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Sample records for plasma-mass spectrometry multi-elemental

  1. Multi-element analysis of compost by laser ablation-inductively coupled plasma mass spectrometry.

    PubMed

    Jiménez, María S; Gómez, María T; Castillo, Juan R

    2007-05-15

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been applied to multi-element determination in compost samples. Since compost is a heterogeneous mixture of organic and inorganic materials, the influence of sample heterogeneity on the accuracy and precision of analysis was investigated. Several parameters related to the following were studied: laser (energy, laser-beam diameter, preablation. rastering speed, carrier-gas flow rate), sample preparation (use of compacted pellets, grinding time, particle size, sample amount, length of hydraulic press treatment, position of line scan), and the ICP-MS system (quantitative versus semiquantitative analysis, matrix-matched standards and liquid standards calibration). The main causes of imprecision in sample preparation were determined to be particle size and grinding time. The effect of sample heterogeneity on precision was also evaluated by using different test samples (pellets). For Ni, Zn and Pb, the greatest contribution to the total relative standard deviation (R.S.D.) was related to analyte determination. For Mn and Cu, sample heterogeneity and analyte determination contributed equally to the total R.S.D., whereas for Cr, Co, Cd and Hg sample heterogeneity accounted for most of the total R.S.D. A comparison of semiquantitative and quantitative analysis modes showed that better precision and very good agreement with certified reference material was obtained with the latter, but semiquantitative analysis could be a practical alternative. Although accuracy of results was improved with matrix-matched standards calibration the use of standard addition calibration with aqueous standards could be another possibility. PMID:19071737

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

    USGS Publications Warehouse

    Wolf, Ruth E.; Adams, Monique

    2015-01-01

    Typically, quadrupole inductively coupled plasma-mass spectrometry (ICP-MS) is used to determine as many as 57 major, minor, and trace elements in aqueous geochemical samples, including natural surface water and groundwater, acid mine drainage water, and extracts or leachates from geological samples. The sample solution is aspirated into the inductively coupled plasma (ICP) which is an electrodeless discharge of ionized argon gas at a temperature of approximately 6,000 degrees Celsius. The elements in the sample solution are subsequently volatilized, atomized, and ionized by the ICP. The ions generated are then focused and introduced into a quadrupole mass filter which only allows one mass to reach the detector at a given moment in time. As the settings of the mass analyzer change, subsequent masses are allowed to impact the detector. Although the typical quadrupole ICP-MS system is a sequential scanning instrument (determining each mass separately), the scan speed of modern instruments is on the order of several thousand masses per second. Consequently, typical total sample analysis times of 2–3 minutes are readily achievable for up to 57 elements.

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

    NASA Astrophysics Data System (ADS)

    Desaulty, Anne-Marie; Mariet, Clarisse; Dillmann, Philippe; Joron, Jean Louis; Fluzin, Philippe

    2008-11-01

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

  4. Evaluation of the multi-element capabilities of collision/reaction cell inductively coupled plasma-mass spectrometry in wine analysis.

    PubMed

    Grindlay, Guillermo; Mora, Juan; de Loos-Vollebregt, Margaretha T C; Vanhaecke, Frank

    2014-10-01

    This work explores the multi-element capabilities of inductively coupled plasma-mass spectrometry with collision/reaction cell technology (CCT-ICP-MS) for the simultaneous determination of both spectrally interfered and non-interfered nuclides in wine samples using a single set of experimental conditions. The influence of the cell gas type (i.e. He, He+H2 and He+NH3), cell gas flow rate and sample pre-treatment (i.e. water dilution or acid digestion) on the background-equivalent concentration (BEC) of several nuclides covering the mass range from 7 to 238u has been studied. Results obtained in this work show that, operating the collision/reaction cell with a compromise cell gas flow rate (i.e. 4 mL min(-1)) improves BEC values for interfered nuclides without a significant effect on the BECs for non-interfered nuclides, with the exception of the light elements Li and Be. Among the different cell gas mixtures tested, the use of He or He+H2 is preferred over He+NH3 because NH3 generates new spectral interferences. No significant influence of the sample pre-treatment methodology (i.e. dilution or digestion) on the multi-element capabilities of CCT-ICP-MS in the context of simultaneous analysis of interfered and non-interfered nuclides was observed. Nonetheless, sample dilution should be kept at minimum to ensure that light nuclides could be quantified in wine. Finally, a direct 5-fold aqueous dilution is recommended for the simultaneous trace and ultra-trace determination of spectrally interfered and non-interfered elements in wine by means of CCT-ICP-MS. The use of the CCT is mandatory for interference-free ultra-trace determination of Ti and Cr. Only Be could not be determined when using the CCT due to a deteriorated limit of detection when compared to conventional ICP-MS. PMID:25059175

  5. Laser ablation inductively coupled plasma mass spectrometry

    SciTech Connect

    Durrant, S.F.

    1996-07-01

    Laser ablation for solid sample introduction to inductively coupled plasma mass spectrometry for bulk and spatially-resolved elemental analysis is briefly reviewed. {copyright} {ital 1996 American Institute of Physics.}

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

    PubMed

    Spada, Nicholas; Bozlaker, Ayse; Chellam, Shankararaman

    2012-07-20

    Platinum group elements (PGEs) including Rh, Pd, and Pt are important tracers for vehicular emissions, though their measurement is often challenging and difficult to replicate in environmental campaigns. These challenges arise from sample preparation steps required for PGE quantitation, which often cause severe isobaric interferences and spectral overlaps from polyatomic species of other anthropogenically emitted metals. Consequently, most previous road dust studies have either only quantified PGEs or included a small number of anthropogenic elements. Therefore a novel analytical method was developed to simultaneously measure PGEs, lanthanoids, transition and main group elements to comprehensively characterize the elemental composition of urban road and tunnel dusts. Dust samples collected from the vicinity of high-traffic roadways and a busy underwater tunnel restricted to single-axle (predominantly gasoline-driven) vehicles in Houston, TX were analyzed for 45 metals with the newly developed method using dynamic reaction cell-quadrupole-inductively coupled plasma-mass spectrometry (DRC-q-ICP-MS). Average Rh, Pd and Pt concentrations were 152±52, 770±208 and 529±130 ng g(-1) respectively in tunnel dusts while they varied between 6 and 8 ng g(-1), 10 and 88 ng g(-1) and 35 and 131 ng g(-1) in surface road dusts. Elemental ratios and enrichment factors demonstrated that PGEs in dusts originated from autocatalyst attrition/abrasion. Strong evidence is also presented for mobile source emissions of Cu, Zn, Ga, As, Mo, Cd, Sn, Sb, Ba, W and Pb. However, all other elements including rare earths most likely arose from weathering, erosion and resuspension of crustal material. These are the first such detailed measurements in Houston, the largest city in TX and fourth largest in the United States. We posit that such investigations will assist in better understanding PGE concentrations in urban environments while providing elemental data necessary to better understand

  7. Lead in feed incident--multi-element analysis of cattle feed and tissues by inductively coupled plasma-mass spectrometry and co-operative quality assurance scheme for lead analysis of milk.

    PubMed

    Crews, H M; Baxter, M J; Bigwood, T; Burrell, J A; Owen, L M; Robinson, C; Wright, C; Massey, R C

    1992-01-01

    Contaminated cattle feed was imported into the UK in 1989 and resulted in lead toxicity in some animals. Rapid analyses for lead and several other possible contaminating elements were required for feed and cattle tissues. Microwave dissolution of samples with measurement by ICP-MS was used for multi-element determinations. Lead was found to be the major contaminant. Lead levels in milk samples were measured by several laboratories during the crisis and an analytical quality assurance scheme was devised to monitor the quality of the data. The scheme allowed any poorly performing laboratories to be rapidly identified and excluded from the survey. PMID:1337328

  8. Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Hutchinson, Robert W.; McLachlin, Katherine M.; Riquelme, Paloma; Haarer, Jan; Broichhausen, Christiane; Ritter, Uwe; Geissler, Edward K.; Hutchinson, James A.

    2015-01-01

    ABSTRACT New analytical techniques for multiparametric characterisation of individual cells are likely to reveal important information about the heterogeneity of immunological responses at the single-cell level. In this proof-of-principle study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied to the problem of concurrently detecting 24 lineage and activation markers expressed by human leucocytes. This approach was sufficiently sensitive and specific to identify subpopulations of isolated T, B, and natural killer cells. Leucocyte subsets were also accurately detected within unfractionated peripheral blood mononuclear cells preparations. Accordingly, we judge LA-ICP-MS to be a suitable method for assessing expression of multiple tissue antigens in solid-phase biological specimens, such as tissue sections, cytospins, or cells grown on slides. These results augur well for future development of LA-ICP-MS–based bioimaging instruments for general users. PMID:27500232

  9. Laser spectrometry for multi-elemental imaging of biological tissues

    PubMed Central

    Sancey, L.; Motto-Ros, V.; Busser, B.; Kotb, S.; Benoit, J. M.; Piednoir, A.; Lux, F.; Tillement, O.; Panczer, G.; Yu, J.

    2014-01-01

    An increasing interest has arisen in research focused on metallic and organic ions that play crucial roles in both physiological and pathological metabolic processes. Current methods for the observation of trace elements in biological tissues at microscopic spatial resolution often require equipment with high complexity. We demonstrate a novel approach with an all-optical design and multi-elemental scanning imaging, which is unique among methods of elemental detection because of its full compatibility with standard optical microscopy. This approach is based on laser-induced breakdown spectroscopy (LIBS), which allows the elements in a tissue sample to be directly detected and quantified under atmospheric pressure. We successfully applied this method to murine kidneys with 10 µm resolution and a ppm-level detection limit to analyze the renal clearance of nanoparticles. These results offer new insight into the use of laser spectrometry in biomedical applications in the field of label-free elemental mapping of biological tissues. PMID:25338518

  10. Imaging mass spectrometry in biological tissues by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Becker, J S; Becker, J Su; Zoriy, M V; Dobrowolska, J; Matucsh, A

    2007-01-01

    Of all the inorganic mass spectrometric techniques, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) plays a key role as a powerful and sensitive microanalytical technique enabling multi- element trace analysis and isotope ratio measurements at trace and ultratrace level. LA-ICP-MS was used to produce images of detailed regionally-specific element distribution in 20 microm thin sections of different parts of the human brain. The quantitative determination of copper, zinc, lead and uranium distribution in thin slices of human brain samples was performed using matrix-matched laboratory standards via external calibration procedures. Imaging mass spectrometry provides new information on the spatially inhomogeneous element distribution in thin sections of human tissues, for example, of different brain regions (the insular region) or brain tumor tissues. The detection limits obtained for Cu, Zn, Pb and U were in the ng g(-1) range. Possible strategies of LA-ICP-MS in brain research and life sciences include the elemental imaging of thin slices of brain tissue or applications in proteome analysis by combination with matrix-assisted laser desorption/ionization MS to study phospho- and metal- containing proteins will be discussed. PMID:17885277

  11. Plasma mass spectrometry as a detector for chemical speciation studies.

    PubMed

    Tomlinson, M J; Lin, L; Caruso, J A

    1995-03-01

    Inductively coupled plasma mass spectrometry (ICP-MS), when coupled with the unique separating power of various chromatographic techniques, allows the detection of various elements at ultra-trace levels. The investigation of various toxic elements of environmental concern coupling relatively recent techniques, such as supercritical fluid chromatography (SFC) and capillary zone electrophoresis (CZE), to ICP-MS, is discussed. Comparisons have been made with detection limits obtained by using the flame ionization detector. The conventional technique of liquid chromatography for the speciation of vanadium, chromium and nickel is also discussed. PMID:7741220

  12. Fission Yield Measurements by Inductively Coupled Plasma Mass-Spectrometry

    SciTech Connect

    Irina Glagolenko; Bruce Hilton; Jeffrey Giglio; Daniel Cummings; Karl Grimm; Richard McKnight

    2009-11-01

    Correct prediction of the fission products inventory in irradiated nuclear fuels is essential for accurate estimation of fuel burnup, establishing proper requirements for spent fuel transportation and storage, materials accountability and nuclear forensics. Such prediction is impossible without accurate knowledge of neutron induced fission yields. Unfortunately, the accuracy of the fission yields reported in the ENDF/B-VII.0 library is not uniform across all of the data and much of the improvement is desired for certain isotopes and fission products. We discuss our measurements of cumulative fission yields in nuclear fuels irradiated in thermal and fast reactor spectra using Inductively Coupled Plasma Mass Spectrometry.

  13. Inductively coupled plasma mass spectrometry determination of metals in honeybee venom.

    PubMed

    Kokot, Zenon J; Matysiak, Jan

    2008-11-01

    Inductively coupled plasma mass spectrometry (ICP-MS) technique was used to analyze the contamination of selected 20 metals in 32 samples of honeybee venom and to demonstrate differences in the content of these elements. Among the analyzed metal microelements (Al, Co, Cu, Zn, Mn, Mo, B, V, Sr and Ni), macro-elements (Ca, Mg, K and Na) and toxic metals (As, Ba, Pb, Cd, Sb and Cr) were identified. The presented results showed that the metal levels in honeybee venom are much lower than the tolerable upper intake levels for the elements. Also the toxic metal contamination is much lower than the permissible levels for drugs established by the United States Pharmacopeia and the European Pharmacopeia. As opposed to the pharmacopeial tests for metals, a multi-element ICP-MS method has been developed. In order to confirm data obtained, the following steps and parameters were taken into account for the validation of the method: calibration verification, recovery, accuracy, precision, detection limit (LOD), quantitation limit (LOQ), spectral and matrix interference and comparison between ICP-MS and GFAAS (graphite furnace atomic absorption spectrometry) for Mn. All steps of validation proved the accuracy of the results. This is most likely the first study in which the metal content in honeybee venom was evaluated by ICP-MS. PMID:18617350

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

    NASA Astrophysics Data System (ADS)

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

    1994-02-01

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

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

    PubMed

    Todorov, Todor I; Ejnik, John W; Guandalini, Gustavo; Xu, Hanna; Hoover, Dennis; Anderson, Larry; Squibb, Katherine; McDiarmid, Melissa A; Centeno, Jose A

    2013-01-01

    In this study we report uranium analysis for human semen samples. Uranium quantification was performed by inductively coupled plasma mass spectrometry. No additives, such as chymotrypsin or bovine serum albumin, were used for semen liquefaction, as they showed significant uranium content. For method validation we spiked 2g aliquots of pooled control semen at three different levels of uranium: low at 5 pg/g, medium at 50 pg/g, and high at 1000 pg/g. The detection limit was determined to be 0.8 pg/g uranium in human semen. The data reproduced within 1.4-7% RSD and spike recoveries were 97-100%. The uranium level of the unspiked, pooled control semen was 2.9 pg/g of semen (n=10). In addition six semen samples from a cohort of Veterans exposed to depleted uranium (DU) in the 1991 Gulf War were analyzed with no knowledge of their exposure history. Uranium levels in the Veterans' semen samples ranged from undetectable (<0.8 pg/g) to 3350 pg/g. This wide concentration range for uranium in semen is consistent with known differences in current DU body burdens in these individuals, some of whom have retained embedded DU fragments. PMID:22944582

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

    PubMed

    Li, Tan-ping; Xie, Hua-lin; Nie, Xi-du

    2015-10-01

    A method for the determination of Na, Mg, Si, P, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Mo, Cd, Hg and Pb in castor oil after direct dilution with ethanol by inductively coupled plasma mass spectrometry (ICP-MS) was established. The sample was diluted by ethanol before ICP-MS determination. The condensation and deposition of high concentrations of carbon in mass cone interface and ion lens, which will decrease the sensitivity of element analysis, were avoided effectively by introducing O2 to plasma. The mass spectral interferences were eliminated by octopole reaction system (ORS). The matrix effects were calibrated to using Sc, Ge, Rh and Ir as internal standard elements. Au standard solution, which could form amalgam alloy with Hg, was dropped to eliminate the memory effect of Hg. The results show that the correlation coefficient for analyte is no less than 0.999 5, the detection limits is in the range of 0.06 - 20.1 ng x L(-1), the recovery is in the range of 990.4% - 110.2%, and the RSD is less than 4.8%. This method was very fast, simple and accurate to simultaneously analyze multi-elements in castor oil. PMID:26904837

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

    NASA Astrophysics Data System (ADS)

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

    2009-01-01

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

  18. Inductively Coupled Plasma Mass Spectrometry Uranium Error Propagation

    SciTech Connect

    Hickman, D P; Maclean, S; Shepley, D; Shaw, R K

    2001-07-01

    The Hazards Control Department at Lawrence Livermore National Laboratory (LLNL) uses Inductively Coupled Plasma Mass Spectrometer (ICP/MS) technology to analyze uranium in urine. The ICP/MS used by the Hazards Control Department is a Perkin-Elmer Elan 6000 ICP/MS. The Department of Energy Laboratory Accreditation Program requires that the total error be assessed for bioassay measurements. A previous evaluation of the errors associated with the ICP/MS measurement of uranium demonstrated a {+-} 9.6% error in the range of 0.01 to 0.02 {micro}g/l. However, the propagation of total error for concentrations above and below this level have heretofore been undetermined. This document is an evaluation of the errors associated with the current LLNL ICP/MS method for a more expanded range of uranium concentrations.

  19. Aerosol detection efficiency in inductively coupled plasma mass spectrometry

    DOE PAGESBeta

    Hubbard, Joshua A.; Zigmond, Joseph A.

    2016-03-02

    We used an electrostatic size classification technique to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Moreover, we counted size-segregated particles with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized bymore » the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10-5 to 10-11. Free molecular heat and mass transfer theory was

  20. Aerosol detection efficiency in inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Hubbard, Joshua A.; Zigmond, Joseph A.

    2016-05-01

    An electrostatic size classification technique was used to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Size-segregated particles were counted with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized by the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10- 5 to 10- 11. Free molecular heat and mass transfer theory was applied, but

  1. Iron-Isotopic Fractionation Studies Using Multiple Collector Inductively Coupled Plasma Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Anbar, A. D.; Zhang, C.; Barling, J.; Roe, J. E.; Nealson, K. H.

    1999-01-01

    The importance of Fe biogeochemistry has stimulated interest in Fe isotope fractionation. Recent studies using thermal ionization mass spectrometry (TIMS) and a "double spike" demonstrate the existence of biogenic Fe isotope effects. Here, we assess the utility of multiple-collector inductively-coupled plasma mass spectrometry(MC-ICP-MS) with a desolvating sample introduction system for Fe isotope studies, and present data on Fe biominerals produced by a thermophilic bacterium. Additional information is contained in the original extended abstract.

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

    NASA Astrophysics Data System (ADS)

    Resano, M.; García-Ruiz, E.; Vanhaecke, F.

    2005-11-01

    In this work, the potential of laser ablation-inductively coupled plasma-mass spectrometry for the fast analysis of polymers has been explored. Different real-life samples (polyethylene shopping bags, an acrylonitrile butadiene styrene material and various plastic bricks) as well as several reference materials (VDA 001 to 004, Cd in polyethylene) have been selected for the study. Two polyethylene reference materials (ERM-EC 680 and 681), for which a reference or indicative value for the most relevant metals is available, have proved their suitability as standards for calibration. Special attention has been paid to the difficulties expected for the determination of Cr at the μg g - 1 level in this kind of materials, due to the interference of ArC + ions on the most abundant isotopes of Cr. The use of ammonia as a reaction gas in a dynamic reaction cell is shown to alleviate this problem, resulting in a limit of detection of 0.15 μg g - 1 for this element, while limiting only modestly the possibilities of the technique for simultaneous multi-element analysis. In this regard, As is the analyte most seriously affected by the use of ammonia, and its determination has to be carried out in vented mode, at the expense of measuring time. In all cases studied, accurate results could be obtained for elements ranging in content from the sub-μg g - 1 level to tens of thousands of μg g - 1 . However, the use of an element of known concentration as internal standard may be needed for materials with a matrix significantly different from that of the standard (polyethylene in this work). Precision ranged between 5% and 10% RSD for elements found at the 10 μg g - 1 level or higher, while this value could deteriorate to 20% for analytes found at the sub-μg g - 1 level. Overall, the technique evaluated presents many advantages for the fast and accurate multi-element analysis of these materials, avoiding laborious digestion procedures and minimizing the risk of analyte losses due

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

    USGS Publications Warehouse

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

    2014-01-01

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

  4. Chemical recoveries of technetium-99 for various procedures using inductively coupled plasma-mass spectrometry

    SciTech Connect

    Ihsanullah; East, B.W.

