS data on Bronze Age ceramics from Failaka Island (Kuwait) and Bahrain

    NASA Astrophysics Data System (ADS)

    Stremtan, Ciprian; Ashkanani, Hasan; Tykot, Robert H.

    2013-04-01

    The study of bi-phase (i.e. matrix and clasts) geochemical composition of ceramic artifacts is a very powerful tool in fingerprinting the raw materials used by ancient manufacturers (clay sources, tempering materials, coloring agents, etc.), as well as in understanding the physical parameters of the manufacturing techniques. Reliable datasets often require the deployment of destructive techniques that will irremediably damage the artifact. Recent advances in portable X-ray fluorescence instrumentation (pXRF) allow for quick measurements of a range of chemical elements that not too long ago were available only through complicated and often destructive means of analytical chemistry (instrumental neutron activation analysis - INAA, inductively coupled plasma mass spectrometry - ICP-MS, direct coupled plasma-optical emission spectroscopy - DCP-OES etc.). In this contribution we present a comparison of datasets acquired by means of pXRF, DCP-OES, and ICP-MS on Bronze Age ceramics from Failaka Island (Kuwait) and Bahrain. The samples chosen for this study are fine grained, with very well sorted mineral components, and lack any visible organic material fragments. The sample preparation for ICP-MS and DCP-OES analyses was carried out on powdered samples, by using LiBO2 flux fusion and Ge (for the DCP-OES) and In (for ICP-MS) were used as internal standards. The measurements were calibrated against certified reference materials ranging from shales to rhyolites (SGR-1, SDo-1, JA-2, and JR-1) and performed at Univerity of South Florida's Center for Geochemical Analyses. The analytical errors for major elements was smaller than 5 %, while for selected trace elements the error was usually smaller than 3 %. The same set of elements was measured on the same samples at University of South Florida's Anthropology Department using a pXRF device equipped with obsidian filter. Each sample was measured three times and the values were averaged. Two certified reference materials (NIST-612

  8. Elemental analysis of soils using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS) with multivariate discrimination: tape mounting as an alternative to pellets for small forensic transfer specimens.

    PubMed

    Jantzi, Sarah C; Almirall, José R

    2014-01-01

    Elemental analysis of soil is a useful application of both laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS) in geological, agricultural, environmental, archeological, planetary, and forensic sciences. In forensic science, the question to be answered is often whether soil specimens found on objects (e.g., shoes, tires, or tools) originated from the crime scene or other location of interest. Elemental analysis of the soil from the object and the locations of interest results in a characteristic elemental profile of each specimen, consisting of the amount of each element present. Because multiple elements are measured, multivariate statistics can be used to compare the elemental profiles in order to determine whether the specimen from the object is similar to one of the locations of interest. Previous work involved milling and pressing 0.5 g of soil into pellets before analysis using LA-ICP-MS and LIBS. However, forensic examiners prefer techniques that require smaller samples, are less time consuming, and are less destructive, allowing for future analysis by other techniques. An alternative sample introduction method was developed to meet these needs while still providing quantitative results suitable for multivariate comparisons. The tape-mounting method involved deposition of a thin layer of soil onto double-sided adhesive tape. A comparison of tape-mounting and pellet method performance is reported for both LA-ICP-MS and LIBS. Calibration standards and reference materials, prepared using the tape method, were analyzed by LA-ICP-MS and LIBS. As with the pellet method, linear calibration curves were achieved with the tape method, as well as good precision and low bias. Soil specimens from Miami-Dade County were prepared by both the pellet and tape methods and analyzed by LA-ICP-MS and LIBS. Principal components analysis and linear discriminant analysis were applied to the multivariate data

  9. 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

  10. 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

  11. Distribution of incompatible trace elements between the constituents of spinel peridotite xenoliths: ICP-MS data from the East African rift

    NASA Astrophysics Data System (ADS)

    Bedini, R. M.; Bodinier, J.-L.

    1999-11-01

    To constrain the geochemical models of the lithospheric mantle, we have carried out a detailed study of the distribution of incompatible trace elements between the various constituents of spinel peridotites. Predominant and accessory minerals were separated in 12 mantle xenoliths from Mega (East African Rift, Sidamo region, SE Ethiopia). The samples range in composition from cpx-rich lherzolites to refractory harzburgites and are devoid of modal metasomatism, except for minor amount of apatite in some of them. Their trace element concentration encompasses almost the whole range reported in the literature for basalt-born xenoliths. Mineral separates (ol, opx, cpx, spinel and apatite) and their leachates were analyzed by ICP-MS, for rare earth elements (REE) and several incompatible trace elements (Rb, Sr, Ba, Zr, Hf, Nb, Ta, Th, U, and Ti). Spinel surfaces were investigated by SEM and EPMA to determine the composition of the attached micro-phases. Mass-balance inversion shows that the trace element composition of whole rocks is controlled by five distinct components: 1). the silicate minerals which account for the total HREE abundance, and 50-90% of LREE, Sr, and Zr-Hf, in the apatite-free peridotites; 2). the mineral-hosted fluid inclusions which play a significant role for Rb (20-25%), and to a lesser degree for the other LILEs; 3). a pervasive grain-boundary component selectively enriched in highly incompatible elements, which contributes 25-90% of the whole-rock budget for Ba, Th and U, and 10-50% for Nb and LREE, in the apatite-free samples; 4). thin reaction layers (<10 μm thick) coating the surfaces of spinel grains and mainly composed of Ti-oxides and phlogopite. They are the predominant repository of Nb-Ta (45-60%) and Rb-Ba (30-80%) in all the studied xenoliths; 5). apatite which largely predominates the budget of Th, U, Sr and LREE (25-75%) in the samples containing this mineral. Compared to the other peridotite constituents, fluid-derived inclusions in

  12. Mid-Paleozoic arc granitoids in SW Japan with Neoproterozoic xenocrysts from South China: New zircon U-Pb ages by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Aoki, Kazumasa; Isozaki, Yukio; Yamamoto, Atsushi; Sakata, Shuhei; Hirata, Takafumi

    2015-01-01

    The Kurosegawa belt in SW Japan preserves fragments of Early-Middle Paleozoic granitoids traditionally called the Mitaki igneous rocks and previously dated ca. 470-435 Ma by several isotope analyses such as Rb-Sr, K-Ar and U-Pb, together with high-grade metamorphic rocks and Silurian strata, in a narrow belt. However, the timing of the oldest arc-related plutonism in Japan is constrained by laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb ages of zircon from Mitaki granitoids in 3 areas in SW Japan; i.e. Kyushu, Shikoku, and Kii Peninsula. Weighted mean U-Pb ages of these zircons are 431.8 ± 3.9 for a granodiorite from the Mt. Mitaki area in Shikoku, 444.1 ± 5.8 Ma for a granodiorite from Kuraoka area in central Kyushu, and 444.5 ± 7.6 Ma for a quartzdiorite from the Nabaenohana area in western Kii peninsula, respectively. These ages confirm that the Mitaki igneous rocks have ca. 445-435 Ma (late Ordovician to mid-Silurian) ages. They are some of the oldest subduction-related plutonic rocks in SW Japan. Particularly noteworthy is a "tonalite" from the Nabaenohana area, which has a unique spectrum of zircon U-Pb ages with distinct 3 clusters; ca. 700-500 Ma (Neoproterozoic-Cambrian), ca. 1350-830 Ma (Meo-Neoproterozoic), and ca. 3230-1560 Ma (Paleoarchean-Mesoproterozoic). Of the 44 dated zircon grains, the youngest (possibly xenocrystic) grains are ca. 500 Ma. Older zircon grains with ages >500 Ma range up to 3230 Ma and are interpreted as inherited xenocrysts in the "tonalite". The Mitaki igneous rocks are interpreted to have been derived by melting of post-500 Ma terrigenous sedimentary rocks that yielded a unique tonalitic S-type granitoid magma. From the presence of abundant 1350-700 Ma (Meso- to Neoproterozoic) zircon grains in the "tonalite" we conclude that during the Early Paleozoic, proto-Japan was located close to the Cathaysian margin of South China.

  13. Importance of LA-ICP-MS Zircon Geochronology and Geochemistry in Determining the History of Magmatic Systems: Insights from the Graciosa A-type Province, Southern Brazil

    NASA Astrophysics Data System (ADS)

    Braun, S.; Gualda, G. A.; Bream, B. R.; Vlach, S. R.

    2010-12-01

    The Graciosa Province comprises more than 20 A-type granitic and syenitic plutons in southern Brazil. This province was emplaced during a period of tectonic change, with A-type magmatism post-dating syntectonic I- and S-type magmatism to the east. Dating the age of magmatism has proven challenging, with current published results showing a wide range of ages (550-590 Ma), most of which with low analytical resolution (2σ errors >15 Ma). We use Laser Ablation ICP-MS to determine U-Pb ages and trace element compositions of zircon crystals in-situ. We analyzed zircon from ten samples representative of the petrographic diversity observed in the 5 plutons located in the Serra da Graciosa region1, which include monzodiorites, granites, and alkali-feldspar granites and syenites. The graintoids include rocks with aluminous affinity (biotite-bearing), and others with alkaline affinity (sodic amphibole-bearing). Our results show three age populations with concordant ages at ~633±6, 581±3, and 539±4 Ma (all errors 2σ): - The oldest zircon ages come from analyses of zircon cores that display overgrowth and resorption textures. - The majority of zircon grains analyzed yield ages ~581 Ma. Zircons of this age can be found in all but two samples analyzed. Spots yielding these ages come from rim regions free of fractures or inclusions. REE patterns show enrichment in HREE, and pronounced positive Ce anomaly, as typically seen in magmatic zircons. - Strongly altered grains from alkali-feldspar granites with biotite dominate the youngest zircon population. These grains have myriad inclusions of thorite, REE fluorides (fluocerite, CeF3 - confirmed by EBSD), and REE phosphates. A few analyses in other rocks yield similar ages. REE patterns are much less steep for these zircons, and Ce anomalies are much more subdued, as characteristic of hydrothermal zircons. Further, these zircons are enriched in high field-strength elements such as Nb and Hf, as well as in Th and U. Based on

  14. Certification of new Pb iCRM (Candidate ERM-38xx series) via Gravimetric Isotope Mixtures and MC-ICP-MS Measurements

    NASA Astrophysics Data System (ADS)

    Ponzevera, E.; Quetel, C. R.

