Science.gov

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. 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.

  20. 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.

  1. 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.

  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. 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

  6. 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).

  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. 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.

  10. 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

  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. 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.

  15. 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

  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. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  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. 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

  5. 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.

  6. 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

  7. 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

  8. [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

  9. 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

  10. 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

  11. 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.

  12. 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

  13. 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".

  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. 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

  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. 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.

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. 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)

  4. 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.

  5. 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

  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. 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

  8. 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.

  9. 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.

  10. 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

  11. 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.

  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. 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...

  15. 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.

  16. 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...

  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. 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.

  1. [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

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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

  7. [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

  8. 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

  9. [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

  10. 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

  11. 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

  12. 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

  13. 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

  14. 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

  15. 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.

  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. 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

  18. 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.

  19. 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

  20. 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

  1. [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

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. Speciation And Uptake of Arsenic Accumulated By Corn Seedlings Using XAS And DRC-ICP-MS

    SciTech Connect

    Parsons, J.G.; Martinez-Martinez, A.; Peralta-Videa, J.R.; Gardea-Torresdey, J.L.

    2009-05-21

    ICP-MS was used to investigate the uptake of As(III) and As(V) from hydroponics growth media by corn seedlings. It was found that arsenic uptake by the plant roots for the arsenic(V) and arsenic(III) treatments were 95 and 112 ppm, respectively. However, in the shoots of the arsenic (V) treatments had 18 ppm whereas arsenic(III) treatments had 12 ppm. XANES studies showed that As for both treatments arsenic was present as a mixture of an As(III) sulfur complex and an As(V) oxygen complex. The XANES data was corroborated by the EXAFS studies showing the presence of both oxygen and sulfur ligands coordinated to the arsenic. Iron concentrations were found to increase by 4 fold in the As(V) contaminated growth media and 7 fold in the As(III) treatment compared to the control iron concentration of 500 ppm. Whereas, the total iron concentration in the shoots was found to decrease by approximately the same amount for both treatments from 360 ppm in the control to approximately 125 ppm in both arsenic treatments. Phosphorus concentrations were found to decrease in both the roots and shoots compared to the control plants. The total sulfur in the roots was found to increase in the arsenic(III) and arsenic(V) treatments to 560 ppm and 800 ppm, respectively, compared to the control plants 358 ppm. In addition, the total sulfur in shoots of the plants was found to remain relatively constant at approximately 1080 ppm. The potassium concentrations in the plants were found to increase in the roots and decrease in the shoots.

  7. 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

  8. 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.

  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. 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.

  11. 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.

  12. [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

  13. 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

  14. 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

  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. 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.

  20. [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

  1. [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

  2. 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

  3. [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

  4. 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

  5. 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

  6. 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

  7. 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

  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. 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

  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.; 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.

  14. 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.

  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. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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

  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. 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

  6. [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

  7. 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

  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. 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

  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. 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

  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. 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.

  1. 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

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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

  7. 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.

  8. 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

  9. 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

  10. 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

  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. [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

  13. 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

  14. 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

  15. 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.

  16. 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

  17. 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

  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. 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.

  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. 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.

  3. 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.

  4. 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 ...

  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. 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.

  7. 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

  8. 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

  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. 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

  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. 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

  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. 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.

  16. [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

  17. 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

  18. 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

  19. 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.

  20. 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

  1. 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

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  10. 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