    1993-12-31

    The procedure for the determination of {sup 99}Tc inductively coupled plasma-mass spectrometry (ICP-MS) was based on the modification of a variety of available separation techniques. Standard Ru and Rh solutions were used for checking decontaminations and instrument response respectively. Technetium-99 and {sup 95m}Tc tracers were applied as yield monitors using ICP-MS and gamma-ray spectrometry respectively. Percent recoveries are reported for a variety of radiochemical separation procedures for water (58-83%), seaweed (10-76%), and for soil matrices (19-79%).

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

    SciTech Connect

    Rob Henry; Dagmar Koller; Phil Marriott

    1998-12-31

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

  6. Determination of trace metals in marine biological reference materials by inductively coupled plasma mass spectrometry

    SciTech Connect

    Beauchemin, D.; McLaren, J.W.; Willie, S.N.; Berman, S.S.

    1988-04-01

    Inductively coupled plasma mass spectrometry (ICP-MS) was used for the analysis of two marine biological reference materials (dogfish liver tissue (DOLT-1) and dogfish muscle tissue (DORM-1)). The materials were put into solution by digestion in a nitric acid/hydrogen peroxide mixture. Thirteen elements (Na, Mg, Cr, Fe, Mn, Co, Ni, Cu, Zn, As, Cd, Hg, and Pb) were then determined. Accurate results were obtained by standard additions or isotope dilution techniques for all of these elements in DORM-1 and for all but Cr in DOLT-1.

  7. Time-resolved studies of particle effects in laser ablation inductively coupled plasma-mass spectrometry

    SciTech Connect

    Perdian, D.; Bajic, S.; Baldwin, D.; Houk, R.

    2007-11-13

    Time resolved signals in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) are studied to determine the influence of experimental parameters on ICP-induced fractionation effects. Differences in sample composition and morphology, i.e., ablating brass, glass, or dust pellets, have a profound effect on the time resolved signal. Helium transport gas significantly decreases large positive signal spikes arising from large particles in the ICP. A binder for pellets also reduces the abundance and amplitude of spikes in the signal. MO{sup +} ions also yield signal spikes, but these MO{sup +} spikes generally occur at different times from their atomic ion counterparts.

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

  9. Microwave assisted extraction of iodine and bromine from edible seaweed for inductively coupled plasma-mass spectrometry determination.

    PubMed

    Romarís-Hortas, Vanessa; Moreda-Piñeiro, Antonio; Bermejo-Barrera, Pilar

    2009-08-15

    The feasibility of microwave energy to assist the solubilisation of edible seaweed samples by tetramethylammonium hydroxide (TMAH) has been investigated to extract iodine and bromine. Inductively coupled plasma-mass spectrometry (ICP-MS) has been used as a multi-element detector. Variables affecting the microwave assisted extraction/solubilisation (temperature, TMAH volume, ramp time and hold time) were firstly screened by applying a fractional factorial design (2(5-1)+2), resolution V and 2 centre points. When extracting both halogens, results showed statistical significance (confidence interval of 95%) for TMAH volume and temperature, and also for the two order interaction between both variables. Therefore, these two variables were finally optimized by a 2(2)+star orthogonal central composite design with 5 centre points and 2 replicates, and optimum values of 200 degrees C and 10 mL for temperature and TMAH volume, respectively, were found. The extraction time (ramp and hold times) was found statistically non-significant, and values of 10 and 5 min were chosen for the ramp time and the hold time, respectively. This means a fast microwave heating cycle. Repeatability of the over-all procedure has been found to be 6% for both elements, while iodine and bromine concentrations of 24.6 and 19.9 ng g(-1), respectively, were established for the limit of detection. Accuracy of the method was assessed by analyzing the NIES-09 (Sargasso, Sargassum fulvellum) certified reference material (CRM) and the iodine and bromine concentrations found have been in good agreement with the indicative values for this CRM. Finally, the method was applied to several edible dried and canned seaweed samples. PMID:19576469

  10. Laser ablation inductively coupled plasma mass spectrometry measurement of isotope ratios in depleted uranium contaminated soils.

    PubMed

    Seltzer, Michael D

    2003-09-01

    Laser ablation of pressed soil pellets was examined as a means of direct sample introduction to enable inductively coupled plasma mass spectrometry (ICP-MS) screening of soils for residual depleted uranium (DU) contamination. Differentiation between depleted uranium, an anthropogenic contaminant, and naturally occurring uranium was accomplished on the basis of measured 235U/238U isotope ratios. The amount of sample preparation required for laser ablation is considerably less than that typically required for aqueous sample introduction. The amount of hazardous laboratory waste generated is diminished accordingly. During the present investigation, 235U/238U isotope ratios measured for field samples were in good agreement with those derived from gamma spectrometry measurements. However, substantial compensation was required to mitigate the effects of impaired pulse counting attributed to sample inhomogeneity and sporadic introduction of uranium analyte into the plasma. PMID:14611049

  11. Assessment of the analytical capabilities of inductively coupled plasma-mass spectrometry

    USGS Publications Warehouse

    Taylor, H.E.; Garbarino, J.R.

    1988-01-01

    A thorough assessment of the analytical capabilities of inductively coupled plasma-mass spectrometry was conducted for selected analytes of importance in water quality applications and hydrologic research. A multielement calibration curve technique was designed to produce accurate and precise results in analysis times of approximately one minute. The suite of elements included Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Se, Sr, V, and Zn. The effects of sample matrix composition on the accuracy of the determinations showed that matrix elements (such as Na, Ca, Mg, and K) that may be present in natural water samples at concentration levels greater than 50 mg/L resulted in as much as a 10% suppression in ion current for analyte elements. Operational detection limits are presented.

  12. Determination of elemental content off rocks by laser ablation inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Lichte, F.E.

    1995-01-01

    A new method of analysis for rocks and soils is presented using laser ablation inductively coupled plasma mass spectrometry. It is based on a lithium borate fusion and the free-running mode of a Nd/YAG laser. An Ar/N2 sample gas improves sensitivity 7 ?? for most elements. Sixty-three elements are characterized for the fusion, and 49 elements can be quantified. Internal standards and isotopic spikes ensure accurate results. Limits of detection are 0.01 ??g/g for many trace elements. Accuracy approaches 5% for all elements. A new quality assurance procedure is presented that uses fundamental parameters to test relative response factors for the calibration.

  13. Determination of mercury in fish samples by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Liaw, Ming-Jyh; Jiang, Shiuh-Jen; Li, Yi-Ching

    1997-06-01

    Ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) has been applied to the determination of mercury in several fish samples. The effects of instrument operating conditions and slurry preparation on the ion signals are reported. Palladium was used as modifier to delay the vaporization of mercury in this study. As the vaporization behavior of mercury in fish slurry and aqueous solution is quite different, the standard addition method was used for the determination of mercury in reference materials. The detection limit of mercury estimated from the standard addition curve was in the range 0.002-0.004 μg g -1 for different samples. This method has been applied to the determination of mercury in dogfish muscle reference material (DORM-1 and DORM-2) and dogfish liver reference material (DOLT-1). Accuracy was better than 4% and precision was better than 7% with the USS-ETV-ICP-MS method.

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

    USGS Publications Warehouse

    Garbarino, J.R.; Taylor, H.E.

    1987-01-01

    Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

  15. Multielement analysis of deep-sea sediments by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Xia, Ning; Wu, Zhaohui; Guo, Dongfa; Yao, De

    2008-05-01

    Marine sediments were dissolved by HNO3-HF-HClO4 in a sealed container at low pressure; HF was evaporated in an open container and salts were dissolved in HCl by heating, then transferred to 2% HNO3 solution. A total of 45 elements, including Li, Be, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Tl, Pb, Bi, Th and U, were measured by inductively coupled plasma mass spectrometry (ICP-MS). Conditions and sample experiments showed that this procedure defines a good experimental method which has the advantages of clear interference, easy operation and reliable results. The concentrations of the 45 elements could be used for resource exploration, environmental assessment and academic research.

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

    NASA Astrophysics Data System (ADS)

    Veverková, Lenka; Hradilová, Šárka; Milde, David; Panáček, Aleš; Skopalová, Jana; Kvítek, Libor; Petrželová, Kamila; Zbořil, Radek

    2014-12-01

    This study examined recoveries of silver determination in animal tissues after wet digestion by inductively coupled plasma mass spectrometry. The composition of the mineralization mixture for microwave assisted digestion was optimized and the best recoveries were obtained for mineralization with HNO3 and addition of HCl promptly after digestion. The optimization was performed on model samples of chicken meat spiked with silver nanoparticles and a solution of ionic silver. Basic calculations of theoretical distribution of Ag among various silver-containing species were implemented and the results showed that most of the silver is in the form of soluble complexes AgCl2- and AgCl32 - for the optimized composition of the mineralization mixture. Three animal tissue certified reference materials were then analyzed to verify the trueness and precision of the results.

  17. Pulsed radio-frequency discharge inductively coupled plasma mass spectrometry for oxide analysis

    NASA Astrophysics Data System (ADS)

    Li, Weifeng; Yin, Zhibin; Hang, Wei; Li, Bin; Huang, Benli

    2016-08-01

    A direct solid sampling technique has been developed based on a pulsed radio-frequency discharge (RFD) in mixture of N2 and Ar environment at atmospheric pressure. With an averaged input power of 65 W, a crater with the diameter of 80 μm and depth of 50 μm can be formed on sample surface after discharge for 1 min, suggesting the feasibility of the pulsed RFD for sampling nonconductive solids. Combined with inductively coupled plasma mass spectrometry (ICPMS), this technique allows to measure elemental composition of solids directly with relative standard deviation (RSD) of ~ 20%. Capability of quantitative analysis was demonstrated by the use of soil standards and artificial standards. Good calibration linearity and limits of detection (LODs) in range of 10- 8-10- 9 g/g were achieved for most elements.

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

    PubMed

    Bua, Daniel Giuseppe; Annuario, Giovanni; Albergamo, Ambrogina; Cicero, Nicola; Dugo, Giacomo

    2016-09-01

    Objective of this study was to determine the content of Cd, Hg, As and Pb in common spices traded in the Italian market, using inductively coupled plasma-mass spectrometry (ICP-MS). The results were compared with the maximum limits established by the national Legislative Decree (LD) no. 107 implementing the Council Directive 88/388/EEC and by international organisations, such as Food and Agriculture Organization (FAO) and World Health Organization (WHO). Food safety for spices was assessed considering the tolerable weekly intake (TWI) and the provisional tolerable weekly intake (PTWI), respectively, for Cd and Hg and the 95% lower confidence limit of the benchmark dose of 1% extra risk (BMDL01) for As and Pb. Investigated elements in all samples were within the maximum limits as set by the national and international normative institutions. Nevertheless, the heavy metal content of some spices exceeded the PTWI, TWI and BMDL01, which needs attention when considering consumer's health. PMID:27074712

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

    PubMed

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

    2014-10-17

    Here we present a novel coupling of thin-layer chromatography (TLC) to diode laser thermal vaporization inductively coupled plasma mass spectrometry (DLTV ICP MS). DLTV is a new technique of aerosol generation which uses a diode laser to induce pyrolysis of a substrate. In this case the cellulose stationary phase on aluminum-backed TLC sheets overprinted with black ink to absorb laser light. The experimental arrangement relies on economic instrumentation: an 808-nm 1.2-W continuous-wave infrared diode laser attached to a syringe pump serving as the movable stage. Using a glass tubular cell, the entire length of a TLC separation channel is scanned. The 8-cm long lanes were scanned in ∼35 s. The TLC - DLTV ICP MS coupling is demonstrated on the separation of four cobalamins (hydroxo-; adenosyl-; cyano-; and methylcobalamin) with limits of detection ∼2 pg and repeatability ∼15% for each individual species. PMID:25193171

  20. Alleviation of overlap interferences for determination of potassium isotope ratios by inductively coupled plasma mass spectrometry

    SciTech Connect

    Jiang, S.J.; Houk, R.S.; Stevens, M.A.

    1988-06-01

    Positioning the sampling orifice relatively far from the load coil combined with use of low forward power and high aerosol gas flow rate causes the background mass spectrum to become dominated by NO/sup +/. Nearly all the Ar/sup +/ and ArH/sup +/ ions are suppressed under these conditions, which frees m/z 39 and 41 for potassium isotope ratio measurements. The precision is 0.3-0.9% relative standard deviation for potassium concentrations in the range 1-50 mg L/sup -1/. The determined ratios are approx. 9% higher than the accepted value and also vary with the concentration of sodium concomitant, so calibrations and chemical separations are desirable. These observations should permit use of inductively coupled plasma mass spectrometry for rapid isotope ratio determinations of potassium from biological organisms or water sources.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

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

    PubMed

    Nie, Xi-du; Fu, Liang

    2015-11-01

    This study established a method for determining Be, Cr, Ni, As, Cd, Sb, Sn, Tl, Hg and Pb, total 10 heavy metals in diatomite filter aid. The diatomite filter aid was digested by using the mixture acid of HNO₃ + HF+ H₃PO₄ in microwave system, 10 heavy metals elements were determined by inductively coupled plasma mass spectrometry (ICP-MS). The interferences of mass spectrometry caused by the high silicon substrate were optimized, first the equipment parameters and isotopes of test metals were selected to eliminate these interferences, the methane was selected as reactant gas, and the mass spectral interferences were eliminated by dynamic reaction cell (DRC). Li, Sc, Y, In and Bi were selected as the internal standard elements to correct the interferences caused by matrix and the drift of sensitivity. The results show that the detection limits for analyte is in the range of 3.29-15.68 ng · L⁻¹, relative standard deviations (RSD) is less than 4.62%, and the recovery is in the range of 90.71%-107.22%. The current method has some advantages such as, high sensitivity, accurate, and precision, which can be used in diatomite filter aid quality control and safety estimations. PMID:26978934

  3. Determination of metals in marine species by microwave digestion and inductively coupled plasma mass spectrometry analysis

    NASA Astrophysics Data System (ADS)

    Yang, Karl X.; Swami, Kamal

    2007-10-01

    A microwave digestion method suitable for determination of multiple elements in marine species was developed, with the use of cold vapor atomic spectrometry for the detection of Hg, and inductively coupled plasma mass spectrometry for all of the other elements. An optimized reagent mixture composed of 2 ml of HNO 3, 2 ml of H 2O 2 and 0.3 ml of HF used in microwave digestion of about 0.15 g (dry weight) of sample was found to give the best overall recoveries of metals in two standard reference materials. In the oyster tissue standard reference material (SRM 1566b), recoveries of Na, Al, K, V, Co, Zn, Se, Sr, Ag, Cd, Ni, and Pb were between 90% and 110%; Mg, Mn, Fe, Cu, As, and Ba recoveries were between 85% and 90%; Hg recovery was 81%; and Ca recovery was 64%. In a dogfish certified reference material (DORM-2), the recoveries of Al, Cr, Mn, Se, and Hg were between 90% and 110%; Ni, Cu, Zn, and As recoveries were about 85%; and Fe recovery was 112%. Method detection limits of the elements were established. Metal concentrations in flounder, scup, and blue crab samples collected from coastal locations around Long Island and in the Hudson River estuary were determined.

  4. Rapid determination of uranium isotopes in urine by inductively coupled plasma-mass spectrometry.

    PubMed

    Shi, Y; Dai, X; Collins, R; Kramer-Tremblay, S

    2011-08-01

    Following a radiological or nuclear emergency involving uranium exposure, rapid analytical methods are needed to analyze the concentration of uranium isotopes in human urine samples for early dose assessment. The inductively coupled plasma mass spectrometry (ICP-MS) technique, with its high sample throughput and high sensitivity, has advantages over alpha spectrometry for uranium urinalysis after minimum sample preparation. In this work, a rapid sample preparation method using an anion exchange chromatographic column was developed to separate uranium from the urine matrix. A high-resolution sector field ICP-MS instrument, coupled with a high sensitivity desolvation sample introduction inlet, was used to determine uranium isotopes in the samples. The method can analyze up to 24 urine samples in two hours with the limits of detection of 0.0014, 0.10, and 2.0 pg mL(-1) for (234)U, (235)U, and (238)U, respectively, which meet the requirement for isotopic analysis of uranium in a radiation emergency. PMID:21709502

  5. Determination of mercury in whole blood and urine by inductively coupled plasma mass spectrometry.

    PubMed

    Fong, Bonnie Mei Wah; Siu, Tak Shing; Lee, Joseph Sai Kit; Tam, Sidney

    2007-06-01

    The conventional method for the determination of mercury in clinical samples is cold vapor atomic absorption spectrometry. Sample digestion or pretreatment require large sample volume and long sample preparation time. The inductively coupled plasma mass spectrometry (ICP-MS) method developed in this study requires only 100 microL of sample with practically no preparation, except for dilution with diluent. Significant savings in sample volumes, reagents, technician time, and analysis time are realized. Among different types of diluents, the one containing acid, tert-butanol, and potassium dichromate gave the best results to remove the mercury memory effect. The interassay precisions for whole blood and urine were < 5% and < 8%, respectively, and the intra-assay precisions were < 3% and < 7%, respectively. The lower limits of detection were 0.13, 0.17, and 0.26 microg/L for aqueous standard, urine, and whole blood, respectively. The developed ICP-MS method correlated well with the atomic absorption method and can offer an alternative to the atomic absorption method for mercury analysis with less sample volume requirement as well as shorter analysis time. PMID:17579973

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

    NASA Astrophysics Data System (ADS)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

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

    PubMed

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

    2016-02-17

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

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

    SciTech Connect

    Maxwell, S.; Jones, V.; Culligan, B.; Nichols, S.; Noyes, G.

    2010-06-23

    A new method that allows rapid preconcentration and separation of plutonium and neptunium in water samples was developed for the measurement of {sup 237}Np and Pu isotopes by inductively-coupled plasma mass spectrometry (ICP-MS) and alpha spectrometry; a hybrid approach. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via peak tailing. The method provide enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then moving Pu to DGA resin for additional removal of uranium. The decontamination factor for uranium from Pu is almost 100,000 and the decontamination factor for U from Np is greater than 10,000. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration is performed using a streamlined calcium phosphate precipitation method. Purified solutions are split between ICP-MS and alpha spectrometry so that long and short-lived Pu isotopes can be measured successfully. The method allows for simultaneous extraction of 20 samples (including QC samples) in 4 to 6 hours, and can also be used for emergency response. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu, {sup 238}Pu, and {sup 239}Pu were measured by alpha spectrometry.

  9. Determination of arsenic in gold by flow injection inductively coupled plasma mass spectrometry with matrix removal by reductive precipitation

    NASA Astrophysics Data System (ADS)

    Becotte-Haigh, Paul; Tyson, Julian F.; Denoyer, Eric; Hinds, Michael W.

    1996-12-01

    Arsenic was determined in gold by flow injection hydride generation inductively coupled plasma-mass spectrometry following a batch mode reductive precipitation removal of the interfering gold matrix. A solution of potassium iodide, L-ascorbic acid, and hydrochloric acid was used as the reluctant. The recovery of gold by precipitation and filtration was 99 ± 3%. The detection limit for arsenic in gold was 55 ng g -1 in the solid. The concentration of arsenic that was determined in the Royal Canadian Mint gold sample FAU-10 was 29.7 μg g -1 in the solid; this value was indistinguishable, with 95% confidence, from values determined at the Royal Canadian Mint by graphite furnace atomic absorption spectrometry and by inductively coupled plasma-mass spectrometry. The standard deviation for four replicate determinations of the arsenic in FAU-10 was 0.972 μg g -1 in the solid.

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

    NASA Astrophysics Data System (ADS)

    Giner Martínez-Sierra, J.; Galilea San Blas, O.; Marchante Gayón, J. M.; García Alonso, J. I.