    2008-12-01

    Lead is known to be a particularly toxic chemical element. Mining and smelting of Pb and its domestic use over the centuries have contaminated the surface of Earth and jeopardized the health of humans, domestic animals and wildlife. Omnipresence of Pb has however an advantage. It can be used as an isotopic tracer of pollution sources and pathways in the environment. Pb isotopic Certified Reference Materials (iCRM) with undisputed characteristics are then required to validate Pb isotope ratio measurements. The materials currently available worldwide were produced in the 1960's by the National Bureau of Standards (now NIST, USA) and are now the object of polemics regarding the accuracy of some of the accompanying certified values. Moreover, new materials with lower relative uncertainty statements are demanded by users. This presentation is centred on the production and the certification at the EC-JRC-Institute for Reference Materials and Measurements of a new series of Pb iCRM (candidate ERM-38xx series). The production included six Pb gravimetric isotope mixtures, a common Pb material dedicated to routine calibration work and a series of four 207Pb slightly enriched natural-like Pb materials for the validation of the δ-scale method below 0.01%. The gravimetric isotope mixtures method, originally supported by mass spectrometry measurements performed on GS-MS or TI-MS instruments, was applied successfully to MC-ICP-MS. The measurements and certification methods we developed were validated in several ways, including a systematic investigation on possible significant sources of uncertainty and comparisons of results obtained by different laboratories on identical samples. Relative uncertainties on isotope ratios obtained for the newly produced Pb iCRM are as low as 0.017%, which is between 2 and 4 times smaller than the uncertainties carried by the NIST-981 material. Going below 0.01% was not possible mainly because of uncompressible uncertainties coming from the

  15. Determination of (129)I and (127)I concentration in soil samples from the Chernobyl 30-km zone by AMS and ICP-MS.

    PubMed

    Sahoo, Sarata Kumar; Muramatsu, Yasuyuki; Yoshida, Satoshi; Matsuzaki, Hiroyuki; Rühm, Werner

    2009-07-01

    A large amount of radioiodine isotopes (mainly (131)I, t(1/2) = 8 days) was released from the accident at Chernobyl Nuclear Power Plant (CNPP) in April-May 1986. An increase in childhood-thyroid cancer in the contaminated areas in Belarus, Russia and the Ukraine was demonstrated to be caused by radioiodine released at the time of the accident. However, there is a lack of quantitative data on the (131)I levels in the local environment (e.g. air, plant, soil). At this point, a long-lived iodine isotope, (129)I (t(1/2) = 15.7 million years), also released with a certain ratio to (131)I from CNPP, could be used for estimating the (131)I levels in the environment. In this paper we present analytical results of the (129)I concentrations and (129)I/(127)I atom ratios in soil samples collected from the CNPP exclusion zone (30-km zone), with the aim of assessing current contamination levels and distribution patterns. For the analysis of the iodine fraction in the investigated soil samples, the pyrohydrolysis method was utilized for separation of (127)I and (129)I nuclides, and subsequently their concentration was determined using inductively coupled plasma mass spectrometry (ICP-MS) and accelerator mass spectrometry (AMS), respectively. The concentration of (129)I and the (129)I/(127)I atom ratio in the surface soil samples in the 30 km-zone of CNPP ranged from 4.6 to 170 mBq/kg, and from 1.4 x 10(-6) to 13 x 10(-6), respectively. These values are significantly higher than those from global (129)I fallout, indicating that most of the measured (129)I was due to the deposition of the accident. Stable iodine concentrations in this area were found to be very low (below 1 ppm) for most of the samples, suggesting the environmental iodine levels in this area to be potentially low. The (129)I/(137)Cs activity ratio in surface and sub-surface soils was not so constant, i.e., in the range (7.3-20.2) x 10(-7). This might be due to the different behavior of deposition and/or migration

  16. Sulfur and chalcophile elements in subduction zones: constraints from a laser ablation ICP-MS study of melt inclusions from Galunggung Volcano, Indonesia

    NASA Astrophysics Data System (ADS)

    de Hoog, J. C. M.; Mason, P. R. D.; van Bergen, M. J.

    2001-09-01

    Mafic melt inclusions hosted in olivine phenocrysts (Fo 89-78) in high-Mg basalts of Galunggung volcano (Java, Indonesia) were analyzed in situ by laser ablation ICP-MS to determine concentrations of chalcophile and associated trace elements. Our results indicate that sulfur in the mantle beneath Galunggung is significantly enriched relative to MORB source mantle, suggesting large-scale fluxing of sulfur into the mantle wedge during slab dehydration. Melt-inclusion compositions range from strongly undersaturated to transitional basaltic and are characterized by a wide range of sulfur contents (350-2900 ppm). Chalcophile element concentrations are not affected by exsolution of immiscible sulfide liquids and generally fall within the range of whole-rock samples from other arcs. We infer that primary Galunggung melts contain approximately 290 ppm Ni, 60 ppm Co, 190 ppm Cu, and 3 ppm Pb. Patterns of refractory trace elements point to ˜15% melting of a MORB-source mantle below Galunggung, which was enriched in LILE and LREE by slab-derived fluids before melting. Based on this value, we use melting model calculations to investigate whether slab-derived contributions to a MORB-source mantle are required to balance the budgets of sulfur and associated chalcophile elements, assuming that all Cu and S originally resided in sulfides and adopting a Cu concentration of 28 ppm in the presubduction mantle, similar to that in MORB-type mantle. Modeling results predict at least 256 to 465 ppm S in the magma source of Galunggung, which is up to twice the amount commonly assumed for MORB sources. A slab-derived origin of the excess sulfur is consistent with 34S enrichments that commonly characterize arc magmas and gases. Although modeling suggests that elevated copper concentrations relative to MORB can be the consequence of the higher solubility of sulfur in Galunggung melts, the results do not rule out that the subarc mantle was enriched by slab-derived Cu. Lead must have been

  17. Determination of Cr isotopic composition in low-level carbonates by MC-ICP-MS: a sensitive proxy for redox changes?

    NASA Astrophysics Data System (ADS)

    Bonnand, Pierre; Parkinson, Ian; James, Rachael; Karjalainen, Anne-Mari; Fehr, Manuela; Fairchild, Ian

    2010-05-01

    Geochemical data suggest that atmospheric oxygen increased during two major steps: the Great oxidation event (~2.4 Ga) and the Neoproterozoic (~1Ga-545Ma). The O2 concentration in the atmosphere is strongly linked to the redox condition of the oceans. Therefore the study of redox sensitive elements in marine sediments can be used to evaluate the evolution of O2 concentrations in the atmosphere. Chromium is a redox sensitive element which significantly fractionates its isotopes during the reduction of Cr(VI) to Cr(III) (Ellis et al., 2002). Thus, Cr isotopes can be used to assess redox changes in the past oceans. Chromium isotopic compositions in sedimentary rocks (BIFs) have been used to determine the evolution of the O2 concentration in the atmosphere during the Proterozoic (Frei et al., 2009). We have developed a chemical procedure for the purification of Cr in carbonates by using a single cation column to separate the Cr from the matrix, Fe, Ti and V. Cr isotopic compositions are determined used a 50Cr-54Cr double spike method and analysed on a ThermoFisher Neptune MC-ICP-MS using HR and MR in order to be able to discriminate Ar interferences. Standards and samples are analysed as 50ppb Cr solutions and yield an external reproducibility 50 and 70ppm. This new method allowed us to analyse samples with a Cr concentrations as low as 1ppm. We have analysed a suite of Neoproterozoic carbonates from Australia, but also modern ooids and oolithic limestones through the Phanerozoic. The Cr isotopic data for carbonates record a range of δ53Cr between -0.1 and +1.7. This range indicates that some of these carbonates clearly reflect oxidising conditions in the ocean. By comparison, the Neoproterozoic samples have Cr isotopic compositions close to the continental crust value (-0.1 to 0.1), indicating the Neoproterozoic samples reflect deposition under more reducing conditions These data suggests that the redox condition during the deposition of shallow-water carbonates

  18. 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

  19. Direct Quantification of Rare Earth Elements Concentrations in Urine of Workers Manufacturing Cerium, Lanthanum Oxide Ultrafine and Nanoparticles by a Developed and Validated ICP-MS

    PubMed Central

    Li, Yan; Yu, Hua; Zheng, Siqian; Miao, Yang; Yin, Shi; Li, Peng; Bian, Ying

    2016-01-01

    Rare earth elements (REEs) have undergone a steady spread in several industrial, agriculture and medical applications. With the aim of exploring a sensitive and reliable indicator of estimating exposure level to REEs, a simple, accurate and specific ICP-MS method for simultaneous direct quantification of 15 REEs (89Y, 139La, 140Ce, 141Pr, 146Nd, 147Sm, 153Eu, 157Gd, 159Tb, 163Dy, 165Ho, 166Er, 169Tm, 172Yb and 175Lu) in human urine has been developed and validated. The method showed good linearity for all REEs in human urine in the concentrations ranging from 0.001–1.000 μg∙L−1 with r2 > 0.997. The limits of detection and quantification for this method were in the range of 0.009–0.010 μg∙L−1 and 0.029–0.037 μg∙L−1, the recoveries on spiked samples of the 15 REEs ranged from 93.3% to 103.0% and the relative percentage differences were less than 6.2% in duplicate samples, and the intra- and inter-day variations of the analysis were less than 1.28% and less than 0.85% for all REEs, respectively. The developed method was successfully applied to the determination of 15 REEs in 31 urine samples obtained from the control subjects and the workers engaged in work with manufacturing of ultrafine and nanoparticles containing cerium and lanthanum oxide. The results suggested that only the urinary levels of La (1.234 ± 0.626 μg∙L−1), Ce (1.492 ± 0.995 μg∙L−1), Nd (0.014 ± 0.009 μg∙L−1) and Gd (0.023 ± 0.010 μg∙L−1) among the exposed workers were significantly higher (p < 0.05) than the levels measured in the control subjects. From these, La and Ce were the primary components, and accounted for 88% of the total REEs. Lanthanum comprised 27% of the total REEs while Ce made up the majority of REE content at 61%. The remaining elements only made up 1% each, with the exception of Dy which was not detected. Comparison with the previously published data, the levels of urinary La and Ce in workers and the control subjects show a higher trend

  20. 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

  1. Detrital zircon geochronology by LA-ICP-MS of the Neoarchean Manjeri Formation in the Archean Zimbabwe craton- the disappearance of Eoarchean crust by 2.7 Ga?

    NASA Astrophysics Data System (ADS)

    Sawada, Hikaru; Maruyama, Shigenori; Sakata, Shuhei; Hirata, Takafumi

    2016-01-01

    For the ca. 2.7 Ga (Neoarchean) clastic rocks in the Belingwe greenstone belt (Manjeri Formation), U-Pb age of detrital zircon grains were analyzed by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). The Manjeri Formation, composed of sandstone, quartzite, and limestone with stromatolites, was deposited in a shallow marine setting along the ancient passive continental margin of the Zimbabwe craton. Nearly 100 detrital zircon grains, for each from two sandstone samples in central Zimbabwe, were separated for U-Pb dating. Age spectra of detrital zircon grains of two analyzed sandstones of the Manjeri Formation show more or less the same multiple age clusters: i.e., ca. 2.9 Ga, ca. 3.15 Ga, ca. 3.3 Ga, and ca. 3.5 Ga. These age spectra reflect nature of the provenance of proto-Zimbabwe, which was considerably different from that of the modern Zimbabwe craton. The age clusters of ca. 2.9 Ga, ca. 3.3 Ga, and ca. 3.5 Ga are correlated with those of extant basement rocks of the present Zimbabwe craton, whereas the ca. 3.15 Ga cluster has no corresponding unit within the craton, except for detrital zircons from the 2.65 Ga Shamvaian Group in a neighboring area of the Zimbabwe craton. The extremely old (3.85 Ga; Eoarchean) detrital zircon grains, previously reported from the ca. 2.9 Ga and ca. 3.4 Ga sandstones elsewhere in the craton, were not detected at all in the present two analyzed samples. As no Eoarchean (>3.8 Ga) basement rocks remain in the Zimbabwe craton at present either, the present study confirmed that the Eoarchean crustal rocks once occurred in the proto-Zimbabwe craton but they had been removed secondarily from the provenance of Neoarchean and younger basins prior to 2.7 Ga. Possible geologic processes for such disappearance of older crusts may include the physiological separation by continental rifting, subduction erosion, and/or other crustal recycling processes.

  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. Exploring the in vitro formation of trimethylarsine sulfide from dimethylthioarsinic acid in anaerobic microflora of mouse cecum using HPLC-ICP-MS and HPLC-ESI-MS

    SciTech Connect

    Kubachka, Kevin M.; Kohan, Michael C.; Herbin-Davis, Karen; Creed, John T. Thomas, David J.