    2015-06-01

    In recent years the number of applications of sulfur (S) analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. In this article we describe in some depth the application of ICP-MS for S analysis with emphasis placed on the sulfur-specific detection by hyphenated techniques such as LC, GC, CE and LA coupled on-line to ICP-MS. The different approaches available for sulfur isotope ratio measurements by ICP-MS are also detailed. Particular attention has been paid to the quantification of peptides/proteins and the analysis of metallopeptides/metalloproteins via sulfur by LC-ICP-MS. Likewise, the speciation analysis of metal-based pharmaceuticals and metallodrugs and non-metal selective detection of pharmaceuticals via S are highlighted. Labeling procedures for metabolic applications are also included. Finally, the measurement of natural variations in S isotope composition with multicollector ICP-MS instruments is also covered in this review.

  11. Determination of the rare-earth elements in geological materials by inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Lichte, F.E.; Meier, A.L.; Crock, J.G.

    1987-01-01

    A method of analysis of geological materials for the determination of the rare-earth elements using the Inductively coupled plasma mass spectrometric technique (ICP-MS) has been developed. Instrumental parameters and factors affecting analytical results have been first studied and then optimized. Samples are analyzed directly following an acid digestion, without the need for separation or preconcentration with limits of detection of 2-11 ng/g, precision of ?? 2.5% relative standard deviation, and accuracy comparable to inductively coupled plasma emission spectrometry and instrumental neutron activation analysis. A commercially available ICP-MS instrument is used with modifications to the sample introduction system, torch, and sampler orifice to reduce the effects of high salt content of sample solutions prepared from geologic materials. Corrections for isobaric interferences from oxide ions and other diatomic and triatomic ions are made mathematically. Special internal standard procedures are used to compensate for drift in metahmetal oxide ratios and sensitivity. Reference standard values are used to verify the accuracy and utility of the method.

  12. Inductively coupled plasma mass spectrometry applied to isotopic analysis of iron in human fecal matter

    SciTech Connect

    Ting, B.T.G.; Janghorbani, M.

    1986-06-01

    Inductively coupled plasma mass spectrometry combined with stable isotope dilution is applied to accurate isotopic analysis of human fecal matter for /sup 54/Fe and /sup 58/Fe. Argon plasma generated interferences are of minor concern. The interference from /sup 54/Cr can be corrected instrumentally, whereas /sup 58/Ni must be removed chemically. The ratio of the stable isotopes of interest can be measured routinely with a relative standard deviation of about 1%. The overall accuracy of the method for quantitative isotopic analyses is evaluated in Standard Reference Material (SRM) 1577a (Bovine Liver), fecal homogenate subsamples, and synthetic solutions of iron. For SRM 1577a, the respective comparisons are (..mu..g/g) 192.2 +/- 2.2 (present method) vs. 194 +/- 20 (certified value). For the fecal matrix, the present method yields (..mu..g/mL) 15.14 +/- 0.36 vs. 15.82 +/- 0.48 based on atomic absorption spectrophotometry. For an iron solution (250 ppm), replicate analyses yield the value of 245.4 +/- 1.5 ppm.

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

    NASA Astrophysics Data System (ADS)

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

    2000-12-01

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

  14. Determination of long-lived actinides in soil leachates by inductively coupled plasma: Mass spectrometry

    SciTech Connect

    Crain, J.S.; Smith, L.L.; Yaeger, J.S.; Alvarado, J.A.

    1994-06-01

    Inductively coupled plasma -- mass spectrometry (ICP-MS) was used to concurrently determine multiple long-lived (t{sub 1/2} > 10{sup 4} y) actinide isotopes in soil samples. Ultrasonic nebulization was found to maximize instrument sensitivity. Instrument detection limits for actinides in solution ranged from 50 mBq L{sup {minus}1} ({sup 239}Pu) to 2 {mu}Bq L{sup {minus}1} ({sup 235}U) Hydride adducts of {sup 232}Th and {sup 238}U interfered with the determinations of {sup 233}U and {sup 239} Pu; thus, extraction chromatography was, used to eliminate the sample matrix, concentrate the analytes, and separate uranium from the other actinides. Alpha spectrometric determinations of {sup 230}Th, {sup 239}Pu, and the {sup 234}U/{sup 238}U activity ratio in soil leachates compared well with ICP-MS determinations; however, there were some small systematic differences (ca. 10%) between ICP-MS and a-spectrometric determinations of {sup 234}U and {sup 238}U activities.

  15. Determination of metals in Brazilian soils by inductively coupled plasma mass spectrometry.

    PubMed

    de Carvalho, Rui M; dos Santos, Jéssica A; Silva, Jessee A S; do Prado, Thiago G; da Fonseca, Adriel Ferreira; Chaves, Eduardo S; Frescura, Vera L A

    2015-08-01

    The concentration of metals in Brazilian soil under no-tillage (NT) and an area under native vegetation (NV) was determined by inductively coupled plasma mass spectrometry. The applied method was based on microwave-assisted acid digestion using HNO3, HCl, H2O2, and HF. The accuracy of the method was evaluated by analyzing two certified reference materials (BCR-142 and RS-3). The relative standard deviation for all target elements was below 8% indicating an adequate precision and the limit of detection ranged from 0.03 μg g(-1) (Cd) to 24.0 μg g(-1) (Fe). The concentrations of Al, As, Ba, Cd, Cu, Fe, Mg, Mn, Ni, Pb, Sr, and Zn in the different layers (0-10, 10-20, 20-40, and 40-60 cm) were determined in two types of soils, located in Paraná State in Brazil. The soil layers analysis revealed a different behavior of metals concentrations in soil samples under NT and NV. The obtained results showed a clear impact of anthropogenic action with respect to specific metals due to many years of uncontrolled application rates of limestone and phosphate fertilizers. PMID:26220781

  16. Using inductively coupled plasma-mass spectrometry for calibration transfer between environmental CRMs.

    PubMed

    Turk, G C; Yu, L L; Salit, M L; Guthrie, W F

    2001-06-01

    Multielement analyses of environmental reference materials have been performed using existing certified reference materials (CRMs) as calibration standards for inductively coupled plasma-mass spectrometry. The analyses have been performed using a high-performance methodology that results in comparison measurement uncertainties that are significantly less than the uncertainties of the certified values of the calibration CRM. Consequently, the determined values have uncertainties that are very nearly equivalent to the uncertainties of the calibration CRM. Several uses of this calibration transfer are proposed, including, re-certification measurements of replacement CRMs, establishing traceability of one CRM to another, and demonstrating the equivalence of two CRMs. RM 8704, a river sediment, was analyzed using SRM 2704, Buffalo River Sediment, as the calibration standard. SRM 1632c, Trace Elements in Bituminous Coal, which is a replacement for SRM 1632b, was analyzed using SRM 1632b as the standard. SRM 1635, Trace Elements in Subbituminous Coal, was also analyzed using SRM 1632b as the standard. PMID:11451248

  17. Inductively coupled plasma-mass spectrometry: An emerging method for analysis of long-lived radionuclides

    SciTech Connect

    Ross, R.R.; Noyce, J.R.; Lardy, M.M.

    1993-12-31

    Inductively coupled plasma-mass spectrometry (ICP-MS) is a relatively new technique that can analyze for most of the elements in the periodic table at parts per billion (ng/mL) to parts per trillion (pg/mL). Already in use several years for trace analysis of stable isotopes, ICP-MS is becoming a powerful, complementary method to the counting of decay radiations for the analysis of radionuclides. Most radionuclides with half-lives longer than approximately 1x10{sup 3} years can be quantitatively detected on ICP-MS instruments that have an electrothermal vaporization unit for the injection of sample aliquants. Radionuclides with half-lives greater than approximately 1x10{sup 4} years can be measured routinely with greater sensitivity and more quickly by ICP-MS than by radiation counting. Examples from the literature of applying ICP-MS to radionuclides are the bioassay of uranium in urine, measurement of {sup 237}Np in soil and silt, and analysis for {sup 99}Tc in sea water, seaweed, and marine sediment. This paper discusses the instrumentation, advantages and limitations, and present and potential applications of ICP-MS for radionuclide measurements.

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

    NASA Astrophysics Data System (ADS)

    Ossipov, K.; Seregina, I. F.; Bolshov, M. A.

    2016-04-01

    Inductively coupled plasma mass spectrometry (ICP-MS) is widely used in the analysis of biological samples (whole blood, serum, blood plasma, urine, tissues, etc.) and pharmaceutical drugs. The shortcomings of this method related to spectral and non-spectral interferences are manifested in full measure in determination of the target analytes in these complex samples strongly differing in composition. The spectral interferences are caused by similarity of masses of the target component and sample matrix components. Non-spectral interferences are related to the influence of sample matrix components on the physicochemical processes taking place during formation and transportation of liquid sample aerosols into the plasma, on the value and spatial distribution of plasma temperature and on the transmission of the ion beam from the interface to mass spectrometer detector. The review is devoted to analysis of different mechanisms of appearance of non-spectral interferences and to ways for their minimization or elimination. Special attention is paid to the techniques of biological sample preparation, which largely determine the mechanisms of the influence of sample composition on the results of element determination. The ways of lowering non-spectral interferences by instrumental parameter tuning and application of internal standards are considered. The bibliography includes 189 references.

  19. Quantitative images of metals in plant tissues measured by laser ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Becker, J. S.; Dietrich, R. C.; Matusch, A.; Pozebon, D.; Dressler, V. L.

    2008-11-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for quantitative imaging of toxic and essential elements in thin sections (thickness of 30 or 40 μm) of tobacco plant tissues. Two-dimensional images of Mg, Fe, Mn, Zn, Cu, Cd, Rh, Pt and Pb in leaves, shoots and roots of tobacco were produced. Sections of the plant tissues (fixed onto glass slides) were scanned by a focused beam of a Nd:YAG laser in a laser ablation chamber. The ablated material was transported with argon as carrier gas to the ICP ion source at a quadrupole ICP-MS instrument. Ion intensities of the investigated elements were measured together with 13C +, 33S + and 34S + within the entire plant tissue section. Matrix matching standards (prepared using powder of dried tobacco leaves) were used to constitute calibration curves, whereas the regression coefficient of the attained calibration curves was typically 0.99. The variability of LA-ICP-MS process, sample heterogeneity and water content in the sample were corrected by using 13C + as internal standard. Quantitative imaging of the selected elements revealed their inhomogeneous distribution in leaves, shoots and roots.

  20. Investigation of palladium and platinum levels in food by sector field inductively coupled plasma mass spectrometry.

    PubMed

    Frazzoli, Chiara; Cammarone, Roberta; Caroli, Sergio

    2007-05-01

    Over the last two decades, there has been increased concern regarding the impact of some noble metals, such as Pd and Pt, on human health. These elements pollute the environment due to their widespread use as catalytic converters and in medical applications. The risk they pose to human health and the environment is still controversial; however, literature data point to diet as an important source of uptake by the human body. Within this context, the total Pd and Pt content of several Italian food commodities has been investigated. A total of 90 samples, including flour products, vegetables and foodstuffs of animal origin (meat, milk and eggs), were collected and freeze-dried. Samples were analyzed by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) after chopping or crushing followed by freeze-drying and microwave (MW)-assisted acid digestion in a Class-100 clean-room. A mathematical approach was adopted to correct the mass signals for still unresolved interference (mDeltam = 300, 10 000). The lowest and highest concentrations of Pt, i.e. 17 and 93 ng kg(-1) (dry weight, dw), were found in vegetables and flour products, respectively. The lowest Pd level (2830 ng kg(-1) dw) was found in eggs and the highest (47 800 ng kg(-1) dw) in vegetables. PMID:17487666

  1. Plutonium determination in seawater by inductively coupled plasma mass spectrometry: A review.

    PubMed

    Cao, Liguo; Bu, Wenting; Zheng, Jian; Pan, Shaoming; Wang, Zhongtang; Uchida, Shigeo

    2016-05-01

    Knowing the concentration and isotopic ratio of Pu in seawater is of critical importance for assessing Pu contamination and investigating oceanic processes. In recent decades, the concentration of (239+240)Pu in seawater, particularly for surface seawater, has presented an exponential decreasing trend with time; thus determination of Pu in seawater has become a challenge nowadays. Here, we have summarized and critically discussed a variety of reported analytical methods for Pu determination in seawater sample based on inductively coupled plasma mass spectrometry (ICP-MS) analytical technique for rapid ultra-trace detection of Pu. Generally, pretreatments for seawater sample include co-precipitation, valence adjustment and chemical separation and purification procedures, all of which are comprehensively reviewed. Overall, the selected anion-exchange, extraction resins and operation condition are important for decontamination of interference from matrix elements and achieving satisfactory chemical yields. In addition, other mass spectrometric and radiometric detections are briefly addressed and compared with the focus on assessing ICP-MS. Finally, we discuss some issues and prospects in determination and application of Pu isotopes in seawater samples for future research. PMID:26946007

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

    PubMed Central

    Boaru, Sorina Georgiana; Merle, Uta; Uerlings, Ricarda; Zimmermann, Astrid; Flechtenmacher, Christa; Willheim, Claudia; Eder, Elisabeth; Ferenci, Peter; Stremmel, Wolfgang; Weiskirchen, Ralf

    2015-01-01

    Wilson's disease is an autosomal recessive disorder in which the liver does not properly release copper into bile, resulting in prominent copper accumulation in various tissues. Affected patients suffer from hepatic disorders and severe neurological defects. Experimental studies in mutant mice in which the copper-transporting ATPase gene (Atp7b) is disrupted revealed a drastic, time-dependent accumulation of hepatic copper that is accompanied by formation of regenerative nodes resembling cirrhosis. Therefore, these mice represent an excellent exploratory model for Wilson's disease. However, the precise time course in hepatic copper accumulation and its impact on other trace metals within the liver is yet poorly understood. We have recently established novel laser ablation inductively coupled plasma mass spectrometry protocols allowing quantitative metal imaging in human and murine liver tissue with high sensitivity, spatial resolution, specificity and quantification ability. By use of these techniques, we here aimed to comparatively analyse hepatic metal content in wild-type and Atp7b deficient mice during ageing. We demonstrate that the age-dependent accumulation of hepatic copper is strictly associated with a simultaneous increase in iron and zinc, while the intrahepatic concentration and distribution of other metals or metalloids is not affected. The same findings were obtained in well-defined human liver samples that were obtained from patients suffering from Wilson's disease. We conclude that in Wilson's disease the imbalances of hepatic copper during ageing are closely correlated with alterations in intrahepatic iron and zinc content. PMID:25704483

  3. Determination of rare earth elements in environmental materials by inductively coupled plasma mass spectrometry

    SciTech Connect

    Panday, V.K.; Hoppstock, K.; Becker, J.S.; Dietze, H.J.

    1996-09-01

    Despite the fact that rare earth elements (REE) have found increasing use in modern technology only few data are available on their concentrations in biological and environmental samples. Inductively coupled plasma mass spectrometry (ICP-MS) has been employed to study the concentration of rare earth elements (REE) in various environmental materials (e.g., pine needles, mussel tissue, apple leaves) available from National Institute of Standards and Technology (NIST), the Bureau of European Communities (BCR), and the German Environmental Specimens Bank. After the decomposition of the environmental samples with HNO{sub 3}, the REE (present mostly in the ng/g-range) were separated from the matrix and simultaneously preconcentrated using liquid-liquid extraction with bis(2-ethyl hexyl)-ortho-phosphoric acid (HDEHP) in toluene as a selective reagent at pH = 2 and subsequent back extraction of the elements into the aqueous by 6M HNO{sub 3}. Recoveries of better 90% were obtained for almost all REE. A Perkin Elmer/Sciex ELAN 5000 ICP-MS and HR-ICP-MS ELEMENT from Finnigan MAT were used for quantitative analysis (by external calibration and ID-ICP-MS) of REE. The results of determination of REE concentrations agree well with the data available on some of these materials. Further supplement information on the contents of various REE in these materials.

  4. Studying Arsenite-Humic Acid Complexation Using Size Exclusion Chromatography-Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Liu, Guangliang; Cai, Yong

    2012-01-01

    Arsenic (As) can form complexes with dissolved organic matter (DOM), which affects the fate of arsenic in waste sites and natural environments. It remains a challenge to analyze DOM-bound As, in particular by using a direct chromatographic separation method. Size exclusion chromatography (SEC) hyphenated with UV spectrophotometer and inductively coupled plasma mass spectrometry (ICP-MS) was developed to characterize the complexation of arsenite (AsIII) with DOM. This SEC-UV-ICP-MS method is able to differentiate AsIII-DOM complexes from free As species and has the advantage of direct determination of both free and DOM-bound AsIII through mild separation. The suitability of this method for studying AsIII-DOM complexation was demonstrated by its application, in combination with the Scatchard plot and nonlinear regression of ligand binding model, for characterizing AsIII complexation with humic acid (HA) in the absence or presence of natural sand. The results suggest that, consistent with polyelectrolytic nature of HA, the AsIII-HA complexation should be accounted for by multiple classes of binding sites. By loosely classifying the binding sites into strong (S1) and weak (S2) sites, the apparent stability constants (Ks) of the resulting As-DOM complexes were calculated as log Ks1 = 6.5–7.1 while log Ks2 = 4.7–5.0. PMID:22664255

  5. Improving sensitivity for microchip electrophoresis interfaced with inductively coupled plasma mass spectrometry using parallel multichannel separation.

    PubMed

    Cheng, Heyong; Liu, Jinhua; Xu, Zigang; Wang, Yuanchao; Ye, Meiying

    2016-08-26

    We reported sensitivity enhancement using multichannel parallel separation for microchip electrophoresis hyphenated with inductively coupled plasma mass spectrometry (MCE-ICP-MS) in this study. By using 2-20 array lanes for parallel separation, the sensitivity of the MCE-ICP-MS system was proportionally improved by 2-20 folds. No significantly adverse effect of parallel separation on column efficiency and resolution was observed. Rapid separation of Hg(2+) and methylmercuric (MeHg) ion within 36s under an electric field of 800Vcm(-1) was achieved in the 2-cm twenty-channels with a background electrolyte of 5mmolL(-1) borate buffer (pH 9.2). Detection limits of Hg(2+) and MeHg by the proposed system were decreased to 6.8-7.1ngL(-1). Good agreement between determined values and certified values of a certified reference fish was obtained with recoveries ranged between 94-98%. All results prove its advantages including high sensitivity, high efficiency and low operation cost, which are beneficial to routine analysis of metal speciation in environmental, biological and food fields. PMID:27488720

  6. Determination of selenium urinary metabolites by high temperature liquid chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Terol, A; Ardini, F; Basso, A; Grotti, M

    2015-02-01

    The coupling of high temperature liquid chromatography (HTLC) and inductively coupled plasma mass spectrometry (ICPMS) for the determination of selenium metabolites in urine samples is reported for the first time. In order to achieve "ICPMS-friendly" chromatographic conditions, the retention on a graphite stationary phase of the major selenium urinary metabolites using only plain water with 2% methanol as the mobile phase was investigated. Under the optimal conditions (T=80°C, Ql=1.2 mL min(-1)), methyl 2-acetamido-2-deoxy-1-seleno-β-d-galactopyranoside (selenosugar 1), methyl 2-acetamido-2-deoxy-1-seleno-β-d-glucosopyranoside (selenosugar 2) and trimethylselenonium ion were efficiently separated in less than 7 min, without any interferences due to other common selenium species (selenite, selenate, selenocystine and selenomethionine) or detectable effect of the urine matrix. The limits of detection were 0.3-0.5 ng Se mL(-1), and the precision of the analytical procedure was better than 3% (RSD%, n=5). The HTLC-ICPMS method was applied to the analysis of urine samples from two volunteers before and after ingestion of Brazil nuts or selenium supplements. The developed procedure proved to be adequate for the analytical task, providing results consistent with previous studies. PMID:25582485

  7. Acid retardation method in analysis of strongly acidic solutions by inductively coupled plasma mass-spectrometry.

    PubMed

    Seregina, I F; Perevoznik, O A; Bolshov, M A

    2016-10-01

    Acid retardation on the sorbents as a technique for reduction of the acidity of the solutions prior to their analysis by inductively coupled plasma mass spectrometry was proposed and investigated. The proposed scheme provides substantial separation of the analytes and nitric acid, which allows direct introduction of the eluates in plasma without dilution. Two sorbents were examined - AV-17 anion-exchange resin and the Stirosorb 584 sorbent. Sorption and desorption of 38 elements on these sorbents were investigated. The efficiencies of the REEs' sorption on the anion-exchange and neutral sorbents were compared. The higher efficiency of the REEs and HNO3 separation was revealed for the neutral Stirosorb 584 sorbent. It was also found that most elements come out quantitatively of the column filled with the AV-17 resin after pumping 2-4mL of the solution. Wherein, the concentration of nitric acid decreased by 20 times. The anomalous behaviour of Ag, Pb, Th and U on the AV-17 resin was found. These analytes were eluted only after pumping 4 column volumes of deionized water. Na, K, Fe, Al and Li in concentrations within (50-1000mgL(-1)) range did not affect the recovery of REEs. The potential of ARM technique was demonstrate by the analysis of puriss. HNO3 and silverware. ARM enables to avoid dilution of highly acidic solutions prior to their introduction in ICP-MS. PMID:27474322

  8. Characterization of natural water resources in Israel by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Halicz, L.; Becker, J. S.; Pickhardt, C.; Gavrieli, I.; Burg, A.; Nishri, A.; Platzner, I. T.

    2006-03-01

    Analytical procedures are applied for the determination of plutonium, uranium and strontium concentration, their isotope ratios and the analysis of rare earth elements (REE) at trace and ultratrace level in natural Israeli water resources with relatively high matrix content (Na = 20-150 mg L-1, Mg = 20-50 mg L-1 and Ca = 40-100 mg L-1) by inductively coupled plasma mass spectrometry (ICP-MS). To avoid matrix and clogging effects on the cones during mass spectrometric measurements and to analyze Pu and REE at extremely low concentration levels, separation procedures from matrices were applied. An extremely low Pu contamination of the Sea of Galilee was observed due to global nuclear fallout after the nuclear weapons test in the 1960s. The detection limit, for example, for 239Pu was found to be <10-19 g mL-1. For uranium a natural variation of the 234U/238U isotope ratios by a factor of up to 2 in comparison to the IUPAC table value was detected using ICP-MS. This paper discusses the application of double-focusing sector field ICP-MS with single and multiple ion collection as well as quadrupole-based ICP-MS (ICP-QMS) for the quantitative determination of REE, plutonium, uranium and strontium and their isotope ratios after analyte/matrix separation at trace and ultratrace levels in natural water.

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

    SciTech Connect

    Bricker, T.

    1994-07-27

    Since its development, inductively coupled plasma mass spectrometry (ICP-MS) has been a widely used analytical technique. ICP-MS offers low detection limits, easy determination of isotope ratios, and simple mass spectra from analyte elements. ICP-MS has been successfully employed for many applications including geological, environmental, biological, metallurgical, food, medical, and industrial. One specific application important to many areas of study involves elemental speciation by using ICP-MS as an element specific detector interfaced to liquid chromatography. Elemental speciation information is important and cannot be obtained by atomic spectrometric methods alone which measure only the total concentration of the element present. Part 1 of this study describes the speciation of selenium in human serum by size exclusion chromatography (SEC) and detection by ICP-MS. Although ICP-MS has been widely sued, room for improvement still exists. Difficulties in ICP-MS include noise in the background, matrix effects, clogging of the sampling orifice with deposited solids, and spectral interference caused by polyatomic ions. Previous work has shown that the addition of xenon into the central channel of the ICP decreases polyatomic ion levels. In Part 2 of this work, a fundamental study involving the measurement of the excitation temperature is carried out to further understand xenon`s role in the reduction of polyatomic ions. 155 refs.

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

    USGS Publications Warehouse

    Todorov, T.I.; Xu, H.; Ejnik, J.W.; Mullick, F.G.; Squibb, K.; McDiarmid, M.A.; Centeno, J.A.

    2009-01-01

    In this study we report depleted uranium (DU) analysis in whole blood samples. Internal exposure to DU causes increased uranium levels as well as change in the uranium isotopic composition in blood specimen. For identification of DU exposure we used the 235U/238U ratio in blood samples, which ranges from 0.00725 for natural uranium to 0.002 for depleted uranium. Uranium quantification and isotopic composition analysis were performed by inductively coupled plasma mass spectrometry. For method validation we used eight spiked blood samples with known uranium concentrations and isotopic composition. The detection limit for quantification was determined to be 4 ng L-1 uranium in whole blood. The data reproduced within 1-5% RSD and an accuracy of 1-4%. In order to achieve a 235U/238U ratio range of 0.00698-0.00752% with 99.7% confidence limit a minimum whole blood uranium concentration of 60 ng L??1 was required. An additional 10 samples from a cohort of veterans exposed to DU in Gulf War I were analyzed with no knowledge of their medical history. The measured 235U/ 238U ratios in the blood samples were used to identify the presence or absence of DU exposure within this patient group. ?? 2009 The Royal Society of Chemistry.

  11. Direct solid sampling of fire assay beads by spark ablation inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Van Hoven, R. L.; Nam, Sang-Ho; Montaser, Akbar; Doughten, M. W.; Dorrzapf, A. F.

    1995-06-01

    A spark-based, solid-sampling cell is described for inductively coupled plasma mass spectrometry (ICP-MS). The cell is devised for the direct sampling of gold and silver beads produced by the classical lead fire assay procedure. The sampler produces a solid aerosol composed of submicron-sized vapor condensates and small (< 2 μm) spherules. In contrast to solution nebulization, the mass spectrum for spark-ICP-MS is relatively free of interfering metal oxide, polyatomic, and multiply-charged ions. The measurement precision is 3% RSD for Pt, Pd, and Rh preconcentrated into fire assay beads, but is 6% RSD for Ir due to its heterogeneous distribution in a silver bead. Detection limits determined for Pt, Pd, Rh, and Ir in fire assay beads range from 0.6 μg/g (Pt) to 1.2 μg/g (Pd). Calibration curves for these elements are linear up to the highest concentration in the bead studied (2000 μg/g). The quantitative potential of the method is evaluated using the South African Reference Material (SARM-7) geologic standard.

  12. 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.

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

    SciTech Connect

    Luong, E.

    1999-05-10

    This dissertation focuses on the development of methods for stable isotope metabolic tracer studies in living systems using inductively coupled plasma single and dual quadrupole mass spectrometers. Sub-nanogram per gram levels of molybdenum (Mo) from human blood plasma are isolated by the use of anion exchange alumina microcolumns. Million-fold more concentrated spectral and matrix interferences such as sodium, chloride, sulfate, phosphate, etc. in the blood constituents are removed from the analyte. The recovery of Mo from the alumina column is 82 {+-} 5% (n = 5). Isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is utilized for the quantitative ultra-trace concentration determination of Mo in bovine and human blood samples. The average Mo concentration in reference bovine serum determined by this method is 10.2 {+-} 0.4 ng/g, while the certified value is 11.5 {+-} 1.1 ng/g (95% confidence interval). The Mo concentration of one pool of human blood plasma from two healthy male donors is 0.5 {+-} 0.1 ng/g. The inductively coupled plasma twin quadrupole mass spectrometer (ICP-TQMS) is used to measure the carbon isotope ratio from non-volatile organic compounds and bio-organic molecules to assess the ability as an alternative analytical method to gas chromatography combustion isotope ratio mass spectrometry (GC-combustion-IRMS). Trytophan, myoglobin, and {beta}-cyclodextrin are chosen for the study, initial observation of spectral interference of {sup 13}C{sup +} with {sup 12}C{sup 1}H{sup +} comes from the incomplete dissociation of myoglobin and/or {beta}-cyclodextrin.

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

    PubMed

    Erdemir, Umran Seven; Gucer, Seref

    2014-11-01

    In this study, an analytical fractionation scheme based on water, diethyl ether, n-hexane, and methanol extractions has been developed to identify manganese-bound fractions. Additionally, in vitro simulated gastric and intestinal digestion, n-octanol extraction, and activated carbon adsorption were used to interpret the manganese-bound structures in hazelnuts in terms of bioaccessibility. The total content of manganese in the samples was determined by inductively coupled plasma-mass spectrometry after microwave-assisted digestion, and additional validation was performed using atomic absorption spectroscopy. Water fractions were further evaluated by high-performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry for the identification of water-soluble manganese fractions in hazelnut samples. The limits of detection and quantification were 3.6 and 12.0 μg L(-1), respectively, based on peak height. PMID:25310841

  15. Controlled Dissolution of Surface Layers for Elemental Analysis by Inductively Coupled Plasma-Mass Spectrometry

    SciTech Connect

    Susan Elizabeth Lorge

    2007-12-01

    Determining the composition of thin layers is increasingly important for a variety of industrial materials such as adhesives, coatings and microelectronics. Secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES), glow discharge mass spectrometry (GDMS), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are some of the techniques that are currently employed for the direct analysis of the sample surface. Although these techniques do not suffer from the contamination problems that often plague sample dissolution studies, they do require matrix matched standards for quantification. Often, these standards are not readily available. Despite the costs of clean hoods, Teflon pipette tips and bottles, and pure acids, partial sample dissolution is the primary method used in the semiconductor industry to quantify surface impurities. Specifically, vapor phase decomposition (VPD) coupled to ICP-MS or total reflection x-ray fluorescence (TXRF) provides elemental information from the top most surface layers at detection sensitivities in the 10{sup 7}-10{sup 10}atoms/cm{sup 2} range. The ability to quantify with standard solutions is a main advantage of these techniques. Li and Houk applied a VPD-like technique to steel. The signal ratio of trace element to matrix element was used for quantification. Although controlled dissolution concentrations determined for some of the dissolved elements agreed with the certified values, concentrations determined for refractory elements (Ti, Nb and Ta) were too low. LA-ICP-MS and scanning electron microscopy (SEM) measurements indicated that carbide grains distributed throughout the matrix were high in these refractory elements. These elements dissolved at a slower rate than the matrix element, Fe. If the analyte element is not removed at a rate similar to the matrix element a true representation of the

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

    PubMed

    Maxwell, Sherrod L; Culligan, Brian K; Jones, Vernon D; Nichols, Sheldon T; Noyes, Gary W; Bernard, Maureen A

    2011-08-01

    A new rapid separation method was developed for the measurement of plutonium and neptunium in urine samples by inductively-coupled plasma mass spectrometry (ICP-MS) and/or alpha spectrometry with enhanced uranium removal. This method allows separation and preconcentration of plutonium and neptunium in urine samples using stacked extraction chromatography cartridges and vacuum box flow rates to facilitate rapid separations. There is an increasing need to develop faster analytical methods for emergency response samples. There is also enormous benefit to having rapid bioassay methods in the event that a nuclear worker has an uptake (puncture wound, etc.) to assess the magnitude of the uptake and guide efforts to mitigate dose (e.g., tissue excision and chelation therapy). This new method focuses only on the rapid separation of plutonium and neptunium with enhanced removal of uranium. For ICP-MS, purified solutions must have low salt content and low concentration of uranium due to spectral interference of (238)U(1)H(+) on m/z 239. Uranium removal using this method is enhanced by loading plutonium and neptunium initially onto TEVA resin, then moving plutonium to DGA resin where additional purification from uranium is performed with a decontamination factor of almost 1×10(5). If UTEVA resin is added to the separation scheme, a decontamination factor of ~3 × 10(6) can be achieved. PMID:21709507

  17. [Determination of trace elements in sika bone powder by inductively coupled plasma mass spectrometry with microwave digestion].

    PubMed

    Liu, Yan-Ming; Chen, Zhi-Yong; Han, Jin-Tu; Wang, Hui; Wang, Zhi-Wen

    2006-05-01

    Contents of trace elements in sika bone powder were determined with microwave digestion and inductively coupled plasma mass spectrometry. Under the optimum conditions, the detection limits (3sigma, n = 11) are in the range of 0. 000 6-1. 498 ng x mL(-1) with relative standard deviations of 1.7%-6.8%. The recoveries are between 91% and 109%. The analytical results of national certified reference demonstrated the applicability of the proposed method. PMID:16883876

  18. Determination of Pu in urine at ultratrace level by sector field inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Zoriy, M. V.; Pickhardt, C.; Ostapczuk, P.; Hille, R.; Becker, J. S.

    2004-04-01

    A new analytical procedure has been developed for the determination of Pu in urine at the low ag ml-1 concentration level by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS). One liter of urine doped with 4 pg 242Pu was analyzed after co-precipitation with Ca3(PO4)2 followed by extraction chromatography on TEVA resin in order to enrich the Pu and remove uranium and matrix elements. Figures of merit of ICP-SFMS for the determination of Pu were studied using two nebulizers, PFA-100 and direct injection high-efficiency nebulizer (DIHEN), for solution introduction with uptake rates of 0.58 and 0.06 ml min-1, respectively. The sensitivity for Pu in ICP-SFMS was determined to be 2000 and 1380 MHz ppm-1 for the PFA-100 and DIHEN nebulizers, respectively. Due to the low solution uptake rate of DIHEN the absolute sensitivity was about seven times better and yielded 1380 counts fg-1 in comparison to 207 counts fg-1 measured with the PFA-100 nebulizer. Recovery using 242Pu tracer was about 70%. The limits of detection for 239Pu in 1 l of urine, based on an enrichment factor of 100 for PFA-100 nebulizer and 1000 for DIHEN, were 9×10-18 and 1.02×10-18 g ml-1, respectively. Measurements of 240Pu/239Pu isotopic ratio in synthetically prepared urine standard solution yielded a precision of 1.8 and 1.9% and accuracy of 1.5 and 1.8% for the PFA-100 and DIHEN nebulizers, respectively.

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

    PubMed

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

    2005-07-15

    Element determination in solid waste products from the steel industry usually involves the time-consuming step of preparing a solution of the solid. Laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the analysis of Cr, Ni, Cu, As, Cd and Sn, elements of importance from the point of view of their impact on the environment, in electric arc furnace flue dust (EAFD). A simple method of sample preparation as pressed pellets using a mixture of cellulose and paraffin as binder material was applied. Calibration standards were prepared spiking multielement solution standards to a 1:1 ZnO+Fe(2)O(3) synthetic matrix. The wet powder was dried and mechanically homogenised. Quantitative analysis were based on external calibration using a set of matrix matched calibration standards with Rh as a internal standard. Results obtained using only one-point for calibration without matrix matched, needing less time for standardization and data processing, are also presented. Data are calculated for flue dust reference materials: CRM 876-1 (EAFD), AG-6203 (EAFD), AG-6201 (cupola dust) and AG-SX3705 (coke ashes), and for two representative electrical arc furnace flue dusts samples from Spanish steelmaking companies: MS-1 and MS-2. For the reference materials, an acceptable agreement with certificate values was achieved, and the results for the MS samples matched with those obtained from conventional nebulization solutions (CN). The analytical precision was found to be better than 7% R.S.D. both within a single pellet and between several pellets of the same sample for all the elements. PMID:18970147

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

    USGS Publications Warehouse

    Long, James M.; Schaffler, James J.

    2013-01-01

    RATIONALE The otoliths of the inner ear of fishes record the environment of their surrounding water throughout their life. For paddlefish (Polyodon spathula), otoliths have not been routinely used by scientists since their detriments were outlined in the early 1940s. We sought to determine if paddlefish otoliths were useful for resolving elemental information contained within. METHODS Adult paddlefish were collected from two wild, self-sustaining populations in Oklahoma reservoirs in the Arkansas River basin. Juveniles were obtained from a hatchery in the Red River basin of Oklahoma. Otoliths were removed and laser ablation, inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify eight elements (Li, Mg, Mn, Rb, Sr, Y, Ba, and Pb) along the core and edge portions, which were analyzed for differences between otolith regions and among paddlefish sources. RESULTS Differences were found among samples for six of the eight elements examined. Otoliths from Red River basin paddlefish born in a hatchery had significantly lower amounts of Mg and Mn, but higher levels of Rb than otoliths from wild paddlefish in the Arkansas River basin. Concentrations of Y, Sr, and Ba were reduced on the edges of adult paddlefish from both reservoirs compared with the cores. CONCLUSIONS This research shows the utility of using an ICP-MS analysis of paddlefish otoliths. Future research that seeks to determine sources of paddlefish production, such as which reservoir tributaries are most important for reproduction or what proportion of the population is composed of wild versus hatchery-produced individuals, appears promising. Published in 2013. This article is a U.S. Government work and is in the public domain in the USA.

  1. Slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry for steelmaking flue dust analysis

    NASA Astrophysics Data System (ADS)

    Coedo, A. G.; Dorado, T.; Padilla, I.; Maibusch, R.; Kuss, H.-M.

    2000-02-01

    A commercial atomic absorption graphite furnace (AAGF), with a self-made adapter and valve system, was used as a slurry sampling cell for electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS). The system was applied to the determination of As, Sn, Sb, Se, Te, Bi, Cd, V, Ti and Mo in steelmaking flue dusts. Experimental conditions with respect to ETV and ICP-MS operating parameters were optimized. Compared to aqueous solutions, slurry samples were found to present better analyte transport. Microgram amounts of Rh were used to reduce the difference in analyte response in sensitivity for aqueous solutions of the tested analytes. No such increasing effect was observed for slurry samples and aqueous standards. An added quantity of Rh acting as modifier/carrier resulted in an increase for the same analytes in matrix-slurry solutions, even the addition of an extra Rh quantity has resulted in a decrease in the signals. The effect of Triton X-100 (used as a dispersant agent) on analyte intensity and precision was also studied. External calibration from aqueous standards spiked with 100 μg ml -1 Rh was performed to quantified 0.010 g/100 ml slurry samples. Results are presented for a certified reference electrical arc furnace flue dust (EAF): CRM-876-1 (Bureau of Analysis Samples Ltd., Cleveland, UK), a reference sample of coke ashes X-3705 (from AG der Dillinger Hüttenwerke, Germany), and a representative sample of EAF flue dust from a Spanish steelmaking company (CENIM-1). For the two reference materials an acceptable agreement with certificate values was achieved, and the results for the CENIM sample matched with those obtained from conventional nebulization solution.

  2. Calibration of laser ablation inductively coupled plasma mass spectrometry for quantitative measurements of lead in bone

    PubMed Central

    Bellis, David J.; Hetter, Katherine M.; Jones, Joseph; Amarasiriwardena, Dula

    2012-01-01

    Summary Lead accumulates in bone over many years or decades. Accordingly, the study of lead in bone is important in determining the fate of ingested lead, the potential for remobilization, and for the application of bone lead measurements as a biomarker of lead exposure. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure the spatial distribution of lead in bone on the micrometer scale. In general, LA-ICP-MS studies are somewhat limited by the lack of matrix-matched standards and/or reference materials for calibration and validation purposes. Here we describe the application of pressed pellets prepared from New York State Department of Health candidate Reference Materials for Lead in Bone (levels 1 through 4), to provide a linear calibration for 208Pb/43Ca in the concentration range <1 to 30 μg g−1. The limit of detection was estimated as 0.2 μg g−1. The measured lead values for pelletized NIST SRM 1486 Bone Meal and SRM 1400 Bone Ash were in good agreement with certified reference values. Using this approach, we quantitatively measured the spatial distribution of lead in a cross-section of goat metacarpal from a lead-dosed animal. The lead content was spatially variable in the range of 2 to 30 μg g−1 with a complex distribution. In some sections, lead appeared to be enriched in the center of the bone relative to peripheral areas, indicating preferential accumulation in trabecular (spongy) rather than cortical bone. In addition, there were discrete areas of lead enrichment, or hot spots, of 100 to 200 μm in width. PMID:22833692

  3. Calibration of laser ablation inductively coupled plasma mass spectrometry for quantitative measurements of lead in bone.