    2009-09-01

    Although metabolism of arsenicals to form methylated oxoarsenical species has been extensively studied, less is known about the formation of thiolated arsenical species that have recently been detected as urinary metabolites. Indeed, their presence suggests that the metabolism of ingested arsenic is more complex than previously thought. Recent reports have shown that thiolated arsenicals can be produced by the anaerobic microflora of the mouse cecum, suggesting that metabolism prior to systemic absorption may be a significant determinant of the pattern and extent of exposure to various arsenic-containing species. Here, we examined the metabolism of {sup 34}S labeled dimethylthioarsinic acid ({sup 34}S-DMTA{sup V}) by the anaerobic microflora of the mouse cecum using HPLC-ICP-MS and HPLC-ESI-MS/MS to monitor for the presence of various oxo- and thioarsenicals. The use of isotopically enriched {sup 34}S-DMTA{sup V} made it possible to differentiate among potential metabolic pathways for production of the trimethylarsine sulfide (TMAS{sup V}). Upon in vitro incubation in an assay containing anaerobic microflora of mouse cecum, {sup 34}S-DMTA{sup V} underwent several transformations. Labile {sup 34}S was exchanged with more abundant {sup 32}S to produce {sup 32}S-DMTA{sup V}, a thiol group was added to yield DMDTA{sup V}, and a methyl group was added to yield {sup 34}S-TMAS{sup V}. Because incubation of {sup 34}S-DMTA{sup V} resulted in the formation of {sup 34}S-TMAS{sup V}, the pathway for its formation must preserve the arsenic-sulfur bond. The alternative metabolic pathway postulated for formation of TMAS{sup V} from dimethylarsinic acid (DMA{sup V}) would proceed via a dimethylarsinous acid (DMA{sup III}) intermediate and would necessitate the loss of {sup 34}S label. Structural confirmation of the metabolic product was achieved using HPLC-ESI-MS/MS. The data presented support the direct methylation of DMTA{sup V} to TMAS{sup V}. Additionally, the detection of

  4. Biogeochemistry of sulfur in the Vienna Woods: Study of sulfur stable isotope ratios by MC-ICP-MS as indicator of biogeochemical S cycling

    NASA Astrophysics Data System (ADS)

    Hanousek, Ondrej; Berger, Torsten W.; Prohaska, Thomas

    2014-05-01

    Sulfur entering forest ecosystems originates mainly from combustion of fossil fuels. This source of sulfur has been strongly (by more than 95 %) reduced in last decades and recently, higher sulfur output (in soil solution or stream water) than sulfur input (in rain water) in an ecosystem was registered in many monitored forest ecosystems. This unbalance may be caused by weathering of sulfur-bearing rocks, desorption of sulfur adsorbed in soil in the past or (re)mineralization of organic sulfur compounds. This 'negative' balance leads to mobilization of base cations along with SO42- and as such to an acidification of soils. As hypothesis, δ34S/32S depletion in stream water will be observed if a considerable proportion of atmospherically deposited sulfate is cycled through the organic S pool. Rain water and soil solutions samples were collected for this study at 3 sites (beech stands) in the Vienna Woods, Austria twice a month from May 2010 to April 2012. Due to the expected sulfate concentration gradient with respect to the distance from a tree, sampling was carried out at 5 intervals from a stem. The sulfur concentration in the samples was determined by ion chromatography. Sulfur isotope ratios (δ34S/32SV CDT) were analyzed by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in edge-resolution mode. The method was validated using IAEA-S-1 and IAEA-S-2 isotopic certified reference materials. The combined standard uncertainty of the measurement (uc = 0.10 %, k = 1) proves the suitability of the developed method. The concentration of sulfur in rain water showed expected behavior, with a seasonal maximum in winter months, in contrast to the corresponding δ34S/32SV CDT isotope ratios, where no or low seasonal trends were observed. The sulfur isotope ratios in soil solution samples show a dependence on the distance from a tree stem and the sampling depth with lower δ34S/32SV CDT ratios as compared to the precipitation. The measured isotopic

  5. 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.

  6. LA ICP MS U-Pb ages of detrital zircons from Russia largest rivers: Implications for major granitoid events in Eurasia and global episodes of supercontinent formation

    NASA Astrophysics Data System (ADS)

    Safonova, Inna; Maruyama, Shige; Hirata, Takafumi; Kon, Yoshiaki; Rino, Shuji

    2010-09-01

    The paper presents LA ICP MS U-Pb age data on detrital zircons from sands of major Russian rivers: the Don, Volga, Ob', Yenisey and Amur. The obtained data are discussed in terms of major episodes of granitic magmatism, which are recorded in the continental blocks that form the modern Eurasian continent. Results are compared with published igneous and detrital zircon age data obtained from parental and sedimentary rocks of the river basins under consideration and worldwide. The U-Pb age results allowed us to confirm (i) the episodic character of continent formation; (ii) the Neoarchean global magmatic event and, possibly, formation of the Kenorland supercontinent; (iii) the global episode of crust formation at 2.0-1.8 Ga, which formed the Columbia supercontinent; (iv) the breakup of Columbia at 1.3-1.2 Ga; (v) the major period of Phanerozoic crustal growth in Central Asia which is likely to be a result of the Altaid orogeny. On the other hand, our data did not unambiguously confirm previous idea about the global character of the Grenvillian and Pan-African orogenies as a result of the assembly of Rodinia and Gondwana, respectively. The "Rodinia" peak is not observed in the histograms of the Ob', Yenisey and Amur, whereas the "Gondwana" signature is not obvious in the histograms of the Don, Volga and Amur. Of special interest are the 2.7-2.5 Ga and 2.0-1.7 Ga peaks in the Ob' zircon age spectrum in spite of the absence of so far identified Archean and Paleoproterozoic parental rocks in the Ob' catchment area. The obtained age spectra were joined into three groups based on statistics: Baltica (Don and Volga), Siberia (Ob' and Yenisey) and East Asia (Amur). For future reconstructions we suggest to include all the available results on Don and Volga rivers into a North America-Baltica Group corresponding to Laurentia-derived continental blocks, and to consider a Siberia Group (Siberian Craton; Ob', Yenisey, Lena, Indigirka rivers) and an East Asia Group (North and South

  7. Direct Quantification of Rare Earth Elements Concentrations in Urine of Workers Manufacturing Cerium, Lanthanum Oxide Ultrafine and Nanoparticles by a Developed and Validated ICP-MS.

    PubMed

    Li, Yan; Yu, Hua; Zheng, Siqian; Miao, Yang; Yin, Shi; Li, Peng; Bian, Ying

    2016-03-01

    Rare earth elements (REEs) have undergone a steady spread in several industrial, agriculture and medical applications. With the aim of exploring a sensitive and reliable indicator of estimating exposure level to REEs, a simple, accurate and specific ICP-MS method for simultaneous direct quantification of 15 REEs ((89)Y, (139)La, (140)Ce, (141)Pr, (146)Nd, (147)Sm, (153)Eu, (157)Gd, (159)Tb, (163)Dy, (165)Ho, (166)Er, (169)Tm, (172)Yb and (175)Lu) in human urine has been developed and validated. The method showed good linearity for all REEs in human urine in the concentrations ranging from 0.001-1.000 μg ∙ L(-1) with r² > 0.997. The limits of detection and quantification for this method were in the range of 0.009-0.010 μg ∙ L(-1) and 0.029-0.037 μg ∙ L(-1), the recoveries on spiked samples of the 15 REEs ranged from 93.3% to 103.0% and the relative percentage differences were less than 6.2% in duplicate samples, and the intra- and inter-day variations of the analysis were less than 1.28% and less than 0.85% for all REEs, respectively. The developed method was successfully applied to the determination of 15 REEs in 31 urine samples obtained from the control subjects and the workers engaged in work with manufacturing of ultrafine and nanoparticles containing cerium and lanthanum oxide. The results suggested that only the urinary levels of La (1.234 ± 0.626 μg ∙ L(-1)), Ce (1.492 ± 0.995 μg ∙ L(-1)), Nd (0.014 ± 0.009 μg ∙ L(-1)) and Gd (0.023 ± 0.010 μg ∙ L(-1)) among the exposed workers were significantly higher (p < 0.05) than the levels measured in the control subjects. From these, La and Ce were the primary components, and accounted for 88% of the total REEs. Lanthanum comprised 27% of the total REEs while Ce made up the majority of REE content at 61%. The remaining elements only made up 1% each, with the exception of Dy which was not detected. Comparison with the previously published data, the levels of urinary La and Ce in workers and

  8. Binding and transport of rare earth elements by organic and iron-rich nanocolloids in Alaskan rivers, as revealed by field-flow fractionation and ICP-MS

    NASA Astrophysics Data System (ADS)

    Stolpe, Björn; Guo, Laodong; Shiller, Alan M.

    2013-04-01

    Water samples were collected from six small rivers in the Yukon River basin in central Alaska to examine the role of nanocolloids (0.5-40 nm) in the dynamics and transport of rare earth elements (REEs) in northern high latitude watersheds influenced by permafrost. Total dissolved (<0.45 μm) concentrations and the 'nanocolloidal size distributions' (0.5-40 nm) of UV-absorbing dissolved organic matter, Fe, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu were determined by on-line coupling of flow field-flow fractionation (FFF) with a UV-absorbance detector and ICP-MS. Total dissolved and nanocolloidal concentrations of the REEs co-varied with dissolved organic carbon (DOC) in all rivers and between spring flood and late summer baseflow. The nanocolloidal size distributions indicated the presence of three major components of nanocolloids: the 0.5-3 nm 'fulvic-rich nanocolloids' occurring throughout the sampling season, the 'organic/iron-rich nanocolloids' residing in the <8 nm size range during the spring flood, and the 4-40 nm iron-rich nanocolloids occurring during summer baseflow. REEs associated with all the three components of nanocolloids, but the proportions associated with the fulvic-rich nanocolloids during summer baseflow increased with increasing REE molar mass, which is consistent with the increase in stability of organic REE-complexes with increasing REE molar mass. Normalization of the measured REE-concentrations with the average REE-concentrations of the upper continental crust revealed a dynamic change in the physicochemical fractionation of REEs. During the spring flood, REE-binding in all the rivers was dominated by the <8 nm organic/iron-rich nanocolloids, likely being eroded from the upper organic-rich soil horizon by the strong surface runoff of snowmelt water. During the summer, the REE-binding in rivers with large groundwater input was dominated by small (<0.5 nm) organic and/or inorganic complexes, while lower proportions of the REEs

  9. Investigations on the use of chemical modifiers for the direct determination of trace impurities in Al2O3 ceramic powders by slurry electrothermal evaporation coupled with inductively-coupled plasma mass spectrometry (ETV-ICP-MS).

    PubMed

    Wende, M C; Broekaert, J A

    2001-07-01

    The direct determination of trace impurities in Al2O3 ceramic basic powders by ICP-MS using electrothermal evaporation (ETV) with slurry sampling has been investigated. To increase interference-free analyte volatilization, the use of the palladium-group modifiers (PGM) IrCl3, Pd(NO3)2, and PdCl2 for the determination of Ca, Fe, Ga, Mg, Mn, Na, Ni, and V in Al2O3 powders was studied. Their role, which in ETV-ICP-MS and ETV-ICP-OES is to stabilize the investigated analyte during the ashing phase, to increase vaporization of the matrix, and to reduce transport losses was investigated. Optimum analysis results were obtained with PdCl2 modifier when 500 ng Pd was used for a sample weight of 100 microg Al2O3 injected into the ETV. Calibration was performed by standard addition with aqueous solutions of the analytes. The RSDs calculated from triplicate analysis ranged form 5 to 10%. Detection limits between 0.07 microg g(-1) (Ga) and 1.1 microg g(-1) (Na) were achieved. The accuracy was proven for the elements Ca, Fe, Ga, Mg, Mn, Na, Ni, and V by analyzing an NIST standard reference Al2O3 material (SRM 699) with a middle grain size of 16.4 microm. The analytical method was used for the analysis of Al2O3 powder (AKP 30, Sumitomo, Japan) with impurities in the low microg g(-1) range and a middle grain size of 1.1 microm. The results obtained for the elements Ca, Fe, Ga, Mg, Mn, Na, Ni, and V were comparable with those obtained by ICP-MS subsequent to conventional decomposition with hydrochloric acid at high pressure. PMID:11496980

  10. Strontium isotope systematics of scheelite and apatite from the Felbertal tungsten deposit, Austria - results of in-situ LA-MC-ICP-MS analysis

    NASA Astrophysics Data System (ADS)

    Kozlik, Michael; Gerdes, Axel; Raith, Johann G.