    PubMed

    Bellis, David J; Hetter, Katherine M; Jones, Joseph; Amarasiriwardena, Dula; Parsons, Patrick J

    2006-01-01

    Lead accumulates in bone over many years or decades. Accordingly, the study of lead in bone is important in determining the fate of ingested lead, the potential for remobilization, and for the application of bone lead measurements as a biomarker of lead exposure. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to measure the spatial distribution of lead in bone on the micrometer scale. In general, LA-ICP-MS studies are somewhat limited by the lack of matrix-matched standards and/or reference materials for calibration and validation purposes. Here we describe the application of pressed pellets prepared from New York State Department of Health candidate Reference Materials for Lead in Bone (levels 1 through 4), to provide a linear calibration for (208)Pb/(43)Ca in the concentration range <1 to 30 μg g(-1). The limit of detection was estimated as 0.2 μg g(-1). The measured lead values for pelletized NIST SRM 1486 Bone Meal and SRM 1400 Bone Ash were in good agreement with certified reference values. Using this approach, we quantitatively measured the spatial distribution of lead in a cross-section of goat metacarpal from a lead-dosed animal. The lead content was spatially variable in the range of 2 to 30 μg g(-1) with a complex distribution. In some sections, lead appeared to be enriched in the center of the bone relative to peripheral areas, indicating preferential accumulation in trabecular (spongy) rather than cortical bone. In addition, there were discrete areas of lead enrichment, or hot spots, of 100 to 200 μm in width. PMID:22833692

  4. Multi-element analysis of manganese nodules by atomic absorption spectrometry without chemical separation

    USGS Publications Warehouse

    Kane, J.S.; Harnly, J.M.

    1982-01-01

    Five manganese nodules, including the USGS reference nodules A-1 and P-1, were analyzed for Co, Cu, Fe, K, Mg, Mn, Na, Ni and Zn without prior chemical separation by using a simultaneous multi-element atomic absorption spectrometer with an air-cetylene flame. The nodules were prepared in three digestion matrices. One of these solutions was measured using sixteen different combinations of burner height and air/acetylene ratios. Results for A-1 and P-1 are compared to recommended values and results for all nodules are compared to those obtained with an inductively coupled plasma. The elements Co, Cu, Fe, K, Mg, Mn, Na, Ni, and Zn are simultaneously determined with a composite recovery for all elements of 100 ?? 7%, independent of the digestion matrices, heights in the flame, or flame stoichiometries examined. Individual recoveries for Co, K, and Ni are considerably poorer in two digests than this composite figure, however. The optimum individual recoveries of 100 ?? 5% and imprecisions of 1-4%, except for zinc, are obtained when Co, K, Mn, Na and Ni are determined simultaneously in a concentrated digest, and in another analytical sequence, when Cu, Fe, Mg, Mn and Zn are measured simultaneously after dilution. Determination of manganese is equally accurate in the two sequences; its measurement in both assures internal consistency between the two measurement sequences. This approach improves analytical efficiency over that for conventional atomic absorption methods, while minimizing loss of accuracy or precision for individual elements. ?? 1982.

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

    SciTech Connect

    Maxwell, S.; Jones, V.

    2009-05-27

    A new rapid separation method that allows separation and preconcentration of actinides in urine samples was developed for the measurement of longer lived actinides by inductively coupled plasma mass spectrometry (ICP-MS) and short-lived actinides by alpha spectrometry; a hybrid approach. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration, if required, is performed using a streamlined calcium phosphate precipitation. Similar technology has been applied to separate actinides prior to measurement by alpha spectrometry, but this new method has been developed with elution reagents now compatible with ICP-MS as well. Purified solutions are split between ICP-MS and alpha spectrometry so that long- and short-lived actinide isotopes can be measured successfully. The method allows for simultaneous extraction of 24 samples (including QC samples) in less than 3 h. Simultaneous sample preparation can offer significant time savings over sequential sample preparation. For example, sequential sample preparation of 24 samples taking just 15 min each requires 6 h to complete. The simplicity and speed of this new method makes it attractive for radiological emergency response. If preconcentration is applied, the method is applicable to larger sample aliquots for occupational exposures as well. The chemical recoveries are typically greater than 90%, in contrast to other reported methods using flow injection separation techniques for urine samples where plutonium yields were 70-80%. This method allows measurement of both long-lived and short-lived actinide isotopes. 239Pu, 242Pu, 237Np, 243Am, 234U, 235U and 238U were measured by ICP-MS, while 236Pu, 238Pu, 239Pu, 241Am, 243Am and 244Cm were measured by alpha spectrometry. The method can also be adapted so that the separation of uranium isotopes for assay is not required, if uranium assay by direct dilution of the urine sample is preferred instead

  6. Lead geochronology of zircon by LaserProbe-inductively coupled plasma mass spectrometry (LP-ICPMS)

    NASA Astrophysics Data System (ADS)

    Feng, Rui; Machado, Nuno; Ludden, John

    1993-07-01

    LaserProbe-inductively coupled plasma mass spectrometry (LP-ICPMS) provides a sensitive, fast, and simple means to determine 207Pb /206Pb ages in single zircon grains. A Nd:YAG laser is used to irradiate the zircon surface and leaves a cylindrical pit of 30-60 μm, from which the vaporised materials are transported by argon gas to a Fisons-VG PQII+ ICPMS for analysis. No zircon abrasion, cleaning nor chemical separation procedures are required. The accuracy and the limitation of the method were evaluated by analyzing twenty-one zircon samples ranging in age from 2.7 Ga to 1.0 Ga, which have also been dated by the conventional U-Pb thermal ionization mass spectrometry technique (TIMS). The LP-ICPMS 207Pb /206Pb ages for zircons with grain size > 60 μm and 207Pb concentration > 3 ppm are within 1% of the TIMS ages. Smaller zircons (≤60 μm) and those with 207Pb concentration < 2 ppm yield inaccurate ages. Operating the LP-ICPMS at conditions that give a compromise between the ideal spatial resolution and instrument sensitivity, the limits of detection were found to be 0.2 ppm for 206Pb, 207Pb, and 208Pb. The precision of the 207Pb /206Pb ratio is generally 0.5-6% (1σ) from each sampling pit and is strongly dependent on the lead concentration. However, the precision for the average of the mean ratios from different pits in one grain or several grains of the same population are generally <1.5% (1σ). The results presented here demonstrate that the LP-ICPMS can be used to determine 207Pb /206Pb ages of zircons and that reliable ages can be obtained from high quality, limpid zircons with a simple Pb-loss history. Uses of the technique include screening of zircon populations from different rocks in areas of poorly known age relationships and provenance studies of detrital zircons from ancient and modern sedimentary sequences. Other applications include the study of growth zones and of inherited components in complex zircon populations. In comparison with the SHRIMP

  7. MICROSCALE FLOW INJECTION AND MICROBORE HIGH-PERFORMANCE LIQUID CHROMATORGRAPHY COUPLED WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY VIA A HIGH-EFFICIENCY NEBULIZER

    EPA Science Inventory

    A high-effeciency nebulizer has been used for coupling microscale flow injection and microbore high-performance liquid chromatography with inductively coupled plasma mass spectrometry (ICPMS). The microscale flow injection system was configured to minimize band broadening between...

  8. Comparison of thermal ionization mass spectrometry and Multiple Collector Inductively Coupled Plasma Mass Spectrometry for cesium isotope ratio measurements

    NASA Astrophysics Data System (ADS)

    Isnard, H.; Granet, M.; Caussignac, C.; Ducarme, E.; Nonell, A.; Tran, B.; Chartier, F.

    2009-11-01

    In the nuclear domain, precise and accurate isotopic composition determination of elements in spent nuclear fuels is mandatory to validate neutron calculation codes and for nuclear waste disposal. The present study presents the results obtained on Cs isotope ratio by mass spectrometric measurements. Natural cesium is monoisotopic ( 133Cs) whereas cesium in spent fuels has 4 isotopes ( 133Cs, 134Cs, 135Cs, and 137Cs). As no standard reference material is available to evaluate the accuracy of Cs isotopic measurements, a comparison of cesium isotopic composition in spent nuclear fuels has been performed between Thermal Ionization Mass Spectrometry (TIMS) and a new method involving Multiple Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) measurements. For TIMS measurements, isotopic fractionation has been evaluated by studying the behavior of cesium isotope ratios ( 133Cs/ 137Cs and 135Cs/ 137Cs) during the analyses. For MC-ICPMS measurements, the mass bias effects have been corrected with an external mass bias correction using elements (Eu and Sb) close to cesium masses. The results obtained by the two techniques show good agreement: relative difference on 133Cs/ 137Cs and 135Cs/ 137Cs ratios for two nuclear samples, analyzed after chemical separation, ranges from 0.2% to 0.5% depending on the choice of reference value for mass bias correction by MC-ICPMS. Finally the quantification of the 135Cs/ 238U ratio by the isotope dilution technique is presented in the case of a MOx (mixed oxide) spent fuel sample. Evaluation of the global uncertainties shows that this ratio could be defined at an uncertainty of 0.5% ( k = 2). The intercomparison between two independent mass spectrometric techniques is fundamental for the evaluation of uncertainty when no isotopic standard is available.

  9. Direct analysis of samples by mass spectrometry: From elements to bio-molecules using laser ablation inductively couple plasma mass spectrometry and laser desorption/ionization mass spectrometry

    SciTech Connect

    Perdian, David C.

    2009-01-01

    Mass spectrometric methods that are able to analyze solid samples or biological materials with little or no sample preparation are invaluable to science as well as society. Fundamental research that has discovered experimental and instrumental parameters that inhibit fractionation effects that occur during the quantification of elemental species in solid samples by laser ablation inductively coupled plasma mass spectrometry is described. Research that determines the effectiveness of novel laser desorption/ionization mass spectrometric methods for the molecular analysis of biological tissues at atmospheric pressure and at high spatial resolution is also described. A spatial resolution is achieved that is able to analyze samples at the single cell level.

  10. Physicochemical characterization of titanium dioxide pigments using various techniques for size determination and asymmetric flow field flow fractionation hyphenated with inductively coupled plasma mass spectrometry.

    PubMed

    Helsper, Johannes P F G; Peters, Ruud J B; van Bemmel, Margaretha E M; Rivera, Zahira E Herrera; Wagner, Stephan; von der Kammer, Frank; Tromp, Peter C; Hofmann, Thilo; Weigel, Stefan

    2016-09-01

    Seven commercial titanium dioxide pigments and two other well-defined TiO2 materials (TiMs) were physicochemically characterised using asymmetric flow field flow fractionation (aF4) for separation, various techniques to determine size distribution and inductively coupled plasma mass spectrometry (ICPMS) for chemical characterization. The aF4-ICPMS conditions were optimised and validated for linearity, limit of detection, recovery, repeatability and reproducibility, all indicating good performance. Multi-element detection with aF4-ICPMS showed that some commercial pigments contained zirconium co-eluting with titanium in aF4. The other two TiMs, NM103 and NM104, contained aluminium as integral part of the titanium peak eluting in aF4. The materials were characterised using various size determination techniques: retention time in aF4, aF4 hyphenated with multi-angle laser light spectrometry (MALS), single particle ICPMS (spICPMS), scanning electron microscopy (SEM) and particle tracking analysis (PTA). PTA appeared inappropriate. For the other techniques, size distribution patterns were quite similar, i.e. high polydispersity with diameters from 20 to >700 nm, a modal peak between 200 and 500 nm and a shoulder at 600 nm. Number-based size distribution techniques as spICPMS and SEM showed smaller modal diameters than aF4-UV, from which mass-based diameters are calculated. With aF4-MALS calculated, light-scattering-based "diameters of gyration" (Øg) are similar to hydrodynamic diameters (Øh) from aF4-UV analyses and diameters observed with SEM, but much larger than with spICPMS. A Øg/Øh ratio of about 1 indicates that the TiMs are oblate spheres or fractal aggregates. SEM observations confirm the latter structure. The rationale for differences in modal peak diameter is discussed. PMID:27469116

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

    NASA Astrophysics Data System (ADS)

    Arnquist, Isaac J.; Holcombe, James A.

    2012-10-01

    The coupling of separation by preparative ultracentrifugation and metal detection by inductively coupled plasma mass spectrometry (ICP-MS) has been explored for metal-protein equilibrium determinations. This study characterizes the stoichiometry as well as apparent (Kapp) and intrinsic (Kint) binding affinities of the metal-protein association for a model protein. In particular, the affinity of Cu2 + for the high affinity binding site in bovine serum albumin (BSA) is determined. Once equilibrium is established between Cu2 + and BSA, preparative ultracentrifugation moves the metalloprotein away from the meniscus, leaving unbound equilibrium copper in the protein free solution. Since the initial (total) concentrations of purified BSA and Cu2 + can be determined, the free copper concentration at equilibrium can also be determined by taking a small aliquot above the sedimenting boundary for analysis using ICP-MS. This analysis allows for the determination of free Cu2 + ion, which is identical to the equilibrium concentration prior to ultracentrifugation. From these data Kapp and Kint were determined at two different conditions, 100 mM Tris(hydroxymethyl)aminomethane (Tris) at pH 9.53 and pH 7.93. log Kapp values of 17.6 and 14.6 were determined at pH 9.53 and pH 7.93, respectively. Furthermore, pH-independent log Kint values of - 1.43 and - 1.04 were determined at pH 9.53 and 7.93, respectively. While the log Kint at pH 9.53 was in good agreement with literature values obtained from alternative methods, Kint at pH 7.93 was about 2.5 × larger than previously reported. BSA undergoes a structural rearrangement between pH 7-9, and the generally accepted pH-dependency of protein tertiary structure may be responsible for the variations in the "intrinsic" binding constant. The Cu-BSA binding affinity was also monitored in 100 mM Tris 0.1% sodium dodecyl sulfate (SDS) solution at pH 7.93 in order to determine the effect of a denaturant on metal binding. Results for both log

  12. {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.

  13. ULTRASONIC NEBULIZATION AND ARSENIC VALENCE STATE CONSIDERATIONS PRIOR TO DETERMINATION VIA INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

    EPA Science Inventory

    An ultrasonic nebulizer (USN) was utilized as a sample introduction device for an inductively coupled plasma mass spectrometer in an attempt to increase the sensitivity for As. The USN produced a valence state response difference for As. The As response was suppressed approximate...

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

    ERIC Educational Resources Information Center

    Donnell, Anna M.; Nahan, Keaton; Holloway, Dawone; Vonderheide, Anne P.

    2016-01-01

    Arsenic is a toxic element to which humans are primarily exposed through food and water; it occurs as a result of human activities and naturally from the earth's crust. An experiment was developed for a senior level analytical laboratory utilizing an Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) for the analysis of arsenic in household…

  15. CAPILLARY ELECTROPHORESIS COUPLED ON-LINE WITH INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY FOR ELEMENTAL SPECIATION

    EPA Science Inventory

    A novel interface to connect a capillary electrophoresis (CE) system with an inductively coupled plasma mass spectrometric (ICPMS) detector is reported here. The interface was built using a direct injection nebulizer (DIN) system. In this interface, the CE capillary was placed co...

  16. Measurement of low radioactivity background in a high voltage cable by high resolution inductively coupled plasma mass spectrometry

    SciTech Connect

    Vacri, M. L. di; Nisi, S.; Balata, M.

    2013-08-08

    The measurement of naturally occurring low level radioactivity background in a high voltage (HV) cable by high resolution inductively coupled plasma mass spectrometry (HR ICP MS) is presented in this work. The measurements were performed at the Chemistry Service of the Gran Sasso National Laboratory. The contributions to the radioactive background coming from the different components of the heterogeneous material were separated. Based on the mass fraction of the cable, the whole contamination was calculated. The HR ICP MS results were cross-checked by gamma ray spectroscopy analysis that was performed at the low background facility STELLA (Sub Terranean Low Level Assay) of the LNGS underground lab using HPGe detectors.

  17. Determination of hexavalent chromium in traditional Chinese medicines by high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

    PubMed

    Li, Peng; Li, Li-Min; Xia, Jing; Cao, Shuai; Hu, Xin; Lian, Hong-Zhen; Ji, Shen

    2015-12-01

    An analytical method that combined high-performance liquid chromatography with inductively coupled plasma mass spectrometry has been developed for the determination of hexavalent chromium in traditional Chinese medicines. Hexavalent chromium was extracted using the alkaline solution. The parameters such as the concentration of alkaline and the extraction temperature have been optimized to minimize the interconversion between trivalent chromium and hexavalent chromium. The extracted hexavalent chromium was separated on a weak anion exchange column in isocratic mode, followed by inductively coupled plasma mass spectrometry determination. To obtain a better chromatographic resolution and sensitivity, 75 mM NH4 NO3 at pH 7 was selected as the mobile phase. The linearity of the proposed method was investigated in the range of 0.2-5.0 μg L(-1) (r(2) = 0.9999) for hexavalent chromium. The limits of detection and quantitation are 0.1 and 0.3 μg L(-1) , respectively. The developed method was successfully applied to the determination of hexavalent chromium in Chloriti lapis and Lumbricus with satisfactory recoveries of 95.8-112.8%. PMID:26541101

  18. Calibration of laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for the quantitative analysis of solid samples

    SciTech Connect

    Leach, J.

    1999-02-12

    Inductively coupled plasma mass spectrometry (ICP-MS) has become the method of choice for elemental and isotopic analysis. Several factors contribute to its success. Modern instruments are capable of routine analysis at part per trillion levels with relative detection limits in part per quadrillion levels. Sensitivities in these instruments can be as high as 200 million counts per second per part per million with linear dynamic ranges up to eight orders of magnitude. With standards for only a few elements, rapid semiquantitative analysis of over 70 elements in an individual sample can be performed. Less than 20 years after its inception ICP-MS has shown to be applicable to several areas of science. These include geochemistry, the nuclear industry, environmental chemistry, clinical chemistry, the semiconductor industry, and forensic chemistry. In this introduction, the general attributes of ICP-MS will be discussed in terms of instrumentation and sample introduction. The advantages and disadvantages of current systems are presented. A detailed description of one method of sample introduction, laser ablation, is given. The paper also gives conclusions and suggestions for future work. Chapter 2, Quantitative analysis of solids by laser ablation inductively coupled plasma mass spectrometry using dried solution aerosols for calibration, has been removed for separate processing.

  19. Controlled dissolution of silicon dioxide layers for depth resolved multielement analysis by inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lorge, Susan E.; Houk, R. S.

    2009-11-01

    Dissolution procedures were developed to control the number of surface layers removed, in an attempt to achieve depth resolved analysis by inductively coupled plasma-mass spectrometry (ICP-MS). NIST 612 glass was chosen because it is a homogeneous material with many elements at interesting concentrations, ~ 50 ppm. Varying dissolution time and HF concentration resulted in the reproducible removal of SiO 2 layers as thin as 70 Å deep. Dissolved trace metals were determined after dilution by inductively coupled plasma-mass spectrometry (ICP-MS) with a magnetic sector instrument. The amount removed was determined from the concentration of a major element, Ca. With the exception of Zn, trace metal concentrations agreed reasonably well with their certified values for removal depths of 500, 300 and 150 Å. Zinc concentration was significantly high in all dissolutions indicating either a contamination problem or that Zn is removed at a faster rate than Ca. For the dissolutions that removed 70 Å of SiO 2, Cr, Mn, Co, Sr, Cd, Ce, Dy, Er, Yb and U recovery results agreed with their certified values (~ 50 ppm); Ti, As, Mo, Ba, and Th could not be determined because net intensities were below 3 σ of the blank; and measured concentrations for Cu, Pb and Zn were well above the certified values.

  20. Rapid identification and analysis of airborne plutonium using a combination of alpha spectroscopy and inductively coupled plasma mass spectrometry.

    PubMed

    Farmer, Dennis E; Steed, Amber C; Sobus, Jon; Stetzenbach, Klaus; Lindley, Kaz; Hodge, Vernon F

    2003-10-01

    Recent wildland fires near two U.S. nuclear facilities point to a need to rapidly identify the presence of airborne plutonium during incidents involving the potential release of radioactive materials. Laboratory turn-around times also need to be shortened for critical samples collected in the earliest stages of radiological emergencies. This note discusses preliminary investigations designed to address both these problems. The methods under review are same day high-resolution alpha spectroscopy to screen air filter samples for the presence of plutonium and inductively coupled plasma mass spectrometry to perform sensitive plutonium analyses. Thus far, using modified alpha spectroscopy techniques, it has been possible to reliably identify the approximately 5.2 MeV emission of 239Pu on surrogate samples (air filters artificially spiked with plutonium after collection) even though the primary alpha-particle emissions of plutonium are, as expected, superimposed against a natural alpha radiation background dominated by short-lived radon and thoron progeny (approximately 6-9 MeV). Several processing methods were tested to prepare samples for analysis and shorten laboratory turn-around time. The most promising technique was acid-leaching of air filter samples using a commercial open-vessel microwave digestion system. Samples prepared in this way were analyzed by both alpha spectroscopy (as a thin-layer iron hydroxide co-precipitate) and inductively coupled plasma mass spectrometry. The detection levels achieved for 239Pu--approximately 1 mBq m(-3) for alpha spectroscopy screening, and, < 0.1 mBq m(-3) for inductively coupled plasma mass spectrometry analysis--are consistent with derived emergency response levels based on EPA's Protective Action Guides, and samples can be evaluated in 36 to 72 h. Further, if samples can be returned to a fixed-laboratory and processed immediately, results from mass spectrometry could be available in as little as 24 h. When fully implemented

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

    NASA Astrophysics Data System (ADS)

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

    2004-06-01

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

  2. Separation of actinides using capillary extraction chromatography-inductively coupled plasma mass spectrometry

    SciTech Connect

    Peterson, Dominic S

    2008-01-01

    Trace levels of actinides have been separated on extraction chromatography columns. Detection of the actinides was achieved using an inductively coupled plasma mass spectrometer (ICP-MS), which was coupled with the extraction chromatography system. In this study we compare 30 cm long, 4.6 mm ID columns to capillary columns (750 {micro}m ID) with lengths from 30 cm up to 150 cm. The columns that were tested were packed with TRU resin. We were able to separate a mixture of five actinides ({sup 232}Th, {sup 238}U, {sup 237}Np, {sup 239}pU, {sup 241}Am). This work has application to rapid bioassay as well as for automated separations of actinide materials.

  3. 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

  4. Determination of organomercury in biological reference materials by inductively coupled plasma mass spectrometry using flow injection analysis

    SciTech Connect

    Beauchemin, D.; Siu, K.W.; Berman, S.S.

    1988-12-01

    Inductively coupled plasma mass spectrometry was used for the determination of organomercury in two marine biological standard reference materials for trace metals (dogfish muscle tissue DORM-1 and lobster hepatopancreas TORT-1). In most parts of this study, the organomercury was extracted as the chloride from the material with toluene and back extracted into an aqueous medium of cysteine acetate. Since the final extracts contained more than 4% sodium, isotope dilution and flow injection analysis were used to respectively counter the effect of concomitant elements and avoid clogging the interface. Comparison of results with gas chromatography shows that the only significant organomercury is methyl-mercury. At least 93% of mercury in DORM-1 and 39% of mercury in TORT-1 exist as methylmercury.

  5. Time-resolved measurements of individual ion cloud signals to investigate space-charge effects in plasma mass spectrometry.

    PubMed

    Olesik, J W; Dziewatkoski, M P

    1996-04-01

    A new approach to directly monitor space charge induced effects due to high concentrations of efficiently ionized elements in inductively coupled plasma mass spectrometry (ICP-MS) is described. The broadening of ion clouds produced from individual, monodisperse drops of sample is measured by using time-resolved ICP-MS. The extent of broadening due to high concentrations of Pb in the sample is related inversely to the analyte mass. For the lightest analyte investigated, Li(+), the relative width of the time-resolved analyte peak increases and then shows a dip in the center as the Pb concentration is increased to 500 and then 1500 µg/mL. The initial results of experiments that investigated chemical matrix effects as a function of concomitant species concentration, analyte mass, and sampling location in ICP-MS are consistent with space-charge effects. PMID:24203362

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

    PubMed

    İzgi, Belgin; Kayar, Murat

    2015-07-01

    The polybrominated flame retardants and organotin compounds were screened in terms of bromine and tin content using laser ablation inductively coupled plasma mass spectrometry in plastics. The calibration standards were prepared using the fused-disk technique, and all samples were investigated under optimal conditions. Using a central composite experimental design, laser parameters, laser energy, pulse rate, scan rate and spot size were identified. The detection limits of the method were 1000 mgkg(-1) and 1600 mgkg(-1) for bromide and tin, whereas the relative standard deviation (%) values of the analysis were 9% and 6% (n=3) for ERM EC681k with 770 ± 70 mgkg(-1) Br and 86 ± 6 mgkg(-1) Sn respectively, and 106-115% of Br and 102-104% of Sn were observed for the tetrabromobisphenol A and butyltin trichloride spike plastics, respectively. PMID:25882416

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

    NASA Astrophysics Data System (ADS)

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

    2000-07-01

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

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

    NASA Astrophysics Data System (ADS)

    Smith, F.; Clarke, D.; Moody, S.

    2014-12-01

    In this work, inductively coupled plasma mass spectrometry (ICP-MS) is applied to a geological sample for the determination of rare earth elements (REEs) using a specialized nebulizer system. The low flow desolvating nebulizer has been shown to decrease metal oxide formation which leads to a reduction in mass spectral interferences. Traditional nebulizers and spray chambers may be suitable for similar sample types, but reduction of water vapor loading to the plasma can improve REE detection limits for quadrupole-based ICP-MS. The Green River formation holds the largest oil shale deposits in the world and understanding the elemental composition of these samples is important in its study. A certified reference material, USGS Green River Shale (SGR-1), was microwave digested prior to analysis, and recoveries of REEs compared to historical values are discussed.

  9. Simplified sample preparation procedure for measuring isotope-enriched methylmercury by gas chromatography and inductively coupled plasma mass spectrometry.

    PubMed

    Avramescu, Mary-Luyza; Zhu, Joy; Yumvihoze, Emmanuel; Hintelmann, Holger; Fortin, Danielle; Lean, David R S

    2010-06-01

    Many procedures have been developed to measure the concentration of monomethylmercury (MeHg) from different sample matrices, and the use of stable isotopes of mercury now provides opportunities to determine its formation and degradation rates. Here, a modified procedure for measuring mercury isotopes in sediment samples that uses acid leaching-ion exchange-thiosulfate extraction (TSE) to isolate and purify the methylated mercury from the matrix is proposed. The latter is followed by aqueous-phase ethylation, purge and trap on Tenax, gas chromatography separation of ethylated mercury compounds, and inductively coupled plasma mass spectrometry detection. The new TSE procedure bridges together two well-known methods, the acid-leaching and distillation-derivatization procedures, offering the advantages of artifact-free formation of the first, and low detection limits and the possibility of quantification of individual isotopes of mercury of the second. The modified procedure retains the derivatization, purge and trap, and gas chromatography and inductively coupled plasma mass spectrometry (GC-ICP-MS) detection steps from the distillation-derivatization procedure, and eliminates the distillation step, which is not only laborious but also expensive, due to the high cost of installation and time-consuming cleaning process. Major advantages of the TSE procedure proposed include the extraction and analysis of a large number of samples in a short time, excellent analyte recoveries, and the lack of artifact formation. Sediment certified reference materials (CRMs), BCR 580 and IAEA 405, were used to test the TSE procedure accuracy. Recoveries between 94 to 106% and 95 to 96% were obtained for CRMs and spiked samples (Milli-Q(R) water), respectively. Comparisons among thiosulfate extraction, distillation, and acid-leaching procedures have shown good agreement of methylmercury values. PMID:20821567

  10. Determination of 237Np and Pu isotopes in large soil samples by inductively coupled plasma mass spectrometry.

    PubMed

    Maxwell, Sherrod L; Culligan, Brian K; Jones, Vernon D; Nichols, Sheldon T; Bernard, Maureen A; Noyes, Gary W

    2010-12-01

    A new method for the determination of (237)Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of (237)Np and Pu isotopes by ICP-MS. (238)U can interfere with (239)Pu measurement by ICP-MS as (238)UH(+) mass overlap and (237)Np via (238)U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1×10(6). Alpha spectrometry can also be applied so that the shorter-lived (238)Pu isotope can be measured successfully. (239) Pu, (242)Pu and (237)Np were measured by ICP-MS, while (236)Pu and (238)Pu were measured by alpha spectrometry. PMID:21056724

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

    SciTech Connect

    Maxwell, S.

    2010-07-26

    A new method for the determination of {sup 237}Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of {sup 237}Np and Pu isotopes by ICP-MS. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via {sup 238}U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1 x 10{sup 6}. Alpha spectrometry can also be applied so that the shorter-lived {sup 238}Pu isotope can be measured successfully. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu and {sup 238}Pu were measured by alpha spectrometry.

  12. Elemental Bioimaging by Means of Fast Scanning Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Wehe, Christoph A.; Thyssen, Georgina M.; Herdering, Christina; Raj, Indra; Ciarimboli, Giuliano; Sperling, Michael; Karst, Uwe

    2015-08-01

    One of the most common setups for elemental bioimaging, the hyphenation of a laser ablation (LA) system and an inductively coupled plasma mass spectrometer (ICP-MS), was expanded by adding full scan mass spectrometric information as another dimension of information. While most studies deal with the analysis of typically not more than up to 10 isotopes per scan cycle, a fast scanning quadrupole mass analyzer was utilized to record the full mass spectrum of interest in this work. Mass-to-charge ratios from 6 to 250 were observed within one cycle. Besides the x- and y-position on the ablated sample and the intensity, the m/z-ratio served as fourth variable for each pixel of the obtained data, closing thereby the gap between "inorganic" and "organic" mass spectrometric imaging techniques. The benefits of this approach include an improved control of interferences, the discovery of unexpected elemental distributions, the possibility to plot isotopic ratios, and to integrate the intensities of a certain number of mass channels recorded for each isotope, thus virtually increasing sensitivity. The respective data are presented for dried droplets as well as embedded animal and human tissue slices. Limits of detection were calculated and found to be in accordance with counting statistics. A dedicated software macro was developed for data manipulation prior to common evaluation and image creation.

  13. Elemental Bioimaging by Means of Fast Scanning Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry.

    PubMed

    Wehe, Christoph A; Thyssen, Georgina M; Herdering, Christina; Raj, Indra; Ciarimboli, Giuliano; Sperling, Michael; Karst, Uwe

    2015-08-01

    One of the most common setups for elemental bioimaging, the hyphenation of a laser ablation (LA) system and an inductively coupled plasma mass spectrometer (ICP-MS), was expanded by adding full scan mass spectrometric information as another dimension of information. While most studies deal with the analysis of typically not more than up to 10 isotopes per scan cycle, a fast scanning quadrupole mass analyzer was utilized to record the full mass spectrum of interest in this work. Mass-to-charge ratios from 6 to 250 were observed within one cycle. Besides the x- and y-position on the ablated sample and the intensity, the m/z-ratio served as fourth variable for each pixel of the obtained data, closing thereby the gap between "inorganic" and "organic" mass spectrometric imaging techniques. The benefits of this approach include an improved control of interferences, the discovery of unexpected elemental distributions, the possibility to plot isotopic ratios, and to integrate the intensities of a certain number of mass channels recorded for each isotope, thus virtually increasing sensitivity. The respective data are presented for dried droplets as well as embedded animal and human tissue slices. Limits of detection were calculated and found to be in accordance with counting statistics. A dedicated software macro was developed for data manipulation prior to common evaluation and image creation. PMID:25947196

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

    EPA Science Inventory

    Surface coating thickness and aggregation state have strong influence on the environmental fate, transport, and toxicity of engineered nanomaterials. In this study, flow-field flow fractionation coupled on-line with single particle inductively coupled plasma-mass spectrometry i...

  15. THE DEVELOPMENT OF IODINE BASED IMPINGER SOLUTIONS FOR THE EFFICIENT CAPTURE OF HG USING DIRECT INJECTION NEBULIZATION - INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY ANALYSIS

    EPA Science Inventory

    Inductively coupled plasma mass spectrometry (ICP/MS) with direct injection nebulization (DIN) was used to evaluate novel impinger solution compositions capable of capturing elemental mercury (Hgo) in EPA Method 5 type sampling. An iodine based impinger solutoin proved to be ver...

  16. Determination of lead, cadmium and mercury in blood for assessment of environmental exposure: A comparison between inductively coupled plasma mass spectrometry and atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Palmer, Christopher D.; Lewis, Miles E.; Geraghty, Ciaran M.; Barbosa, Fernando; Parsons, Patrick J.

    2006-08-01

    A biomonitoring method for the determination of Pb, Cd, and Hg at background levels in whole blood by inductively coupled plasma-mass spectrometry is described. While this method was optimized for assessing Pb, Cd and Hg at environmental levels, it also proved suitable for assessing concentrations associated with occupational exposure. The method requires as little as 200 μl of blood that is diluted 1 + 49 for direct analysis in the inductively coupled plasma-mass spectrometer. Method performance is compared to well-established AAS methods. Initial method validation was accomplished using National Institute of Standards and Technology (NIST) Standard Reference Material 966, Toxic Metals in Bovine Blood. Method detection limits (3s) are 0.05 μg dl - 1 for Pb, 0.09 μg l - 1 for Cd; and 0.17 μg l - 1 for Hg. Repeatability ranged from 1.4% to 2.8% for Pb; 3% to 10% for Cd; and 2.6% to 8.8% for Hg. In contrast, AAS method detection limits were 1 μg dl - 1 , 0.54 μg l - 1 , and 0.6 μg l - 1 , for Pb, Cd, and Hg, respectively. Further performance assessments were conducted over a 2-year period via participation in four international External Quality Assessment Schemes (EQAS) operated specifically for toxic metals in blood. This includes schemes operated by (a) the New York State Department of Health's Wadsworth Center, Albany, NY, USA (b) L'Institut National de Santé Publique du Québec, Centre de Toxicologie du Québec, Canada, (c) Friedrich-Alexander University, Erlangen, Germany, and (d) the University of Surrey, Guildford, UK Trace Elements scheme. The EQAS data reflect analytical performance for blind samples analyzed independently by both inductively coupled plasma-mass spectrometry and AAS methods.

  17. Measurement of femtogram quantities of protactinium in silicate rock samples by multicollector inductively coupled plasma mass spectrometry.

    PubMed

    Regelous, Marcel; Turner, Simon P; Elliott, Tim R; Rostami, Kia; Hawkesworth, Chris J

    2004-07-01

    We describe a new method for the chemical separation and analysis of Pa in silicate rock samples by isotope dilution. Our new technique has the following advantages over previous methods: (a) The initial separation of Pa from the rock matrix is carried out using anionic exchange resin and HCl-HF mixtures, avoiding the need to remove F(-) quantitatively from the sample solution prior to this step, (b) Efficient ionization of Pa is achieved using a multicollector inductively coupled plasma mass spectrometer, so that smaller sample sizes and shorter measurement times are required, compared to previous methods using thermal ionization mass spectrometry or alpha spectrometry. (c) Plasma ionization requires less efficient separation of the high field strength elements from Pa, thus reducing reagent volumes, blanks, and sample preparation times. Instrumental mass fractionation can be corrected for using admixed U of known isotopic composition. Using this method, Pa concentrations can be measured to a precision of approximately 0.5% and an accuracy of approximately 1% using only a few tens of femtograms of Pa. PMID:15228328

  18. 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

  19. Iodine speciation in dog foods and treats by high performance liquid chromatography with inductively coupled plasma mass spectrometry detection.

    PubMed

    Wilson, Robert A; Yanes, Enrique G; Kemppainen, Robert J

    2016-06-01

    An analytical method for determination of the iodine species 3-monoiodotyrosine (MIT), iodide, 3,5-diiodotyrosine (DIT), 3,5-diiodothyronine (3, 5-T2), 3,5,3'-triiodothyronine (T3), and thyroxine (T4) in dog foods and treats is reported. Iodine speciation was carried out using a HPLC method capable of both anion-exchange and reversed-phase retention coupled with inductively coupled plasma mass spectrometry detection (LC-ICP-MS). The method was evaluated by the analysis of the iodine species concentrations in twelve dog foods and treats following enzymatic digestion. The concentrations of MIT, iodide, DIT, T3, and T4 in the samples ranged from 0.64-59.5μg/g, 0.86-4.05μg/g, spectrometry (LC-MS/MS) to cross-validate the results obtained by LC-ICP-MS. Both methods were in good agreement for the concentrations of DIT, T3, and T4. PMID:27107244

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

    NASA Astrophysics Data System (ADS)

    Cheng, Heyong; Liu, Jinhua; Xu, Zigang; Yin, Xuefeng

    2012-07-01

    A microfluidic sub-microliter sample introducing system was developed for direct analysis of Chinese rice wine by inductively coupled plasma mass spectrometry (ICP-MS). It consisted of a microfluidic chip integrating variable-volume sampling channels (0.1-0.8 μL), an eight-way multi-functional valve used in flow injection analysis (FIA), a syringe pump and a peristaltic pump of the Ar ICP-MS instrument. Three solutions, i.e., 15, 40 and 100 g L- 1 glucose in 20% ethanol were used to simulate Chinese rice wine of the dry type, the semidry type and the semisweet type, each. The effects of their volume introduced into ICP-MS on the plasma stability and ICP-MS intensities were studied. The experimental results showed that neither alteration of plasma stability nor carbon deposition was observed when the sampling volume of 20% ethanol containing 100 g L- 1 glucose was downscaled to 0.8 μL. Further reducing the sampling volume to 0.4 μL, no significant difference between the intensities of multi-element standard prepared in three simulated Chinese rice wine matrices and those in aqueous solution was observed. It indicated no negative effect of Chinese rice wine matrix on the ICP-MS intensities. A sampling volume of 0.4 μL was considered to be a good compromise between sensitivity and matrix effect. The flow rate of the carrier was chosen as 20 μL min- 1 for obtaining peaks with the highest peak height within the shortest time. Based on these observations, a microflow injection (μFI) method for the direct determination of cadmium and lead in Chinese rice wine by ICP-MS using an external aqueous calibration was developed. The sample throughput was 45 h- 1 with the detection limit of 19.8 and 10.4 ng L- 1 for Cd and Pb, respectively. The contents of Cd and Pb in 10 Chinese rice wine samples were measured. The results agreed well with those determined by ICP-MS with the conventional sampling system after microwave assisted digestion. The recoveries of three Chinese

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

    PubMed

    Hirata, Takafumi; Kon, Yoshiaki

    2008-03-01

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

  2. Time-resolved inductively coupled plasma mass spectrometry measurements with individual, monodisperse drop sample introduction.

    PubMed

    Dziewatkoski, M P; Daniels, L B; Olesik, J W

    1996-04-01

    Individual ion clouds, each produced in the ICP from a single drop of sample, were monitored using time-resolved mass spectrometry and optical emission spectrometry simultaneously. The widths of the ion clouds in the plasma as a function of distance from the point of initial desolvated particle vaporization in the ICP were estimated. The Li(+) cloud width (full width at halfmaximum) varied from 85 to 272 μs at 3 and 10 mm from the apparent vaporization point, respectively. The Sr(+) cloud width varied from 97 to 142 μs at 5 and 10 mm from the apparent vaporization point, respectively. The delays between optical and mass spectrometry signals were used to measure gas velocities in the ICP. The velocity data could then be used to convert ion cloud peak widths in time to cloud sizes in the ICP. Li(+) clouds varied from 2.1 to 6.6 mm (full width at half-maximum) and Sr(+) clouds varied from 2.4 to 3.5 mm at the locations specified above. Diffusion coefficients were estimated from experimental data to be 88, 44, and 24 cm(2)/s for Li(+), Mg(+), and Sr(+), respectively. The flight time of ions from the sampling orifice of the mass spectrometer to the detector were mass dependent and varied from 13 to 21 μs for Mg(+) to 93 to 115 μs for Pb(+). PMID:21619140

  3. Production date determination of uranium-oxide materials by inductively coupled plasma mass spectrometry.

    PubMed

    Varga, Zsolt; Surányi, Gergely

    2007-09-01

    The paper describes analytical methods developed for the production date determination of uranium-based nuclear materials by the measurement of 230Th/234U isotope ratio. An improved sample preparation method for the destructive analysis involving extraction chromatographic separation with TEVA resin was applied prior to the measurement by isotope dilution inductively coupled plasma sector field mass spectrometry (ICP-SFMS). The results obtained were compared with the direct, quasi-non-destructive measurement using laser ablation ICP-SFMS technique for age determination. The advantages and limitations of both methods are discussed. PMID:17765059

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

    SciTech Connect

    McIntyre, Sally M.