    2016-02-01

    The in-situ Sr isotopic systematics of scheelite and apatite from the Felbertal W deposit and a few regional Variscan orthogneisses ("Zentralgneise") have been determined by LA-MC-ICP-MS. The 87Sr/86Sr ratios of scheelite and apatite from the deposit are highly radiogenic and remarkably scattering. In the early magmatic-hydrothermal scheelite generations (Scheelite 1 and 2) the 87Sr/86Sr ratios range from 0.72078 to 0.76417 and from 0.70724 to 0.76832, respectively. Metamorphic Scheelite 3, formed by recrystallisation and local mobilisation of older scheelite, is characterised by even higher 87Sr/86Sr values between 0.74331 and 0.80689. Statistics allows discriminating the three scheelite generations although there is considerable overlap between Scheelite 1 and 2; they could be mixtures of the same isotopic reservoirs. The heterogeneous and scattering 87Sr/86Sr ratios of the two primary scheelite generations suggest modification of the Sr isotope system due to fluid-rock interaction and isotopic disequilibrium. Incongruent release of 87Sr from micas in the Early Palaeozoic host rocks of the Habach Complex contributed to the solute budget of the hydrothermal fluids and may explain the radiogenic Sr isotope signature of scheelite. Spatially resolved analyses revealed isotopic disequilibrium even on a sub-mm scale within zoned Scheelite 2 crystals indicating scheelite growth in an isotopic dynamical hydrothermal system. Zoned apatite from the W mineralised Early Carboniferous K1-K3 orthogneiss in the western ore field yielded 87Sr/86Sr of 0.72044-0.74514 for the cores and 0.74535-0.77937 for the rims. Values of magmatic apatite cores from the K1-K3 orthogneiss are comparable to those of primary Scheelite 1; they are too radiogenic to be magmatic. The Sr isotopic composition of apatite cores was therefore equally modified during the hydrothermal mineralisation processes, therefore supporting the single-stage genetic model in which W mineralisation is associated with

  11. Evidence for Archean inheritance in the pre-Panafrican crust of Central Cameroon: Insight from zircon internal structure and LA-MC-ICP-MS Usbnd Pb ages

    NASA Astrophysics Data System (ADS)

    Ganwa, Alembert Alexandre; Klötzli, Urs Stephan; Hauzenberger, Christoph

    2016-08-01

    The main geological feature of Central Cameroon is the wide spread occurrence of granitoids emplaced in close association with transcurrent regional shear zones. The basement of this vast domain is a Paleoproterozoic ortho-and para-derivative formation, which has been intensely reworked, together with subsequent intrusions and sediments, during the Panafrican orogenesis in the Neoproterozoic. As consequence, the area underwent pervasive metamorphism and intense deformation. This makes it difficult to distinguish between Panafrican metasediments or syntectonic plutonites and their respective basement. Our study presents zircon features (CL-BSE-SE) and in-situ U-Th-Pb LA-MC-ICP-MS geochronology of a meta-sedimentary pyroxene-amphibole-bearing gneiss of the Méiganga area in Central Cameroon. Based on the Internal structures of the zircon four characteristic zonation patterns can be deciphered: 1) cores with magmatic oscillatory zonation 2) zircons with oscillatory or sector zonation, 3) zircons with sector zoning or blurred zoning, and 4) narrow bright un-zoned rims. These groups suggest that the rock experienced a number of geological events. Considering this zircon characteristic, the U-Th-Pb data allow to distinguish four ages: 2116 ± 57 Ma, consistent with ages from the Paleoproterozoic West Central African Belt; 2551 ± 33 Ma which marks a late Neoarchean magmatic event; 2721 ± 27 Ma related to a Neoarchean magmatic even in Central Cameroon, similar to one found in the Congo Craton. A zircon core gives ages around 2925 Ma which provides some evidence of the presence of the Mesoarchean basement prior to the Neoarchean magmatism. A weighted average of lower intercepts ages gives a value of 821 ± 50 Ma, representing the age of later metamorphism event. The various characteristic group and related ages reflect not only the complexity of the history of the pyroxene amphibole gneiss, but also show that the meta-sediment has at least three zircon

  12. Trace element incorporation into quartz: A combined study by ICP-MS, electron spin resonance, cathodoluminescence, capillary ion analysis, and gas chromatography

    NASA Astrophysics Data System (ADS)

    Götze, Jens; Plötze, Michael; Graupner, Torsten; Hallbauer, Dieter Klaus; Bray, Colin J.

    2004-09-01

    Pegmatite quartz from different occurrences in Norway and Namibia was investigated by a combination of ICP-MS, Electron Spin Resonance (ESR), Capillary Ion Analysis (CIA) and Gas Chromatography (GC) to quantify trace elements in very low concentrations and to determine their position in the quartz structure. The studied quartz samples show similar geochemical characteristics with low contents of most trace elements. Remarkable are the elevated concentrations of Al (36-636 ppm), Ti (1.6-25.2 ppm), Ge (1.0-7.1 ppm), Na (5.2 to >50 ppm), K (1.6 to >100 ppm) and Li (2.1-165.6 ppm). These elements are preferentially incorporated into the quartz lattice on substitutional (Al, Ti, Ge) and interstitial (Li, Na, K) positions. Li + was found to be the main charge compensating ion for Al, Ge and Ti, whereas some ppm of Na and K may also be hosted by fluid inclusions. Ti may be incorporated as substitutional ion for Si or bound on mineral microinclusions (rutile). The results of the ESR measurements show that there may be a redistribution of alkali ions during irradiation. The diamagnetic [AlO 4/M +] 0 center transforms into the paramagnetic [AlO 4] 0 center, whilst the compensating ions diffuse away and may be captured by the diamagnetic precursor centers of [GeO 4] 0 and [TiO 4] 0 to form paramagnetic centers ([TiO 4/Li +] 0, [GeO 4/Li +] 0). In general, fluid inclusions in pegmatite quartz can be classified as H 2O-CO 2-NaCl type inclusions with water as the predominant volatile. Among the main elements hosted by fluid inclusions in quartz are Na, K, NH 4, Ca, Mg and the anionic complexes Cl -, NO 3-, HCO 3- and SO 42-. Gas analysis of trapped fluids shows volatile components in the following order of abundance: H 2O > CO 2 > N 2(+) ≥ CH 4 > COS > C 2 and C 3 hydrocarbons. Additionally, traces of Co, Ni, Zn, Pb, and Cu were detected by CIA in fluid inclusions of some samples. There are indications that the REE and Rb are also bound in fluid inclusions, however, the

  13. Zirconia-coated graphite adsorption bar micro-extraction combined with ETV-ICP-MS for the determination of trace amounts of Cd, Hg and Pb in environmental and biological samples.

    PubMed

    Pu, Xuli; Jiang, Zucheng; Hu, Bin

    2006-07-01

    In this work, a new and simple micro-extraction method termed graphite adsorption bar micro-extraction was developed, for the first time, for electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) determination of trace Cd, Hg and Pb. In this method, the graphite bar was first coated with zirconia and then inserted into the sample solution for extraction. The graphite bar enriched with the analytes was inserted directly into a graphite tube, and subsequently analyzed by ETV-ICP-MS according to an established temperature program. The experimental parameters, which had influence on the extraction and vaporization, were systematically investigated and the optimal experimental conditions were established. Under the optimized conditions, the detection limits of the method were 0.05, 0.42 and 0.06 pg/ml for Cd, Hg and Pb and the relative standard deviations (RSDs) for 11 replicates at the 0.1 ng/ml level were 7.4, 8.2 and 7.7%, respectively. The proposed method was successfully applied to the determination of trace Cd, Hg and Pb in environmental and biological samples. The results of the experiments indicate that the method has a high enrichment factor and sample utilization efficiency. Furthermore, the method is fast and environment-friendly. PMID:16810641

  14. Asymmetric Flow-Field Flow Fractionation Hyphenated ICP-MS as an Alternative to Cloud Point Extraction for Quantification of Silver Nanoparticles and Silver Speciation: Application for Nanoparticles with a Protein Corona.

    PubMed

    Mudalige, Thilak K; Qu, Haiou; Linder, Sean W

    2015-07-21

    Production and application of nanoparticles in consumer products is at an all-time high due to the emerging field of nanotechnology. Direct detection and quantification of trace levels of nanoparticles within consumer products is very challenging and problematic. Although multiple methodologies are available for this purpose, each method has its own set of limitations. Herein, we developed an analytical platform consisting of asymmetric flow-field flow fractionation (AF4) coupled with inductively coupled plasma mass spectroscopy (ICP-MS) for the speciation and quantification of silver ions and silver nanoparticles at the ng/kg level (ppt). AF4 is utilized to concentrate the nanoparticles, and ICP-MS acts as the detector. The protein corona that forms upon exposure of nanoparticles to bovine serum albumin was utilized as a nanoparticle stabilization and AF4 recovery enhancement mechanism. Speciation of silver ions and nanoparticles was achieved with the assistance of penicillamine as a complexation ligand. The effect of nanoparticle size, surface coating, and ionization state toward the detection and quantification of the developed methodology was evaluated. The detection limit was found to be 4 ng/kg with the application of a 5 mL sample loop. Further application of this developed methodology on environmentally relevant samples was demonstrated by the analysis of Arkansas River water spiked with silver nanoparticles and nanoparticle spiked into humic acid solution (50 mg/L) at an environmentally relevant level. PMID:26095720

  15. LA-ICP-MS analyses of minor and trace elements and bulk Ge isotopes in zoned Ge-rich sphalerites from the Noailhac - Saint-Salvy deposit (France): Insights into incorporation mechanisms and ore deposition processes

    NASA Astrophysics Data System (ADS)

    Belissont, Rémi; Boiron, Marie-Christine; Luais, Béatrice; Cathelineau, Michel

    2014-02-01

    The increasing worldwide demand in germanium (Ge) is driving renewed research for understanding its geological cycle and the factors controlling its concentration in minerals. The advent of accurate, high-resolution trace element analysis by LA-ICP-MS, as well as the advances in MC-ICP-MS technique for Ge isotopes in sulphides, has enhanced studies in this field. Ge isobaric interferences, standard calibration and data interpretation remain outstanding issues needing to be addressed for more precise and comprehensive LA-ICP-MS analyses. An integrated mineralogical and geochemical study was carried out on typical sphalerite (ZnS) samples from the main Ge deposit in western Europe: the vein-type Zn-Ge-Ag-(Pb-Cd) deposit of Noailhac - Saint-Salvy (Tarn, France). In situ coupled measurements of trace elements and S isotopes were performed using LA-ICP-MS and SIMS, respectively, together with bulk Ge isotopes by MC-ICP-MS. Principal component analyses revealed element clusters antithetically distributed within distinct zoning types in sphalerite: sector zonings are enriched in Cu, Ge, Ga, Sb and As, whereas rhythmic bandings (dark brown bands primarily) are enriched in Fe, Cd, In and Sn. This typical distribution points to crystallographic controls on trace element uptake during sphalerite growth, occurring with concomitant microscale variations in fluid compositions at the fluid-crystal interface. Regardless of the zoning type, in all spots, Cu contents approach the sum of tri- and tetravalent cations (Ge, Ga, In, etc.) so that Cu could provide charge-balance for the entire set of coupled substitution mechanisms responsible for the incorporation of the whole range of trace elements in this sphalerite. Strong binary correlations suggest direct substitutions as Zn2+ ↔ (Fe2+, Cd2+) and coupled substitutions as 2Zn2+ ↔ Cu+ + Sb3+, 3Zn2+ ↔ Ge4+ + 2Ag+, and 3Zn2+ ↔ In3+ + Sn3+ + □ (vacancy) despite no clear evidence for the presence of Sn4+. δ74GeNIST3120a in bulk

  16. 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.

  17. Reply to Comment on "Zircon U-Th-Pb dating using LA-ICP-MS: Simultaneous U-Pb and U-Th dating on the 0.1 Ma Toya Tephra, Japan"

    NASA Astrophysics Data System (ADS)

    Ito, Hisatoshi

    2015-04-01

    Guillong et al. (2015) mentioned that corrections for abundance sensitivity for 232Th and molecular zirconium sesquioxide ions (Zr2O3+) are critical for reliable determination of 230Th abundances in zircon for LA-ICP-MS analyses. There is no denying that more rigorous treatments are necessary to obtain more reliable ages than those in Ito (2014). However, as shown in Fig. 2 in Guillong et al. (2015), the uncorrected (230Th)/(238U) for reference zircons except for Mud Tank are only 5-20% higher than unity. Since U abundance of Toya Tephra zircons that have U-Pb ages < 1 Ma is in-between that of FCT and Plesovice, the overestimation of 230Th by both abundance sensitivity and molecular interferences is expected to be 5-20% for the Toya Tephra. Moreover Ito (2014) obtained U-Th ages of the Toya Tephra by comparison with Fish Canyon Tuff (FCT) data. Because both the FCT and the Toya Tephra have similar trends of overestimation of 230Th, the effect of overestimation of 230Th to cause overestimation of U-Th age should be cancelled out or negligible. Therefore the pivotal conclusion in Ito (2014) that simultaneous U-Pb and U-Th dating using LA-ICP-MS is possible and useful for Quaternary zircons holds true.