    2010-01-01

    An inductively coupled plasma-mass spectrometer (ICP-MS) is an elemental analytical instrument capable of determining nearly all elements in the periodic table at limits of detection in the parts per quadrillion and with a linear analytical range over 8-10 orders of magnitude. Three concentric quartz tubes make up the plasma torch. Argon gas is spiraled through the outer tube and generates the plasma powered by a looped load coil operating at 27.1 or 40.6 MHz. The argon flow of the middle channel is used to keep the plasma above the innermost tube through which solid or aqueous sample is carried in a third argon stream. A sample is progressively desolvated, atomized and ionized. The torch is operated at atmospheric pressure. To reach the reduced pressures of mass spectrometers, ions are extracted through a series of two, approximately one millimeter wide, circular apertures set in water cooled metal cones. The space between the cones is evacuated to approximately one torr. The space behind the second cone is pumped down to, or near to, the pressure needed for the mass spectrometer (MS). The first cone, called the sampler, is placed directly in the plasma plume and its position is adjusted to the point where atomic ions are most abundant. The hot plasma gas expands through the sampler orifice and in this expansion is placed the second cone, called the skimmer. After the skimmer traditional MS designs are employed, i.e. quadrupoles, magnetic sectors, time-of-flight. ICP-MS is the leading trace element analysis technique. One of its weaknesses are polyatomic ions. This dissertation has added to the fundamental understanding of some of these polyatomic ions, their origins and behavior. Although mainly continuing the work of others, certain novel approaches have been introduced here. Chapter 2 includes the first reported efforts to include high temperature corrections to the partition functions of the polyatomic ions in ICP-MS. This and other objections to preceeding

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

    NASA Astrophysics Data System (ADS)

    Makonnen, Yoseif; Beauchemin, Diane

    2015-01-01

    In industrial/commercial settings where operators often have minimal expertise in inductively coupled plasma (ICP) mass spectrometry (MS), there is a prevalent need for a response factor indicating robust plasma conditions, which is analogous to the Mg II/Mg I ratio in ICP optical emission spectrometry (OES), whereby a Mg II/Mg I ratio of 10 constitutes robust conditions. While minimizing the oxide ratio usually corresponds to robust conditions, there is no specific target value that is widely accepted as indicating robust conditions. Furthermore, tuning for low oxide ratios does not necessarily guarantee minimal matrix effects, as they really address polyatomic interferences. From experiments, conducted in parallel for both MS and OES, there were some element pairs of similar mass and very different ionization potential that were exploited for such a purpose, the rationale being that, if these elements were ionized to the same extent, then that could be indicative of a robust plasma. The Be II/Li I intensity ratio was directly related to the Mg II/Mg I ratio in OES. Moreover, the 9Be+/7Li+ ratio was inversely related to the CeO+/Ce+ and LaO+/La+ oxide ratios in MS. The effects of different matrices (i.e. 0.01-0.1 M Na) were also investigated and compared to a conventional argon plasma optimized for maximum sensitivity. The suppression effect of these matrices was significantly reduced, if not eliminated in the case of 0.01 M Na, when the 9Be+/7Li+ ratio was around 0.30 on the Varian 820 MS instrument. Moreover, a very similar ratio (0.28) increased robustness to the same extent on a completely different ICP-MS instrument (PerkinElmer NEXION). Much greater robustness was achieved using a mixed-gas plasma with nitrogen in the outer gas and either nitrogen or hydrogen as a sheathing gas, as the 9Be+/7Li+ ratio was then around 1.70. To the best of our knowledge, this is the first report on using a simple analyte intensity ratio, 9Be+/7Li+, to gauge plasma robustness.

  6. High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

    USGS Publications Warehouse

    Morgan, J.L.L.; Gordon, G.W.; Arrua, R.C.; Skulan, J.L.; Anbar, A.D.; Bullen, T.D.

    2011-01-01

    We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios (44Ca/42Ca and 44Ca/43Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10000; Ca/Ti > 10000000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ44/42Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2‰ (2σ).

  7. Influence of sample matrix components on the selection of calibration strategies in electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Fonseca, R. W.; Miller-Ihli, N. J.

    1996-11-01

    Quantification of both digested and slurry samples were studied using ultrasonic slurry electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS). The results of external calibration using aqueous standards, method of additions, and In as an internal standard were compared. The elements studied include: Mn, Ni and Cu and the materials analyzed include: NIST SRM 1548 total diet and SRM 1549 milk powder. Palladium was used as a physical carrier and oxygen ashing was used to remove the organic part of the slurry matrix. Different degrees of matrix suppression effects were observed when different skimmer cones were employed. Aging of the skimmer cone and consequent loss of its original circular symmetry and decrease in orifice size resulted in differences in sampling of the ion beam and changes in the degree of matrix effects were observed as the skimmer cone was rotated. The presence of matrix suppression effects is evidenced by strong suppressions in the Ar 2, C and analyte signals. When matrix suppression effects were present, the method of external calibration provided low recoveries (average accuracy 73 ± 12%), therefore it was necessary to use the method of additions to compensate for these problems, providing an average accuracy of 108 ± 13%. When matrix effects were absent, the external calibration method resulted in an average accuracy of 101 ± 16%.

  8. Determination of plutonium in seawater using co-precipitation and inductively coupled plasma mass spectrometry with ultrasonic nebulisation

    NASA Astrophysics Data System (ADS)

    Eroglu, Ahmet E.; McLeod, Cameron W.; Leonard, Kinson S.; McCubbin, David

    1998-08-01

    A flow injection-inductively coupled plasma-mass spectrometric (FI-ICP-MS) procedure, utilising ultrasonic nebulisation with membrane desolvation (USN/MD), has been developed for the determination of plutonium (Pu) in seawater at fg l -1 concentration levels. Seawater samples (1 l), after filtration, were subjected to co-precipitation with NdF 3, followed by ion exchange to enrich Pu and to reject seawater matrix ions and co-existing uranium. The seawater concentrate (1.0 ml) was then analysed by FI-ICP-MS. The limit of detection for 239Pu in seawater based on an enrichment factor of 1000 was 5 fg l -1, and precision at the 0.80 pg l -1 level was 12% RSD. Accuracy was verified via recovery experiments, and by comparing survey data for the Irish Sea with that derived by standard methodology based on co-precipitation and α-spectrometry. Concentrations for dissolved 239Puand240Pu in the Irish Sea were in the range of 0.267-0.941 pg l -1 (0.614-2.164 mBq l -1) and 0.051-0.196 pg l -1 (0.428-1.646 mBq l -1), respectively.

  9. Determination of total and isotopic uranium and total thorium in soils by inductively coupled plasma-mass spectrometry

    SciTech Connect

    Bolin, R.N.

    1995-12-31

    Inductively coupled plasma-mass spectrometry (ICP-MS), using standard sample introduction by peristaltic pumping, is presented as a method to determine total and isotopic uranium ({sup 234}U, {sup 235}U, {sup 236}U, and {sup 238}U) and thorium ({sup 232}Th) in soil samples. Initial sample preparation consists of oven drying to determine moisture content, and grinding and mixing the soil to make it homogeneous. This is followed by a nitric/hydrofluoric acid digestion to bring the uranium into solution. Bismuth ({sup 209}Bi) is added prior to digestion to monitor for losses due to sample preparation and analysis. An addition digestion, using nitric/perchloric acid is performed if the total thorium concentration is required on the sample. The uranium and thorium content of this solution and the {sup 235}U/{sup 238}U ratio are measured on an initial pass through the ICP-MS. The total uranium measurement is based on the {sup 238}U isotope measurement with correction for the presence of the U isotopes. To determine the concentration of the less abundant {sup 234}U and {sup 236}U isotopes, the digestate is further concentrated by using a solid phase extraction column (TRU.Spec by EiChrom Industries, Inc.) before a second pass through the ICP-MS.

  10. Determination of 90Sr and Pu isotopes in contaminated groundwater samples by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Zoriy, Miroslav V.; Ostapczuk, Peter; Halicz, Ludwik; Hille, Ralf; Becker, J. Sabine

    2005-04-01

    A sensitive analytical method for determining the artificial radionuclides 90Sr, 239Pu and 240Pu at the ultratrace level in groundwater samples from the Semipalatinsk Test Site area in Kazakhstan by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS) was developed. In order to avoid possible isobaric interferences at m/z 90 for 90Sr determination (e.g. 90Zr+, 40Ar50Cr+, 36Ar54Fe+, 58Ni16O2+, 180Hf2+, etc.), the measurements were performed at medium mass resolution under cold plasma conditions. Pu was separated from uranium by means of extraction chromatography using Eichrom TEVA resin with a recovery of 83%. The limits of detection for 90Sr, 239Pu and 240Pu in water samples were determined as 11, 0.12 and 0.1 fg ml-1, respectively. Concentrations of 90Sr and 239Pu in contaminated groundwater samples ranged from 18 to 32 and from 28 to 856 fg ml-1, respectively. The 240Pu/239Pu isotopic ratio in groundwater samples was measured as 0.17. This isotope ratio indicates that the most probable source of contamination of the investigated groundwater samples was the nuclear weapons tests at the Semipalatinsk Test Site conducted by the USSR in the 1960s.

  11. Determination of long-lived beta emitters in nuclear waste by inductively coupled plasma-mass spectrometry

    SciTech Connect

    Bienvenu, P.G.; Brochard, E.A.; Excoffier, E.A.

    1998-12-31

    Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) constitutes a very attractive alternative to radiochemical techniques for the determination of long-lived radionuclides considered critical for the safety of nuclear waste repositories. By measuring isotopic abundance instead of ionizing radiation, it is shown that ICP-MS should exhibit lower detection limits than liquid scintillation counting for the measurement of {beta} emitters with half-lives longer than {approximately} 10{sup 4} years. However, a specific preparative chemistry is generally required prior to measurement in order to separate the analyte from major radioactive contaminants and potentially interfering isotopes. Original methods have recently developed for the determination of three long-lived {beta} emitters: {sup 93}Zr, {sup 107}Pd and {sup 135}Cs in radioactive waste are described in this paper. The procedures involve various separative measurement strategies, such as liquid-liquid extraction, chromatographic separation as well as electrothermal vaporization coupled with ICP-MS. The performances are discussed in terms of selectivity and detection capabilities.

  12. Development and validation of an inductively coupled plasma mass spectrometry method for quantification of levothyroxine in dissolution studies.

    PubMed

    Pabla, Dimple; Akhlaghi, Fatemeh; Ahmed, Aftab; Zia, Hossein

    2008-04-01

    A simple, sensitive and reproducible inductively coupled plasma mass spectrometry (ICP-MS) method for the direct determination of levothyroxine (T4), based on the analysis of iodide content, in aqueous media was developed. The sample preparation consisted of addition of antimony, as the internal standard, and dilution with a 0.5% ammonia solution. The analytes were quantified at m/z 126.90 and 120.90 for iodide and antimony, respectively. The assay was linear in the concentration range of 0.1-50 ng/mL for iodide and 0.3-100 ng/mL for T4. The method was precise and accurate with lower limits of quantification (LLOQs) of 0.1 ng/mL for iodide and 0.3 ng/mL for T4. The inter-day accuracy was >94% for both analytes and the coefficient of variation (%CV) was less than 5%. The method has successfully been used for dissolution studies of T4 formulations and holds immense promise as a simple, precise and sensitive analytical technique for T4 concentration determination in in vitro studies. PMID:18320549

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

    PubMed Central

    Dehelean, Adriana; Magdas, Dana Alina

    2013-01-01

    The presence of potentially toxic elements and compounds in foodstuffs is of intense public interest and thus requires rapid and accurate methods to determine the levels of these contaminants. Inductively coupled plasma mass spectrometry is a powerful tool for the determination of metals and nonmetals in fruit juices. In this study, 21 commercial fruit juices (apple, peach, apricot, orange, kiwi, pear, pineapple, and multifruit) present on Romanian market were investigated from the heavy metals and mineral content point of view by ICP-MS. Our obtained results were compared with those reported in literature and also with the maximum admissible limit in drinking water by USEPA and WHO. For Mn the obtained values exceeded the limits imposed by these international organizations. Co, Cu, Zn, As, and Cd concentrations were below the acceptable limit for drinking water for all samples while the concentrations of Ni and Pb exceeded the limits imposed by USEPA and WHO for some fruit juices. The results obtained in this study are comparable to those found in the literature. PMID:24453811

  14. Analysis of mineral and heavy metal content of some commercial fruit juices by inductively coupled plasma mass spectrometry.

    PubMed

    Dehelean, Adriana; Magdas, Dana Alina

    2013-01-01

    The presence of potentially toxic elements and compounds in foodstuffs is of intense public interest and thus requires rapid and accurate methods to determine the levels of these contaminants. Inductively coupled plasma mass spectrometry is a powerful tool for the determination of metals and nonmetals in fruit juices. In this study, 21 commercial fruit juices (apple, peach, apricot, orange, kiwi, pear, pineapple, and multifruit) present on Romanian market were investigated from the heavy metals and mineral content point of view by ICP-MS. Our obtained results were compared with those reported in literature and also with the maximum admissible limit in drinking water by USEPA and WHO. For Mn the obtained values exceeded the limits imposed by these international organizations. Co, Cu, Zn, As, and Cd concentrations were below the acceptable limit for drinking water for all samples while the concentrations of Ni and Pb exceeded the limits imposed by USEPA and WHO for some fruit juices. The results obtained in this study are comparable to those found in the literature. PMID:24453811

  15. Multielemental analysis in vegetable edible oils by inductively coupled plasma mass spectrometry after solubilisation with tetramethylammonium hydroxide.

    PubMed

    Savio, Marianela; Ortiz, María S; Almeida, César A; Olsina, Roberto A; Martinez, Luis D; Gil, Raúl A

    2014-09-15

    Trace metals have negative effects on the oxidative stability of edible oils and they are important because of possibility for oils characterisation. A single-step procedure for trace elemental analysis of edible oils is presented. To this aim, a solubilisation with tetramethylammonium hydroxide (TMAH) was assayed prior to inductively coupled plasma mass spectrometry detection. Small amounts of TMAH were used, resulting in high elemental concentrations. This method was applied to edible oils commercially available in Argentine. Elements present in small amounts (Cu, Ge, Mn, Mo, Ni, Sb, Sr, Ti, and V) were determined in olive, corn, almond and sunflower oils. The limits of detection were between 0.004 μg g(-1) for Mn and Sr, and 0.32 μg g(-1) for Sb. Principal components analysis was used to correlate the content of trace metals with the type of oils. The two first principal components retained 91.6% of the variability of the system. This is a relatively simple and safe procedure, and could be an attractive alternative for quality control, traceability and routine analysis of edible oils. PMID:24767078

  16. Quantitative analysis of gold nanoparticles in single cells by laser ablation inductively coupled plasma-mass spectrometry.

    PubMed

    Wang, Meng; Zheng, Ling-Na; Wang, Bing; Chen, Han-Qing; Zhao, Yu-Liang; Chai, Zhi-Fang; Reid, Helen J; Sharp, Barry L; Feng, Wei-Yue

    2014-10-21

    Single cell analysis has become an important field of research in recent years reflecting the heterogeneity of cellular responses in biological systems. Here, we demonstrate a new method, based on laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), which can quantify in situ gold nanoparticles (Au NPs) in single cells. Dried residues of picoliter droplets ejected by a commercial inkjet printer were used to simulate matrix-matched calibration standards. The gold mass in single cells exposed to 100 nM NIST Au NPs (Reference material 8012, 30 nm) for 4 h showed a log-normal distribution, ranging from 1.7 to 72 fg Au per cell, which approximately corresponds to 9 to 370 Au NPs per cell. The average result from 70 single cells (15 ± 13 fg Au per cell) was in good agreement with the result from an aqua regia digest solution of 1.2 × 10(6) cells (18 ± 1 fg Au per cell). The limit of quantification was 1.7 fg Au. This paper demonstrates the great potential of LA-ICPMS for single cell analysis and the beneficial study of biological responses to metal drugs or NPs at the single cell level. PMID:25225851

  17. Rapid and sensitive determination of tellurium in soil and plant samples by sector-field inductively coupled plasma mass spectrometry.

    PubMed

    Yang, Guosheng; Zheng, Jian; Tagami, Keiko; Uchida, Shigeo

    2013-11-15

    In this work, we report a rapid and highly sensitive analytical method for the determination of tellurium in soil and plant samples using sector field inductively coupled plasma mass spectrometry (SF-ICP-MS). Soil and plant samples were digested using Aqua regia. After appropriate dilution, Te in soil and plant samples was directly analyzed without any separation and preconcentration. This simple sample preparation approach avoided to a maximum extent any contamination and loss of Te prior to the analysis. The developed analytical method was validated by the analysis of soil/sediment and plant reference materials. Satisfactory detection limits of 0.17 ng g(-1) for soil and 0.02 ng g(-1) for plant samples were achieved, which meant that the developed method was applicable to studying the soil-to-plant transfer factor of Te. Our work represents for the first time that data on the soil-to-plant transfer factor of Te were obtained for Japanese samples which can be used for the estimation of internal radiation dose of radioactive tellurium due to the Fukushima Daiichi Nuclear Power Plant accident. PMID:24148390

  18. A rugged and transferable method for determining blood cadmium, mercury, and lead with inductively coupled plasma-mass spectrometry

    NASA Astrophysics Data System (ADS)

    McShane, William J.; Pappas, R. Steven; Wilson-McElprang, Veronica; Paschal, Dan

    2008-06-01

    A simple, high-throughput method for determining total cadmium, mercury, and lead in blood in cases of suspected exposure, using inductively coupled plasma-mass spectrometry (ICP-MS), has been developed and validated. One part matrix-matched standards, blanks, or aliquots of blood specimens were diluted with 49 parts of a solution containing 0.25% (w/w) tetramethylammonium hydroxide; 0.05% v/v Triton X-100 (blood cell membranes and protein solubilization); 0.01% (w/v) ammonium pyrolidinedithiocarbamate (mercury memory effect prevention and oxidation state stabilization, solubilization by complexation of all three metals); 1% v/v isopropanol (signal enhancement); and 10 μg/L iridium (internal standard). Thus the final dilution factor is 1 + 49. The method provides the basis for the determination of total cadmium, mercury, and lead for assessment of environmental, occupational, accidental ingestion or elevated exposures from other means. Approximately 80 specimens, including blanks, calibration standards, and quality control materials can be processed in an 8-h day. The method has been evaluated by examining reference materials from the National Institute of Standards and Technology, as well as by participation in six rounds of proficiency testing intercomparisons led by the Wadsworth Center of the New York State Department of Health. This method was developed for the purpose of increasing U.S. emergency response laboratory capacity. To this end, 33 U.S. state, and 1 district health department laboratories have validated this method in their own laboratories.

  19. Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

    2006-03-01

    Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1. PMID:16496054

  20. Investigations on the direct introduction of cigarette smoke for trace elements analysis by inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Chang, Michael J.; Naworal, John D.; Walker, Kathleen; Connell, Chris T.

    2003-11-01

    Direct introduction of mainstream cigarette smoke into an inductively coupled plasma mass spectrometry (ICP-MS) has been investigated with respect to its feasibility for on-line analysis of trace elements. An automated apparatus was designed and built interfacing a smoking machine with an ICP-MS for smoke generation, collection, injection and analysis. Major and minor elements present in the particulate phase and the gas phase of mainstream cigarette smoke of 2R4F reference cigarettes have been qualitatively identified by examination of their full mass spectra. This method provides a rapid-screening analysis of the transfer of trace elements into mainstream smoke during cigarette combustion. A full suite of elements present in the whole cigarette smoke has been identified, including As, B, Ba, Br, Cd, Cl, Cs, Cu, Hg, I, K, Li, Mn, Na, Pb, Rb, Sb, Sn, Tl and Zn. Of these elements, the major portions of B, Ba, Cs, Cu, K, Li, Mn, Na, Pb, Rb, Sn, Tl and Zn are present in the particulate phase, whereas the major portion of Hg is present in the gas phase. As, Br, Cd, Cl, I and Sb exist in a distribution between the gas phase and the particulate phase. Depending on the element, the precision of measurement ranges from 5 to 25% in terms of relative standard deviation of peak height and peak area, based on the fourth puff of 2R4F mainstream cigarette smoke analyzed in five smoking replicates.