  18. Determination of trace/ultratrace rare earth elements in environmental samples by ICP-MS after magnetic solid phase extraction with Fe3O4@SiO2@polyaniline-graphene oxide composite.

    PubMed

    Su, Shaowei; Chen, Beibei; He, Man; Hu, Bin; Xiao, Zuowei

    2014-02-01

    A novel Fe3O4@SiO2@polyaniline-graphene oxide composite (MPANI-GO) was prepared through a simple noncovalent method and applied to magnetic solid phase extraction (MSPE) of trace rare earth elements (REEs) in tea leaves and environmental water samples followed by inductively coupled plasma mass spectrometry (ICP-MS) detection. The prepared MPANI-GO was characterized by transmission electron microscopy and vibrating sample magnetometer. Various parameters affecting MPANI-GO MSPE of REEs have been investigated. Under the optimized conditions, the limits of detection (LODs, 3σ) for REEs were in the range of 0.04-1.49 ng L(-1) and the relative standard deviations (RSDs, c=20 ng L(-1), n=7) were 1.7-6.5%. The accuracy of the proposed method was validated by analyzing a Certified Reference Material of GBW 07605 tea leaves. The method was also successfully applied for the determination of trace REEs in tea leaves and environmental water samples. The developed MPANI-GO MSPE-ICP-MS method has the advantages of simplicity, rapidity, high sensitivity, high enrichment factor and is suitable for the analysis of trace REEs in samples with complex matrix. PMID:24401441

  19. Reduction of Matrix-Induced Oxide Interferences on Rare Earth Elements and Platinum Using a Desolvating Nebulizer System with Quadrupole Inductively Coupled Plasma Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Smith, F.

    2013-12-01

    This paper will examine the use of a specialized low-flow desolvating nebulizer system for reduction of oxide mass spectral interferences that can occur in quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). This nebulizer system uses an inert low-flow nebulizer (100 microliters/min) coupled to an inert, heated membrane desolvator for efficient water vapor removal before sample aerosol injection to the Q-ICP-MS instrument. Water vapor from conventional nebulizer / spray chamber systems used with Q-ICP-MS can cause numerous mass spectral interferences. One general example is metal oxides formed from the combination of oxygen (from injected water) with sample matrix components. Two specific examples of metal oxide interferences will be investigated with and without membrane desolvation: Ba and Ce oxides on several low-mass rare earth elements (Sm, Eu, and Gd) and Hf oxides on platinum. Rare earth elements are critically important components of modern electronics (ex. magnets, lasers, cell phones, computers) and platinum is a widely used catalyst. Figures of merit for both a conventional nebulizer/spray chamber and the desolvating nebulizer systems will include operating conditions, interference intensities and reduction factors, background equivalent concentrations (BECs), and instrument detection limits (IDLs).

  20. In vivo determination of aluminum, cobalt, chromium, copper, nickel, titanium and vanadium in oral mucosa cells from orthodontic patients with mini-implants by Inductively coupled plasma-mass spectrometry (ICP-MS).

    PubMed

    Martín-Cameán, Ana; Jos, Angeles; Puerto, Maria; Calleja, Ana; Iglesias-Linares, Alejandro; Solano, Enrique; Cameán, Ana M

    2015-10-01

    Miniscrews are used as orthodontic anchorage devices in the dentistry clinical practice but the in vivo metallic release from these structures has been not previously investigated. The aim of this study was to determine the content of Al, Co, Cr, Cu, Ni, Ti and V in oral mucosa cells of control subjects, patients under orthodontic treatment and with both, orthodontic treatment and miniscrew, in order to know the contribution of these mini-implants to the total metallic content. ICP-MS measurements revealed the following ascending order: Cr

  1. Investigating the adduct formation of organic mercury species with carbonic anhydrase and hemoglobin from human red blood cell hemolysate by means of LC/ESI-TOF-MS and LC/ICP-MS.

    PubMed

    Hogeback, Jens; Schwarzer, Miriam; Wehe, Christoph A; Sperling, Michael; Karst, Uwe

    2016-01-01

    The interaction of mercury species with human erythrocytes is studied to investigate possible high molecular binding partners for mercury species. Human blood hemolysate was spiked with methylmercury and investigated by means of liquid chromatography (LC) coupled to electrospray ionization time of flight mass spectrometry (ESI-ToF-MS) and inductively coupled plasma mass spectrometry (ICP-MS). Beside adduct formation of mercury species with hemoglobin, the main compound of the erythrocytes, mercury binding to the enzyme carbonic anhydrase was revealed. Due to an enzymatic digest of the protein-mercury adduct, the binding site at the free thiol group of the protein was identified. These results indicate that carbonic anhydrase might play a role in mercury toxicity. PMID:26442983

  2. Determination of 234U/238U, 235U/238U and 236U/238U Isotope Ratios in Urine Using Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS)

    PubMed Central

    Xiao, Ge; Jones, Robert L.; Saunders, David; Caldwell, Kathleen L.

    2016-01-01

    Quantification of the isotopic composition of uranium in urine at low levels of concentration is important for assessing both military and civilian populations’ exposures to uranium. However, until now there has been no convenient, precise method established for rapid determination of multiple uranium isotope ratios. Here we report a new method to measure 234U/238U, 235U/238U and 236U/238U. It uses solid phase chelation extraction (via TRU columns) of actinides from the urine matrix, followed by measurement using a magnetic sector field inductively coupled plasma mass spectrometer (SF-ICP-MS - Thermo Element XR) equipped with a high efficiency nebulizer (Apex PFA microflow) and coupled with a membrane desolvating introduction system (Aridus II™). This method provides rapid and reliable results, and has been used successfully to analyze Certified Reference Materials (CRM). PMID:24563523

  3. Measurement of mercury species in whole blood using speciated isotope dilution methodology integrated with microwave-enhanced solubilization and spike equilibration, headspace-solid-phase microextraction, and GC-ICP-MS analysis.

    PubMed

    Rahman, G M Mizanur; Wolle, Mesay Mulugeta; Fahrenholz, Timothy; Kingston, H M Skip; Pamuku, Matt

    2014-06-17

    A biomonitoring method was developed for the determination of inorganic-, methyl-, and ethylmercury (Hg(2+), CH3Hg(+), and C2H5Hg(+), respectively) in whole blood by triple-spiking speciated isotope dilution mass spectrometry (SIDMS) using headspace (HS) solid-phase microextraction (SPME) in combination with gas chromatographic (GC) separation and inductively coupled plasma mass spectrometric (ICP-MS) detection. After spiking the blood sample with isotopically enriched analogues of the analytes ((199)Hg(2+), CH3(200)Hg(+) and C2H5(201)Hg(+)), the endogenous Hg species were solubilized in 2.0 mol L(-1) HNO3 and equilibrated with the spikes using a microwave-enhanced protocol. The microwaved sample was treated with a 1% (w/v) aqueous solution of sodium tetrapropylborate (buffered to pH 5.2), and the propylated Hg species were sampled in the HS using a Carboxen/polydimethylsiloxane-coated SPME fiber. The extracted species were thermally desorbed from the fiber in the GC injection port and determined by GC-ICP-MS. The analytes were quantified, with simultaneous correction for their method-induced transformation, on the basis of the mathematical relationship in triple-spiking SIDMS. The method was validated using a bovine blood standard reference material (SRM 966, Level 2). Analysis of human blood samples demonstrated the accuracy and reproducibility of the method, which can detect the Hg species down to 30 pg g(-1) in blood. The validity of the analytical results found for the blood samples was demonstrated using mass balance by comparing the sum of the concentrations of the individual Hg species with the total Hg in the corresponding samples; the latter was determined by isotope dilution mass spectrometry (IDMS) after decomposing the blood using EPA Method 3052 with single-spiking. PMID:24845130

  4. Quantification of strontium in human serum by ICP-MS using alternate analyte-free matrix and its application to a pilot bioequivalence study of two strontium ranelate oral formulations in healthy Chinese subjects.

    PubMed

    Zhang, Dan; Wang, Xiaolin; Liu, Man; Zhang, Lina; Deng, Ming; Liu, Huichen

    2015-01-01

    A rapid, sensitive and accurate ICP-MS method using alternate analyte-free matrix for calibration standards preparation and a rapid direct dilution procedure for sample preparation was developed and validated for the quantification of exogenous strontium (Sr) from the drug in human serum. Serum was prepared by direct dilution (1:29, v/v) in an acidic solution consisting of nitric acid (0.1%) and germanium (Ge) added as internal standard (IS), to obtain simple and high-throughput preparation procedure with minimized matrix effect, and good repeatability. ICP-MS analysis was performed using collision cell technology (CCT) mode. Alternate matrix method by using distilled water as an alternate analyte-free matrix for the preparation of calibration standards (CS) was used to avoid the influence of endogenous Sr in serum on the quantification. The method was validated in terms of selectivity, carry-over, matrix effects, lower limit of quantification (LLOQ), linearity, precision and accuracy, and stability. Instrumental linearity was verified in the range of 1.00-500ng/mL, corresponding to a concentration range of 0.0300-15.0μg/mL in 50μL sample of serum matrix and alternate matrix. Intra- and inter-day precision as relative standard deviation (RSD) were less than 8.0% and accuracy as relative error (RE) was within ±3.0%. The method allowed a high sample throughput, and was sensitive and accurate enough for a pilot bioequivalence study in healthy male Chinese subjects following single oral administration of two strontium ranelate formulations containing 2g strontium ranelate. PMID:25023847

  5. Determination of Total Iodine in Infant Formula and Adult/ Pediatric Nutritional Formula by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS): Collaborative Study, Final Action 2012.15.

    PubMed

    Zywicki, Richard S; Sullivan, Darryl M

    2015-01-01

    A collaborative study was conducted to determine total iodine in infant formula and adult/pediatric nutritional formula by inductively coupled plasma-MS (ICP-MS) using AOAC First Action Official Method(SM) 2012.15. The purpose of this study was to evaluate the method's intralaboratory and interlaboratory performance and submit the results to AOAC INTERNATIONAL for adoption as a Final Action Official Method for the determination of total iodine in infant formula and adult/pediatric nutritional formula. Upon providing acceptable results for practice samples National Institute of Standard and Technology (NIST) Standard Reference Material (SRM) 1849a and a low-fat adult nutritional powder, 13 laboratories analyzed seven various infant and adult nutritional products including a blind duplicate of each. Products were chosen with varying levels of iodine and included low-fat, soy-based, and milk-based formulas and NIST SRM 1849a. Random identification numbers were assigned to each of the seven fortified test materials. Digestion of the test samples occurred using a potassium hydroxide solution in an oven or open-vessel microwave system. Iodine was stabilized with ammonium hydroxide and sodium thiosulfate after digestion. The solutions were brought to volume followed by filtration. The filtrates were then analyzed by ICP-MS after dilution. Results for all seven test samples met all the AOAC Standard Method Performance Requirements (SMPR(®) 2012.008) guidelines. The RSDr ranged from 0.77 to 4.78% and the RSDR from 5.42 to 11.5%. The Horwitz ratio (HorRat) for each result was excellent, ranging from 0.35 to 1.31%. The results demonstrate that the method is fit-for-purpose to determine iodine in infant formula and adult/pediatric nutritional formula. PMID:26525260

  6. Capillary electrophoresis-electrospray mass spectrometry and HR-ICP-MS for the detection and quantification of 10B-boronophenylalanine (10B-BPA) used in boron neutron capture therapy.

    PubMed

    Pitois, Aurélien; de las Heras, Laura Aldave; Zampolli, Antonella; Menichetti, Luca; Carlos, Ramon; Lazzerini, Guido; Cionini, Luca; Salvatori, Pietro Alberto; Betti, Maria

    2006-02-01

    Boron neutron capture therapy (BNCT) is a bimodal radiotherapeutic treatment based on the irradiation of neoplastic tissues with neutrons after the tissues have selectively accumulated molecules loaded with nuclides with large neutron capture cross-sections (such boron-10). Boron-10 carriers have been tested to a limited extent, and clinical trials have been conducted on sulfhydryl borane (10B-BSH) and boronophenylalanine (10B-BPA). However, precise and accurate measurements of boron-10 concentrations (0.1-100 microg/g) in specimens and samples of limited size (microg scale) are needed in order to be able to biologically characterise new compounds in predictive tissue dosimetry, toxicology and pharmacology studies as well as in clinical investigations. A new approach based on fast separation and detection of 10B-BPA performed by coupling capillary electrophoresis to electrospray mass spectrometry is reported. This method allows the quantitative analysis and characterisation of 10B-BPA in a short time with a high separation efficiency. Detection limits of 3 microM for 10B-BPA and 30 ng/mL for 10B were obtained with CE-ESI-MS. A quantification limit of 10 microM for 10B-BPA (100 ng/mL for 10B) was attained. The total boron-10 concentration was determined by high-resolution inductively coupled mass spectrometry in order to validate the method. Boron-10 isotope measurements were carried out by HR-ICP-MS at medium resolution (R=4000) due to the presence of an isobaric interference at mass 10. Good agreement was obtained between the values from CE-ESI-MS and those from HR-ICP-MS. The method has been successfully used to determine the 10B-BPA in two lines of cultured cells. PMID:16372182

  7. Microwave-assisted wet digestion with H2O2 at high temperature and pressure using single reaction chamber for elemental determination in milk powder by ICP-OES and ICP-MS.

    PubMed

    Muller, Edson I; Souza, Juliana P; Muller, Cristiano C; Muller, Aline L H; Mello, Paola A; Bizzi, Cezar A

    2016-08-15

    In this work a green digestion method which only used H2O2 as an oxidant and high temperature and pressure in the single reaction chamber system (SRC-UltraWave™) was applied for subsequent elemental determination by inductively coupled plasma-based techniques. Milk powder was chosen to demonstrate the feasibility and advantages of the proposed method. Samples masses up to 500mg were efficiently digested, and the determination of Ca, Fe, K, Mg and Na was performed by inductively coupled plasma optical emission spectrometry (ICP-OES), while trace elements (B, Ba, Cd, Cu, Mn, Mo, Pb, Sr and Zn) were determined by inductively coupled plasma mass spectrometry (ICP-MS). Residual carbon (RC) lower than 918mgL(-1) of C was obtained for digests which contributed to minimizing interferences in determination by ICP-OES and ICP-MS. Accuracy was evaluated using certified reference materials NIST 1549 (non-fat milk powder certified reference material) and NIST 8435 (whole milk powder reference material). The results obtained by the proposed method were in agreement with the certified reference values (t-test, 95% confidence level). In addition, no significant difference was observed between results obtained by the proposed method and conventional wet digestion using concentrated HNO3. As digestion was performed without using any kind of acid, the characteristics of final digests were in agreement with green chemistry principles when compared to digests obtained using conventional wet digestion method with concentrated HNO3. Additionally, H2O2 digests were more suitable for subsequent analysis by ICP-based techniques due to of water being the main product of organic matrix oxidation. The proposed method was suitable for quality control of major components and trace elements present in milk powder in consonance with green sample preparation. PMID:27260458

  8. Au-Interaction of Slp1 Polymers and Monolayer from Lysinibacillus sphaericus JG-B53 - QCM-D, ICP-MS and AFM as Tools for Biomolecule-metal Studies.

    PubMed

    Suhr, Matthias; Raff, Johannes; Pollmann, Katrin

    2016-01-01

    In this publication the gold sorption behavior of surface layer (S-layer) proteins (Slp1) of Lysinibacillus sphaericus JG-B53 is described. These biomolecules arrange in paracrystalline two-dimensional arrays on surfaces, bind metals, and are thus interesting for several biotechnical applications, such as biosorptive materials for the removal or recovery of different elements from the environment and industrial processes. The deposition of Au(0) nanoparticles on S-layers, either by S-layer directed synthesis or adsorption of nanoparticles, opens new possibilities for diverse sensory applications. Although numerous studies have described the biosorptive properties of S-layers, a deeper understanding of protein-protein and protein-metal interaction still remains challenging. In the following study, inductively coupled mass spectrometry (ICP-MS) was used for the detection of metal sorption by suspended S-layers. This was correlated to measurements of quartz crystal microbalance with dissipation monitoring (QCM-D), which allows the online detection of proteinaceous monolayer formation and metal deposition, and thus, a more detailed understanding on metal binding. The ICP-MS results indicated that the binding of Au(III) to the suspended S-layer polymers is pH dependent. The maximum binding of Au(III) was obtained at pH 4.0. The QCM-D investigations enabled the detection of Au(III) sorption as well as the deposition of Au(0)-NPs in real-time during the in situ experiments. Further, this method allowed studying the influence of metal binding on the protein lattice stability of Slp1. Structural properties and protein layer stability could be visualized directly after QCM-D experiment using atomic force microscopy (AFM). In conclusion, the combination of these different methods provides a deeper understanding of metal binding by bacterial S-layer proteins in suspension or as monolayers on either bacterial cells or recrystallized surfaces. PMID:26863150

  9. Determination of the total drug-related chlorine and bromine contents in human blood plasma using high performance liquid chromatography-tandem ICP-mass spectrometry (HPLC-ICP-MS/MS).

    PubMed

    Klencsár, Balázs; Bolea-Fernandez, Eduardo; Flórez, María R; Balcaen, Lieve; Cuyckens, Filip; Lynen, Frederic; Vanhaecke, Frank

    2016-05-30

    A fast, accurate and precise method for the separation and determination of the total contents of drug-related Cl and Br in human blood plasma, based on high performance liquid chromatography - inductively coupled plasma - tandem mass spectrometry (HPLC-ICP-MS/MS), has been developed. The novel approach was proved to be a suitable alternative to the presently used standard methodology (i.e. based on a radiolabelled version of the drug molecule and radiodetection), while eliminating the disadvantages of the latter. Interference-free determination of (35)Cl has been accomplished via ICP-MS/MS using H2 as reaction gas and monitoring the (35)ClH2(+) reaction product at mass-to-charge ratio of 37. Br could be measured "on mass" at a mass-to-charge of 79. HPLC was relied on for the separation of the drug-related entities from the substantial amount of inorganic Cl. The method developed was found to be sufficiently precise (repeatability <10% RSD) and accurate (recovery between 95 and 105%) and shows a linear dynamic range (R(2)>0.990) from the limit of quantification (0.05 and 0.01 mg/L for Cl and Br in blood plasma, respectively) to at least 5 and 1mg/L for Cl and Br, respectively. Quantification via either external or internal standard calibration provides reliable results for both elements. As a proof-of-concept, human blood plasma samples from a clinical study involving a newly developed Cl- and Br-containing active pharmaceutical ingredient were analysed and the total drug exposure was successfully described. Cross-validation was achieved by comparing the results obtained on Cl- and on Br-basis. PMID:26942335

  10. 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. PMID:21850305

  11. IsoMark - a comprehensive assessment of the potential of isotopes in hard parts of freshwater fish to determine origin and migratory patterns using LA-(MC)-ICP-MS

    NASA Astrophysics Data System (ADS)

    Zitek, Andreas; Irrgeher, Johanna; Sturm, Monika; Brunner, Marion; Dillinger, Benno; Prohaska, Thomas

    2010-05-01

    The ‘IsoMark' project focuses for the first time on the comprehensive investigation of microchemical information (elemental fingerprint of Ca, Sr, Na, Ba, Mg; isotopic fingerprint of Sr, Ca, and additionally of C and O) in different hard parts of several typical European freshwater fish species like brown trout (Salmo trutta f.f., L.), European grayling (Thymallus thymallus, L.) or nase (Chondrostoma nasus, L.) and the barbel (Barbus barbus, L.). Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used as major technique for the direct in situ analysis of trace elements and isotopes, whereby the employment of a multiple collector - inductively coupled plasma - mass spectrometer (MC-ICP-MS) enables high precise isotope ratio analysis of such sample matrices due to its simultaneous detection capabilities. Microchemical patterns in hard parts of farmed and wild fish are analysed resulting in natural site specific elemental and isotopic signatures. Within a pilot study the potential to discriminate between wild and hatchery trout by chronological microchemical patterns of different otolith regions in relation to site specific water chemistry was documented. 100% accuracy of classification of fish to life stage specific habitats and therefore to their origin was achieved by the elemental ratios 88Sr/43Ca, 23Na/43Ca and the isotope ratio of 87Sr/86Sr. Clear differences in otolith chemistry were found, when fish experienced different geological units or specific environmental situations (e.g. groundwater) in hatcheries during a certain period of their life. These results proved the concept that natural microchemical patterns in hard parts linked to specific life stages of fish represent a valuable tool for a wide variety of ecological questions, e.g. discriminating wild and hatchery fish without the necessity of inducing any other artificial mark, or studying natural migration phenomena on small spatial scales in freshwater systems within

  12. 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. PMID:17429616

  13. Zircon U-Th-Pb dating using LA-ICP-MS: Simultaneous U-Pb and U-Th dating on the 0.1 Ma Toya Tephra, Japan

    NASA Astrophysics Data System (ADS)

    Ito, Hisatoshi

    2014-12-01

    Simultaneous U-Pb and U-Th zircon dating using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was performed on the ~ 0.1 Ma Toya Tephra, Hokkaido, Japan. The method employs the concurrent measurement of 206Pb, 230Th, and 238U signals, which enables the determination of 238U-206Pb (U-Pb) and 238U-230Th (U-Th) ages simultaneously. The U-Pb ages revealed that the Toya Tephra contains zircons with ages that cluster at ~ 0.1 Ma (0.11 ± 0.01 Ma: error shown as 95% confidence level) and xenocrysts with ages > 2 Ma. Excluding zircons > 2 Ma, the U-Th method also gave an isochron age of ~ 0.1 Ma (108 ± 19 ka or 0.11 ± 0.02 Ma; error shown as 2σ). Therefore, both U-Pb and U-Th methods result in similar ages of ~ 0.1 Ma for the Toya Tephra, in agreement with the quartz TL age (104 ± 30 to 118 ± 30 ka) of Ganzawa and Ike (2011). It was revealed that the simultaneous U-Pb and U-Th zircon dating technique using LA-ICP-MS is easy to apply and is useful for Quaternary tephras in that it can give age information on the tephra itself and xenocrystic zircons in a quick and cost-effective manner. The double dating technique employed here has the merit that zircons yielding Quaternary U-Pb ages can be immediately cross-checked by the U-Th method. It was also revealed that the Toya Tephra magma crystallized zircons and experienced eruptions instantaneously at ~ 0.1 Ma, which is an important implication to decipher magmatic and eruptive processes for caldera-forming large volcanic systems.

  14. A novel method for speciation of Pt in human serum incubated with cisplatin, oxaliplatin and carboplatin by conjoint liquid chromatography on monolithic disks with UV and ICP-MS detection.

    PubMed

    Martinčič, Anže; Cemazar, Maja; Sersa, Gregor; Kovač, Viljem; Milačič, Radmila; Ščančar, Janez

    2013-11-15

    Conjoint liquid chromatography (CLC) on monolithic convective interaction media (CIM) disks coupled on-line to UV and inductively coupled plasma mass spectrometry (ICP-MS) detectors was used for the first time in speciation analysis of Pt in human serum spiked with Pt-based chemotherapeutics. CIM Protein G and CIM DEAE disks were assembled together in a single housing forming a CLC monolithic column. Such a set-up allows rapid two-dimensional separation by affinity and ion-exchange (IE) modes to be carried out in a single chromatographic run. By applying isocratic elution with Tris-HCl-NaHCO3 buffer (pH 7.4) in the first minute, followed by gradient elution with 1 mol L(-1) NH4Cl (pH 7.4) in the next 9 min, immunoglobulins (IgG) were retained by the Protein G disk enabling subsequent separation of unbound Pt from Pt bound to transferrin (Tf) and albumin (HSA) on the CIM DEAE disk. Further elution with acetic acid (AcOH) in the next 3 min allowed separation of Pt associated with IgG. Separated Pt species were quantified by post-column isotope dilution-ICP-MS. Pt recovery on the CLC column was close to 100%. In comparison to commonly applied procedures that involve separation of protein peaks by size-exclusion chromatography (SEC) followed by IE separation of metal-based chemotherapeutic fractions bound to serum proteins, the CLC method developed is much faster and simpler. Its sensitivity (LOQs adequate for quantification of all separated Pt species, lower than 2.4 ng Pt mL(-1)), good selectivity and method repeatability (RSD±3%) enabled investigation of the kinetics of interaction of Pt-based chemotherapeutics with serum proteins and the distribution of Pt species in spiked human serum. Pt species present in spiked serum were bound preferentially to HSA. The proportion of Pt associated with IgG and Tf was lower than 13%. Cisplatin and especially oxaliplatin react rapidly with serum proteins, while carboplatin much less. The method developed may be reliably applied

  15. 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

  16. 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

  17. Determination of free amino acids and 18 elements in freeze-dried strawberry and blueberry fruit using an Amino Acid Analyzer and ICP-MS with micro-wave digestion.

    PubMed

    Zhang, Hua; Wang, Zhen-Yu; Yang, Xin; Zhao, Hai-Tian; Zhang, Ying-Chun; Dong, Ai-Jun; Jing, Jing; Wang, Jing

    2014-03-15

    The objective of this study was to investigate the level of 18 trace elements of two freeze-dried samples from the Blueberry (Vaccinium corymbosum) and the Strawberry (Fragaria × Ananassa). The total free amino acid composition in the blueberry and strawberry was determined by an Amino Acid Analyzer. Eleven free amino acids were found in both berries. The trace elements in each dried fruit sample were determined by ICP-MS with microwave digestion. The linearity range of the standard curves was 0-1250.0 μg L(-1) (Mg, P, K, Ca),while in all cases, except for B, Na, Al, Cr, Mn, Fe, Ni, Cu, Zn, Se, Cd, Pb, Ge and As, which was 125.0 μg mL(-1), all related coefficients were above 0.9999; recovery was in the range of 79.0-106.8%. Minor concentrations of nutritional elements were found in each freeze-dried berry. In sum, the toxic trace element analysis found the content of toxic trace elements in each freeze-dried berry sample was safe for human consumption and that the overall quality of the blueberry surpassed that of the strawberry. The results certify that the two freeze-dried berries have potential for human consumption in value-added products and have a certain theoretical and practical significance. PMID:24206704

  18. A method of measurement of (239)Pu, (240)Pu, (241)Pu in high U content marine sediments by sector field ICP-MS and its application to Fukushima sediment samples.

    PubMed

    Bu, Wenting; Zheng, Jian; Guo, Qiuju; Aono, Tatsuo; Tazoe, Hirofumi; Tagami, Keiko; Uchida, Shigeo; Yamada, Masatoshi

    2014-01-01

    An accurate and precise analytical method is highly needed for the determination of Pu isotopes in marine sediments for the long-term marine environment monitoring that is being done since the Fukushima Dai-ichi Nuclear Power Plant accident. The elimination of uranium from the sediment samples needs to be carefully checked. We established an analytical method based on anion-exchange chromatography and SF-ICP-MS in this work. A uranium decontamination factor of 2 × 10(6) was achieved, and the U concentrations in the final sample solutions were typically below 4 pg mL(-1), thus no extra correction of (238)U interferences from the Pu spectra was needed. The method was suitable for the analysis of (241)Pu in marine sediments using large sample amounts (>10 g). We validated the method by measuring marine sediment reference materials and our results agreed well with the certified and the literature values. Surface sediments and one sediment core sample collected after the nuclear accident were analyzed. The characterization of (241)Pu/(239)Pu atom ratios in the surface sediments and the vertical distribution of Pu isotopes showed that there was no detectable Pu contamination from the nuclear accident in the marine sediments collected 30 km off the plant site. PMID:24328266

  19. Liquid-liquid extraction of uranium(VI) with Aliquat® 336 from HCl media in microfluidic devices: Combination of micro-unit operations and online ICP-MS determination.

    PubMed

    Hellé, Gwendolyne; Mariet, Clarisse; Cote, Gérard

    2015-07-01

    The analysis of radionuclides is carried out according to operating protocols which include a series of chemical operations such as separation/purification steps and therefore is usually time-consuming, complex and difficult to put in place in a hostile environment (gloves box). In the present work, the liquid-liquid extraction of uranium in HCl media by Aliquat® 336 was performed in microsystem to demonstrate the potential of miniaturization in radiochemistry compared to classical protocols (decrease in volumes, analysis time, radiations received and feasibility of automation). Through the investigation of the influence of different parameters (flow rates, length of the microchannel, specific interfacial area), it was shown that the same performances of liquid-liquid extraction can be obtained in microsystem and in batch. Then, the coupling of different micro-unit operations for continuous process was performed to highlight the advantages of the miniaturized analytical techniques. The online ICP-MS determination of uranium(VI) was successfully coupled with the stripping of the latter from pre-loaded organic phases in microsystem, which constitutes a proof of concept and a first step towards a global analytical process with continuous flow. PMID:25882417

  20. Uncertainty Measurement for Trace Element Analysis of Uranium and Plutonium Samples by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS)

    SciTech Connect

    Gallimore, David L.

    2012-06-13

    The measurement uncertainty estimatino associated with trace element analysis of impurities in U and Pu was evaluated using the Guide to the Expression of Uncertainty Measurement (GUM). I this evalution the uncertainty sources were identified and standard uncertainties for the components were categorized as either Type A or B. The combined standard uncertainty was calculated and a coverage factor k = 2 was applied to obtain the expanded uncertainty, U. The ICP-AES and ICP-MS methods used were deveoped for the multi-element analysis of U and Pu samples. A typical analytical run consists of standards, process blanks, samples, matrix spiked samples, post digestion spiked samples and independent calibration verification standards. The uncertainty estimation was performed on U and Pu samples that have been analyzed previously as part of the U and Pu Sample Exchange Programs. Control chart results and data from the U and Pu metal exchange programs were combined with the GUM into a concentration dependent estimate of the expanded uncertainty. Comparison of trace element uncertainties obtained using this model was compared to those obtained for trace element results as part of the Exchange programs. This process was completed for all trace elements that were determined to be above the detection limit for the U and Pu samples.

  1. Firing distance estimation based on the analysis of GSR distribution on the target surface using ICP-MS--an experimental study with a 7.65 mm × 17 mm Browning pistol (.32 ACP).

    PubMed

    Santos, Agostinho; Ramos, Patrícia; Fernandes, Luís; Magalhães, Teresa; Almeida, Agostinho; Sousa, António

    2015-02-01

    An experimental study aiming to estimate the firing distance was conducted using a 7.65 mm × 17 mm Browning (.32ACP) pistol. Briefly, test shots were made against a target of cotton tissue (35 cm × 35 cm), and the amounts of antimony (Sb), barium (Ba), and lead (Pb) deposited in quadrangular pieces (1 cm × 1 cm) of the target cut from four radial positions at increasing distances from the bullet entrance hole ("samples") were determined by inductively coupled plasma-mass spectrometry (ICP-MS). The data obtained were used to search for a mathematical model for estimating the firing distance. The best model was a simple linear correlation between FD (the firing distance) and ln c (where c is the content of Sb, Ba or Pb in the samples, expressed in μg/g of target tissue). Best results were obtained with samples collected at radial distances within 2.0-3.0 cm from the bullet entrance hole. Using this approach, it was possible to accurately (±6 cm) estimate the firing distance in the interval [20-90] cm from the target. PMID:25553356

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

    PubMed

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

    2016-02-01

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

  3. 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

  4. LA-ICP-MS zircon U-Pb dating, trace element and Hf isotope geochemistry of the Heyu granite batholith, eastern Qinling, central China: Implications for Mesozoic tectono-magmatic evolution

    NASA Astrophysics Data System (ADS)

    Li, Nuo; Chen, Yan-Jing; Pirajno, Franco; Gong, Hu-Jun; Mao, Shi-Dong; Ni, Zhi-Yong

    2012-06-01

    Mesozoic granitoids are widespread in the southern margin of the North China Craton, and of particular geological interests because of their indication for lithospheric evolution and close association with porphyry Mo mineralization. In this contribution, in situ LA-ICP-MS U-Pb, Hf isotope and trace element analyses of zircon crystals have been combined to constrain the emplacement time and petrogenesis of the Heyu granitic batholith which hosts the Yuchiling porphyry Mo system, Henan Province, China. As inferred from field investigations, the concentrically zoned Heyu batholith mainly consists of four texturally distinguishable phases, and displays a pattern of monotonically decreasing U-Pb age from 143.0 ± 1.6 Ma for Phase 1, through 138.4 ± 1.5 Ma for Phase 2, through to ca. 135 Ma for Phase 3, and to 133.6 ± 1.3 Ma for the Mo-mineralized Yuchiling granite porphyry (Phase 4). The ɛHf(t) values (- 27.7 to - 3.4) and the two stage Hf model ages (1403 to 2924 Ma) of zircon grains, together with the ages of local strata, suggest that the magmas forming the Heyu batholith were dominantly sourced from the crust, with input of a mantle component. The higher Ce/Ce* ratios of the zircon crystals in the mineralized Yuchiling porphyry compared to those in the Mo-barren phases suggests that fluids exsolved from oxidic magmas might be more favorable for Mo enrichment. A regional synthesis suggests that intensive lithospheric thinning in the southern margin of the North China Craton should not be earlier than 130 Ma.

  5. Enrichment adsorption of a labile substance to the surface of particular mineral particles in river water as investigated by SEM-EDX and dilute-acid extraction/ICP-MS.

    PubMed

    Kyotani, Tomohiro; Koshimizu, Satoshi

    2003-06-01

    The selective enrichment behavior of a labile substance, such as hydroxides, to the surface of particular mineral particles in river water was clarified by scanning electron microscopy/energy dispersive X-ray microanalysis (SEM-EDX). Individual particles other than diatom collected on a 0.45 microm filter from the Fuji and Sagami rivers, central Japan, were analyzed by SEM-EDX and classified into seventeen groups according to the chemical composition and shape. Phosphorus, sulfur, chlorine, manganese and copper detected in each particle collected on the 0.45 microm filter could be successfully used as effective indicators of labile substance secondarily formed and adsorbed afresh in river water, because the detection frequencies of such elements are quite low, or negligible, in fresh mineral particles derived from igneous rocks. The labile substance adsorbed on mineral particles collected on the 0.45 microm filter was also evaluated by dilute-acid leaching, followed by inductively coupled plasma mass spectrometry (ICP-MS). Almost all parts of the manganese detected in individual particles were those adsorbed afresh as hydroxides together with iron and aluminum. Also, anionic elements, such as phosphorus, sulfur and chlorine, formed complexes with the hydroxides and/or were incorporated in them. Mg and/or Ca-rich aluminosilicate groups were the most effective adsorbers of such labile species. However, Si-rich and Na-, K- and Na-Ca rich aluminosilicates did not significantly adsorb the labile substance. Consequently, the remarkable selectivity was clarified in the adsorption process of labile substance to individual mineral particles in river water. PMID:12834221

  6. 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

  7. Quantitative determination of selenium and mercury, and an ICP-MS semi-quantitative scan of other elements in samples of eagle tissues collected from the Pacific Northwest--Summer 2011

    USGS Publications Warehouse

    May, Thomas; Walther, Mike; Brumbaugh, William

    2013-01-01

    Eagle tissues from dead eagle carcasses were collected by U.S. Fish and Wildlife Service personnel at various locations in the Pacific Northwest as part of a study to document the occurrence of metal and metalloid contaminants. A group of 182 eagle tissue samples, consisting of liver, kidney, brain, talon, feather, femur, humerus, and stomach contents, were quantitatively analyzed for concentrations of selenium and mercury by atomic absorption techniques, and for other elements by semi-quantitative scan with an inductively coupled plasma-mass spectrometer. For the various tissue matrices analyzed by an ICP-MS semiquantitative scan, some elemental concentrations (micrograms per gram dry weight) were quite variable within a particular matrix; notable observations were as follows: lead concentrations ranged from 0.2 to 31 in femurs, 0.1 to 29 in humeri, 0.1 to 54 in talons, less than (<) 0.05 to 120 in livers, <0.05 to 34 in kidneys, and 0.05 to 8 in brains; copper concentrations ranged from 5 to 9 in feathers, 8 to 47 in livers, 7 to 43 in kidneys, and 7 to 28 in brains; cadmium concentrations ranged from 0.1 to 10 in kidneys. In stomach contents, concentrations of vanadium ranged from 0.08 to 5, chromium 2 to 34, manganese 1 to 57, copper 2 to 69, arsenic <0.05 to 6, rubidium 1 to 13, and barium <0.5 to 18. Selenium concentrations from highest to lowest based on the matrix mean were as follows: kidney, liver, feather, brain, stomach content, talon, femur, and humerus. For mercury, the highest to lowest concentrations were feather, liver, talon, brain, stomach content, femur, and humerus.

  8. Trace element mineral/melt partitioning for basaltic and basaltic andesitic melts: An experimental and laser ICP-MS study with application to the oxidation state of mantle source regions

    NASA Astrophysics Data System (ADS)

    Laubier, Muriel; Grove, Timothy L.; Langmuir, Charles H.

    2014-04-01

    Understanding magmatic processes such as crystallization and melting recorded in natural samples requires calibration of mineral-melt trace element partition coefficients (D) and their dependence on temperature, pressure, oxygen fugacity (fO2) and chemical composition. However, few experimental studies have focused on measuring trace element partition coefficients for a large number of trace elements, in the various minerals present in basaltic rocks, and under diverse conditions, particularly of variable fO2. Twenty-seven 0.1 MPa experiments provide partition coefficients for major elements and Sc, Ti, V, Mn, Co, Ni, Ga, Sr, Y, Nb, Ba, Ce, Nd, Eu, Gd, and Yb for the mineral phases olivine, plagioclase, orthopyroxene and clinopyroxene. The experimental conditions range from 1150 to 1190 °C with oxygen fugacities from QFM to NNO+2. Run products were analyzed by laser-ablation ICP-MS. The new partition coefficients, combined with previously published data, can be used to model crystallization processes at low pressure. Partitioning of multivalent cations V, Fe and Eu varies as a function of the redox conditions, consistent with previous work, and can be used to constrain oxidation states of magmatic source regions. The V/Yb ratio is shown to be a useful proxy for oxidation state. The V/Yb ratio varies during mantle melting as a function of oxidation state of the mantle source, and it is not modified during fractional crystallization of olivine ± plag ± cpx. V/Yb increases from MORB, BABB to arc lavas, suggesting a progressive increase of fO2 from QFM to NNO+2. Apparent fO2 of arc lavas, however, is quite variable. These results demonstrate that sub-arc mantle displays a larger range of redox conditions toward a more oxidized mantle than the MORB mantle.

  9. Cyanovanadate(III) complexes as novel additives for efficient generation of volatile cadmium species in complex samples prior to determinations by inductively coupled plasma mass spectrometry (ICP-MS).

    PubMed

    Yilmaz, Vedat; Arslan, Zikri; Rose, LaKeysha; Little, Maria D

    2013-10-15

    A new method has been described for generation of volatile species of Cd using vanadium(III) cyanide complex. Aqueous solutions of 0.04 mol L(-1) vanadium chloride (VCl3) and 0.12 mol L(-1) potassium cyanide (KCN) were reacted on-line yielding a suspension of vanadium hydroxide, V(OH)3. This suspension was dissolved along the stream of sample solution in dilute HCl to form heptacyanovanadate(III) complex, [V(CN)7]4-. Volatile Cd species were generated by reacting the stream of sample solution and cyanovanadate(III) complex with sodium borohydride (NaBH4). Feasibility of off-line and on-online approaches was investigated for quantitative determinations. Better precision and daily stability were achieved with on-line settings. Optimum signals were obtained from sample solutions within a range of 3 to 5% v/v HCl. A concentration of 2% m/v NaBH4 was adequate to achieve an enhancement of 20-fold in the presence of cyanovanadate(III) complex. The limits of detection were 5.0 and 4.5 ng L(-1) for 110Cd and 111Cd isotopes, respectively. Precision (%RSD) was better than 4.7% for six replicate measurements. The interferences of Cu(II) and Ni(II) were marginal (<10%) at 1.0 µg mL(-1). Depressive effects from Bi, Se and Sn were not significant below 0.1 µg mL(-1). The method was validated by determination of Cd using ICP-MS in certified reference materials of Nearshore seawater (CASS-4), Bone ash (SRM 1400), Dogfish liver (DOLT-4) and Mussel tissue (SRM 2976). PMID:24014893

  10. Study of 3-Ethylamino-but-2-enoic acid phenylamide as a new ligand for preconcentration of lanthanides from aqueous media by liquid-liquid extraction prior to ICP-MS analysis.

    PubMed

    Varbanova, Evelina K; Angelov, Plamen A; Stefanova, Violeta M

    2016-11-01

    In the present work the potential of a new ligand 3-Ethylamino-but-2-enoic acid phenylamide (representing the class of enaminones) for selective preconcentration of lanthanides (La, Ce, Eu, Gd and Er) from aqueous medium is examined. Liquid-liquid extraction parameters, such as pH of the water phase, type and volume of organic solvent, quantity of ligand and reaction time are optimized on model solutions. Recovery of lanthanides by re-extraction with nitric acid makes the LLE procedure compatible with Inductively Coupled Plasma Mass Spectrometry. Spectral and non-spectral interferences are studied. Two isotopes per element are measured (with exception of La) for dynamic evaluation of the potential risk of spectral interference in variable real samples. The selectivity of complex formation reaction towards concomitant alkali and alkali-earth elements eliminates the interferences from sample matrix. Subjecting the standards to the optimized extraction procedure in combination with Re as internal standard is recommended as calibration strategy. The accuracy of developed method is approved by analysis of CRM Bush branches and leaves (NCS DC 73348) and recovery of spiked water and plant samples. The method's limits of detection for both studied objects are in the ranges from 0.2 ((158)Gd) to 3.7 ((139)La) ngl(-1) and 0.02 ((158)Gd) to 0.37((139)La) ngg(-1) for waters and plants respectively. The studied compound is an effective new ligand for preconcentration/separation of lanthanides from aqueous medium by LLE and subsequent determination by ICP-MS. PMID:27591629

  11. Improved 206Pb/238U microprobe geochronology by the monitoring of a trace-element-related matrix effect; SHRIMP, ID-TIMS, ELA-ICP-MS and oxygen isotope documentation for a series of zircon standards

    USGS Publications Warehouse

    Black, L.P.; Kamo, S.L.; Allen, C.M.; Davis, D.W.; Aleinikoff, J.N.; Valley, J.W.; Mundil, R.; Campbell, I.H.; Korsch, R.J.; Williams, I.S.; Foudoulis, C.

    2004-01-01

    Precise isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) documentation is given for two new Palaeozoic zircon standards (TEMORA 2 and R33). These data, in combination with results for previously documented standards (AS3, SL13, QGNG and TEMORA 1), provide the basis for a detailed investigation of inconsistencies in 206Pb/238U ages measured by microprobe. Although these ages are normally consistent between any two standards, their relative age offsets are often different from those established by ID-TIMS. This is true for both sensitive high-resolution ion-microprobe (SHRIMP) and excimer laser ablation-inductively coupled plasma-mass spectrometry (ELA-ICP-MS) dating, although the age offsets are in the opposite sense for the two techniques. Various factors have been investigated for possible correlations with age bias, in an attempt to resolve why the accuracy of the method is worse than the indicated precision. Crystallographic orientation, position on the grain-mount and oxygen isotopic composition are unrelated to the bias. There are, however, striking correlations between the 206Pb/238U age offsets and P, Sm and, most particularly, Nd abundances in the zircons. Although these are not believed to be the primary cause of this apparent matrix effect, they indicate that ionisation of 206Pb/238U is influenced, at least in part, by a combination of trace elements. Nd is sufficiently representative of the controlling trace elements that it provides a quantitative means of correcting for the microprobe age bias. This approach has the potential to reduce age biases associated with different techniques, different instrumentation and different standards within and between laboratories. Crown Copyright ?? 2004 Published by Elsevier B.V. All rights reserved.

  12. 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.

  13. 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.

  14. Simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by 3-(2-aminoethylamino) propyltrimethoxysilane modified multi-wall carbon nanotubes packed microcolumn solid phase extraction and ICP-MS.

    PubMed

    Peng, Hanyong; Zhang, Nan; He, Man; Chen, Beibei; Hu, Bin

    2015-01-01

    Speciation analysis of inorganic arsenic, chromium and selenium in environmental waters is of great significance for the monitoring of environmental pollution. In this work, 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS) functionalized multi-wall carbon nanotubes (MWCNTs) were synthesized and employed as the adsorbent for simultaneous speciation analysis of inorganic arsenic, chromium and selenium in environmental waters by microcolumn solid-phase extraction (SPE)-inductively coupled plasma mass spectrometry (ICP-MS). It was found that As(V), Cr(VI) and Se(VI) could be selectively adsorbed on the microcolumn packed with AAPTS-MWCNTs adsorbent at pH around 2.2, while As(III), Cr(III) and Se(IV) could not be retained at this pH and passed through the microcolumn directly. Total inorganic arsenic, chromium and selenium was determined after the oxidation of As(III), Cr(III) and Se(IV) to As(V), Cr(VI) and Se(VI) with 10.0 μmol L(-1) KMnO4. The assay of As(III), Cr(III) and Se(IV) was based on subtracting As(V), Cr(VI) and Se(VI) from the total As, Cr and Se, respectively. Under the optimized conditions, the detection limits of 15, 38 and 16 ng L(-1) with the relative standard deviations (RSDs) of 7.4, 2.4 and 6.2% (c=1 µg L(-1), n=7) were obtained for As(V), Cr(VI) and Se(VI), respectively. The developed method was validated by analyzing four Certified Reference Materials, rainwater, Yangtze River and East Lake waters. PMID:25281102

  15. Accurate Quantification of Selenoprotein P (SEPP1) in Plasma Using Isotopically Enriched Seleno-peptides and Species-Specific Isotope Dilution with HPLC Coupled to ICP-MS/MS.

    PubMed

    Deitrich, Christian L; Cuello-Nuñez, Susana; Kmiotek, Diana; Torma, Frank Attila; Del Castillo Busto, Maria Estela; Fisicaro, Paola; Goenaga-Infante, Heidi

    2016-06-21

    A novel strategy for the absolute quantification of selenium (Se) included in selenoprotein P (SEPP1), an important biomarker for human nutrition and disease, including diabetes and cancer, is presented here for the first time. It is based on the use of species-specific double isotope dilution mass spectrometry (SSIDA) in combination with HPLC-ICP-MS/MS for the determination of protein bound Se down to the peptide level in a complex plasma matrix with a total content of Se of 105.5 μg kg(-1). The method enabled the selective Se speciation analysis of human plasma samples without the need of extensive cleanup or preconcentration steps as required for traditional protein mass spectrometric approaches. To assess the method accuracy, two plasma reference materials, namely, BCR-637 and SRM1950, for which literature data and a reference value for SEPP1 have been reported, were analyzed using complementary hyphenated methods and the species-specific approach developed in this work. The Se mass fractions obtained via the isotopic ratios (78)Se/(76)Se and (82)Se/(76)Se for each of the Se-peptides, namely, ENLPSLCSUQGLR (ENL) and AEENITESCQUR (AEE) (where U is SeCys), were found to agree within 2.4%. A relative expanded combined uncertainty (k = 2) of 5.4% was achieved for a Se (as SEPP1) mass fraction of approximately 60 μg kg(-1). This work represents a systematic approach to the accurate quantitation of plasma SEPP1 at clinical levels using SSIDA quantification. Such methodology will be invaluable for the certification of reference materials and the provision of reference values to clinical measurements and clinical trials. PMID:27108743