  1. Determination of heavy metals by inductively coupled plasma mass spectrometry after on-line separation and preconcentration

    NASA Astrophysics Data System (ADS)

    Dressler, Valderi L.; Pozebon, Dirce; Curtius, Adilson J.

    1998-10-01

    A method for the determination of Cu, As, Se, Cd, In, Hg, Tl, Pb and Bi in waters and in biological materials by inductively coupled plasma mass spectrometry, after an on-line separation, is described. The matrix separation and analyte preconcentration is accomplished by retention of the analytes complexed with the ammonium salt of O,O-diethyl dithiophosphoric acid in a HNO 3 solution on C 18 immobilized on silica in a minicolumn. Methanol, as eluent, is introduced in the conventional pneumatic nebulizer of the instrument. In order to use the best compromise conditions, concerning the ligand and acid concentrations, the analytes were determined in two separate groups. The enrichment factors were in the range from 5 to 61, depending on the analyte. The limits of detection varied from 0.43 ng L -1 for Bi to 33 ng L -1 for Cu. The sample consumption is only 2.3 mL for each group and the sampling frequency is 21 h -1. The accuracy was tested by analysing five certified reference materials: water, riverine water, urine, bovine muscle and bovine liver. The agreement between obtained and certified concentrations was very good, except for As. The relatively small volume of methanol, used as eluent, minimizes the problems produced by the introduction of organic solvent into the plasma.

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

    PubMed

    Giussani, Barbara; Monticelli, Damiano; Rampazzi, Laura

    2009-03-01

    Cultural heritage represents a bridge between the contemporary society and the past populations, and a strong collaboration between archaeologists, art historians and analysts may lead to the decryption of the information hidden in an ancient object. Quantitative elemental compositional data play a key role in solving questions concerning dating, provenance, technology, use and the relationship of ancient cultures with the environment. Nevertheless, the scientific investigation of an artifact should be carried out complying with some important constraints: above all the analyses should be as little destructive as possible and performed directly on the object to preserve its integrity. Laser ablation sampling coupled to inductively coupled plasma-mass spectrometry (LA-ICP-MS) fulfils these requirements exhibiting comparably strong analytical performance in trace element determination. This review intends to show through the applications found in the literature how valuable is the contribution of LA-ICP-MS in the investigation of ancient materials such as obsidian, glass, pottery, human remains, written heritage, metal objects and miscellaneous stone materials. The main issues related to cultural heritage investigation are introduced, followed by a brief description of the features of this technique. An overview of the exploitation of LA-ICP-MS is then presented. Finally, advantages and drawbacks of this technique are critically discussed: the fit for purpose and prospects of the use of LA-ICP-MS are presented. PMID:19200475

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

    USGS Publications Warehouse

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

    2009-01-01

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

  4. Tracking traces of transition metals present in concrete mixtures by inductively-coupled plasma mass spectrometry studies.

    PubMed

    Bassioni, Ghada; Pillay, Alvin E; El Kadi, Mirella; Fegali, Fadi; Fok, Sai Cheong; Stephen, Sasi

    2010-01-01

    Transition metals can have a significant impact in research related to the dosage optimization of superplasticizers. It is known that the presence of transition metals can influence such doses, and the application of a contemporary instrumental method to obtain the profiles of subsisting transition elements in concrete mixtures would be useful. In this work, inductively-coupled plasma mass spectrometry (ICP-MS) is investigated as a possible tool to track traces of transition metals in concrete mixtures. Depth profiling using ICP-MS on proofed and unproofed concrete shows the presence of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn at trace intensities in the bulk of the samples under investigation. The study demonstrates that the transition metals present in the concrete sample are largely a part of the cement composition and, to a minor degree, a result of exposure to the seawater after curing. The coated concrete samples have a metal distribution pattern similar to the uncoated samples, but slight differences in intensity bear testimony to the very low levels that originate from the exposure to seawater. While X-ray diffraction fails to detect these traces of metals, ICP-MS is successful in detecting ultra-trace intensities to parts per trillion. This method is not only a useful application to track traces of transition metals in concrete, but also provides information to estimate the pore size distribution in a given sample by very simple means. PMID:21173466

  5. Application of Inductively Coupled Plasma Mass Spectrometry to the determination of uranium isotope ratios in individual particles for nuclear safeguards

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao Zhi; Esaka, Fumitaka; Esaka, Konomi T.; Magara, Masaaki; Sakurai, Satoshi; Usuda, Shigekazu; Watanabe, Kazuo

    2007-10-01

    The capability of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of uranium isotope ratios in individual particles was determined. For this purpose, we developed an experimental procedure including single particle transfer with a manipulator, chemical dissolution and isotope ratio analysis, and applied to the analysis of individual uranium particles in certified reference materials (NBL CRM U050 and U350). As the result, the 235U/ 238U isotope ratio for the particle with the diameter between 0.5 and 3.9 μm was successfully determined with the deviation from the certified ratio within 1.8%. The relative standard deviation (R.S.D.) of the 235U/ 238U isotope ratio was within 4.2%. Although the analysis of 234U/ 238U and 236U/ 238U isotope ratios gave the results with inferior precision, the R.S.D. within 20% was possible for the measurement of the particle with the diameter more than 2.1 μm. The developed procedure was successfully applied to the analysis of a simulated environmental sample prepared from a mixture of indoor dust (NIST SRM 2583) and uranium particles (NBL CRM U050, U350 and U950a). From the results, the proposed procedure was found to be an alternative analytical tool for nuclear safeguards.

  6. Determination of arsenic species in Solanum Lyratum Thunb using capillary electrophoresis with inductively coupled plasma mass spectrometry.

    PubMed

    Shuai, Pei-Yu; Yang, Xiao-Jun; Qiu, Zong-Qing; Wu, Xiao-Hui; Zhu, Xi; Pokhrel, Ganga Raj; Fu, Yu-Ying; Ye, Hui-Min; Lin, Wen-Xiong; Yang, Gui-Di

    2016-08-01

    A simple and highly efficient interface to couple capillary electrophoresis with inductively coupled plasma mass spectrometry by a microflow polyfluoroalkoxy nebulizer and a quadruple ion deflector was developed in this study. By using this interface, six arsenic species, including arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, were baseline-separated and determined in a single run within 11 min under the optimized separation conditions. The instrumental detection limit was in the range of 0.02-0.06 ng/mL for the six arsenic compounds. Repeatability expressed as the relative standard deviation (n = 5) of both migration time and peak area were better than 2.5 and 4.3% for six arsenic compounds. The proposed method, combined with a closed-vessel microwave-assisted extraction procedure, was successfully applied for the determination of arsenic species in the Solanum Lyratum Thunb samples from Anhui province in China with the relative standard deviations (n = 5) ≤4%, method detection limits of 0.2-0.6 ng As/g and a recovery of 98-104%. The experimental results showed that arsenobetaine was the main speciation of arsenic in the Solanum Lyratum Thunb samples from different provinces in China, with a concentration of 0.42-1.30 μg/g. PMID:27378629

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

    PubMed

    Li, X Sherry; Glasauer, Susan; Le, X Chris

    2007-10-17

    A simple and sensitive method for the speciation of vanadium(III), (IV), and (V) was developed by using high performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC-ICPMS). The EDTA-complexed vanadium species were separated on a strong anion exchange column with an eluent containing 2 mM EDTA, 3% acetonitrile, and 80 mM ammonium bicarbonate at pH 6. Each analysis was complete in 5 min. The detection limits were 0.6, 0.7 and 1.0 microg L(-1) for V(III), V(IV), and V(V), respectively. The method was applied to coke pore water samples from an oilsand processing/upgrading site in Fort McMurray, Alberta, Canada and to Shewanella putrefaciens CN32 bacterial cultures incubated with V(V). In the coke pore water samples, V(IV) and V(V) were found to be the major species. For the first time, V(III) was detected in the bacterial cultures incubated with V(V). PMID:17936102

  8. Submicrometer Imaging by Laser Ablation-Inductively Coupled Plasma Mass Spectrometry via Signal and Image Deconvolution Approaches.

    PubMed

    Van Malderen, Stijn J M; van Elteren, Johannes T; Vanhaecke, Frank

    2015-06-16

    In this work, pre- and postacquisition procedures for enhancing the lateral resolution of laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) in two- and three-dimensional (2D, 3D) nuclide distribution mapping beyond the laser beam waist are described. 2D images were constructed by projecting a rectangular grid of discrete LA positions, arranged at interspacings smaller than the dimensions of the laser beam waist, onto the sample surface, thus oversampling the region of interest and producing a 2D image convolved in the spatial domain. The pulse response peaks of a low-dispersion LA cell were isolated via signal deconvolution of the transient mass analyzer response. A 3D stack of 2D images was deconvolved by an iterative Richardson-Lucy algorithm with Total Variance regularization, enabling submicrometer image fidelity, demonstrated in the analysis of trace level features in corroded glass. A point spread function (PSF) could be derived from topography maps of single pulse craters from atomic force microscopy. This experimental PSF allows the approach to take into account the laser beam shape, beam aberrations, and the laser-solid interaction, which in turn enhances the spatial resolution of the reconstructed volume. PMID:25975805

  9. The effect of ultrafast laser wavelength on ablation properties and implications on sample introduction in inductively coupled plasma mass spectrometry

    SciTech Connect

    LaHaye, N. L.; Harilal, S. S.; Diwakar, P. K.; Hassanein, A.; Kulkarni, P.

    2013-07-14

    We investigated the role of femtosecond (fs) laser wavelength on laser ablation (LA) and its relation to laser generated aerosol counts and particle distribution, inductively coupled plasma-mass spectrometry (ICP-MS) signal intensity, detection limits, and elemental fractionation. Four different NIST standard reference materials (610, 613, 615, and 616) were ablated using 400 nm and 800 nm fs laser pulses to study the effect of wavelength on laser ablation rate, accuracy, precision, and fractionation. Our results show that the detection limits are lower for 400 nm laser excitation than 800 nm laser excitation at lower laser energies but approximately equal at higher energies. Ablation threshold was also found to be lower for 400 nm than 800 nm laser excitation. Particle size distributions are very similar for 400 nm and 800 nm wavelengths; however, they differ significantly in counts at similar laser fluence levels. This study concludes that 400 nm LA is more beneficial for sample introduction in ICP-MS, particularly when lower laser energies are to be used for ablation.

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

    PubMed Central

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

    2011-01-01

    Currently there are few ideal methods for the characterization of nanoparticles in complex, environmental samples, leading to significant gaps in toxicity and exposure assessments of nanomaterials. Single particle-inductively coupled plasma-mass spectrometry (spICP-MS) is an emerging technique that can both size and count metal-containing nanoparticles. A major benefit of the spICP-MS method is its ability to characterize nanoparticles at concentrations relevant to the environment. This paper presents a practical guide on how to count and size nanoparticles using spICP-MS. Different methods are investigated for measuring transport efficiency (i.e. nebulization efficiency), an important term in the spICP-MS calculations. In addition, an alternative protocol is provided for determining particle size that broadens the applicability of the technique to all types of inorganic nanoparticles. Initial comparison, using well-characterized, monodisperse silver nanoparticles, showed the importance of having an accurate transport efficiency value when determining particle number concentration and, if using the newly presented protocol, particle size. Ultimately, the goal of this paper is to provide improvements to nanometrology by further developing this technique for the characterization of metal-containing nanoparticles. PMID:22074486

  11. On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials.

    PubMed

    Fernández, Beatriz; Rodríguez-González, Pablo; García Alonso, J Ignacio; Malherbe, Julien; García-Fonseca, Sergio; Pereiro, Rosario; Sanz-Medel, Alfredo

    2014-12-01

    We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6-21% for pressed pellets and 3-21% for fused solids were obtained from n=3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches. PMID:25440666

  12. The effect of ultrafast laser wavelength on ablation properties and implications on sample introduction in inductively coupled plasma mass spectrometry

    PubMed Central

    LaHaye, N. L.; Harilal, S. S.; Diwakar, P. K.; Hassanein, A.; Kulkarni, P.

    2015-01-01

    We investigated the role of femtosecond (fs) laser wavelength on laser ablation (LA) and its relation to laser generated aerosol counts and particle distribution, inductively coupled plasma-mass spectrometry (ICP-MS) signal intensity, detection limits, and elemental fractionation. Four different NIST standard reference materials (610, 613, 615, and 616) were ablated using 400 nm and 800 nm fs laser pulses to study the effect of wavelength on laser ablation rate, accuracy, precision, and fractionation. Our results show that the detection limits are lower for 400 nm laser excitation than 800 nm laser excitation at lower laser energies but approximately equal at higher energies. Ablation threshold was also found to be lower for 400 nm than 800 nm laser excitation. Particle size distributions are very similar for 400 nm and 800 nm wavelengths; however, they differ significantly in counts at similar laser fluence levels. This study concludes that 400 nm LA is more beneficial for sample introduction in ICP-MS, particularly when lower laser energies are to be used for ablation. PMID:26640294

  13. Measurements of gunshot residues by sector field inductively coupled plasma mass spectrometry--further studies with pistols.

    PubMed

    Sarkis, Jorge E Souza; Neto, Osvaldo N; Viebig, Sônia; Durrant, Steven F

    2007-10-01

    The most popular handgun in Brazil is the single round-barrel caliber 0.38 revolver. In recent years, however, owing to the modernization of police arms and their availability on the legal and illicit markets, pistols have become increasingly popular and currently represent about 20% of police seizures. In a previous paper we presented a novel collection method for gunshot residues (GSR) using a sampling procedure based on ethylenediamine-tetraacetic acid (EDTA) solution as a complexing agent on moistened swabs with subsequent detection using sector field-high resolution-inductively coupled plasma-mass spectrometry (SF-HR-ICP-MS). In the present paper, we discuss the capability of this methodology to identify antimony (Sb), barium (Ba) and lead (Pb) on the hands of volunteers after shot tests with 9 mm and 0.40 in. caliber pistols. Two types of munitions were tested: 9 mm Taurus and clean range. The use of a technique with high sensitivity, such as SF-HR-ICP-MS, permits the identification of low concentrations (less than 1 microg/L) of metals in firearm residue and constitutes a powerful tool in forensic science. We also discuss the importance of the sampling procedure, including collection from a different body part than the gun hand of the suspect. Comparison of the analytical data obtained allows clear discrimination between samples from the hands of shooters and non-shooters. PMID:17254727

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

    NASA Astrophysics Data System (ADS)

    Duyck, Christiane Béatrice; Saint'Pierre, Tatiana Dillenburg; Miekeley, Norbert; da Fonseca, Teresa Cristina Oliveira; Szatmari, Peter

    2011-05-01

    A method was developed for the determination of V and Ni as tetrapyrroles by High Performance Liquid Chromatography hyphenated to Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) using reversed phase and elution gradient. Chlorinated solvents and tetrahydrofuran were investigated as regard to separation time and ICP-MS detection efficiencies. The final elution gradient program started from pure methanol to a mixture of 20:80 (v/v) chloroform:methanol. External quantification of V and Ni with inorganic standards by flow injection ICP-MS, used online with HPLC, resulted in 95% of recoveries. The Limits of Detection for V during methanol elution and for Ni during the 20% chloroform gradient elution were evaluated by their minimum detectable concentrations, which were, respectively, 5 μg L - 1 and 8 μg L - 1 . The methodology was applied to polar and resin fractions separated from a Brazilian crude oil and a sediment extract from an oil-polluted area in the Guanabara Bay, Rio de Janeiro, Brazil. Vanadium as tetrapyrroles represented the totality of V content in the polar fraction, whereas Ni was in different polar forms in the resin and sediment extract.

  15. Characterization of a Sealed Americium-Beryllium (AmBe) Source by Inductively Coupled Plasma Mass Spectrometry

    SciTech Connect

    James Sommers; Marcos Jimenez; Mary Adamic; Jeffrey Giglio; Kevin Carney

    2009-12-01

    Two Americium-Beryllium neutron sources were dismantled, sampled (sub-sampled) and analyzed via inductively coupled plasma mass spectrometry (ICP-MS). Characteristics such as “age” since purification, actinide content, trace metal content and inter and intra source composition were determined. The “age” since purification of the two sources was determined to be 25.0 and 25.4 years, respectively. The systematic errors in the “age” determination were ± 4 % 2s. The amount and isotopic composition of U and Pu varied substantially between the sub-samples of Source 2 (n=8). This may be due to the physical means of sub-sampling or the way the source was manufactured. Source 1 was much more consistent in terms of content and isotopic composition (n=3 sub-samples). The Be-Am ratio varied greatly between the two sources. Source 1 had an Am-Be ratio of 6.3 ± 52 % (1s). Source 2 had an Am-Be ratio of 9.81 ± 3.5 % (1s). In addition, the trace element content between the samples varied greatly. Significant differences were determined between Source 1 and 2 for Sc, Sr, Y, Zr, Mo, Ba and W.

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

    PubMed

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

    2012-03-01

    A new method based on scanning laser ablation and inductively coupled plasma-mass spectrometry (LA-ICPMS) for the detection and identification of gunshot residue (GSR) particles from firearms discharges has been developed. Tape lifts were used to collect inorganic residues from skin surfaces. The laser ablation pattern and ICPMS conditions were optimized for the detection of metals present in GSR, such as (121)Sb, (137)Ba, and (208)Pb. Other isotopes ((27)Al, (29)Si, (31)P, (33)S, (35)Cl, (39)K, (44)Ca, (57)Fe, (60)Ni, (63)Cu, (66)Zn, and (118)Sn) were monitored during the ICPMS analyses to obtain additional information to possibly classify the GSR particles as either characteristic of GSR or consistent with GSR. In experiments with real samples, different firearms, calibers, and ammunitions were used. The performed method evaluation confirms that the developed methodology can be used as an alternative to the standard scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) technique, with the significant advantage of drastically reducing the analysis time to less than 66 min. PMID:22304477

  17. Importance of sample form and surface temperature for analysis by ambient plasma mass spectrometry (PADI).

    PubMed

    Salter, Tara La Roche; Bunch, Josephine; Gilmore, Ian S

    2014-09-16

    Many different types of samples have been analyzed in the literature using plasma-based ambient mass spectrometry sources; however, comprehensive studies of the important parameters for analysis are only just beginning. Here, we investigate the effect of the sample form and surface temperature on the signal intensities in plasma-assisted desorption ionization (PADI). The form of the sample is very important, with powders of all volatilities effectively analyzed. However, for the analysis of thin films at room temperature and using a low plasma power, a vapor pressure of greater than 10(-4) Pa is required to achieve a sufficiently good quality spectrum. Using thermal desorption, we are able to increase the signal intensity of less volatile materials with vapor pressures less than 10(-4) Pa, in thin film form, by between 4 and 7 orders of magnitude. This is achieved by increasing the temperature of the sample up to a maximum of 200 °C. Thermal desorption can also increase the signal intensity for the analysis of powders. PMID:25137443

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

    PubMed

    Tanaka, Kazuya; Takahashi, Yoshio; Shimizu, Hiroshi

    2007-02-01

    In this study, we examined the influence of the matrix on rare earth element (REE) analyses of carbonate with laser-ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) using carbonate and NIST glass standards. A UV 213 nm Nd:YAG laser system was coupled to an ICP-MS. Laser-ablation was carried out in both He and Ar atmospheres to investigate the influence of ablation gas on the analytical results. A small amount of N2 gas was added to the carrier gas to enhance the signal intensities. Synthetic CaCO3 standards, doped with REEs, as well as NIST glasses (NIST SRM 610 and 612) were used as calibration standards. Carbonatite, which is composed of pure calcite, was analyzed as carbonate samples. The degree of the influence of the matrix on the results was evaluated by comparing the results, which were calibrated by the synthetic CaCO3 and NIST glass standards. With laser-ablation in a He atmosphere, the differences between the results calibrated by the synthetic CaCO3 and NIST glass standards were less than 10% across the REE series, except for those of La which were 25%. In contrast, for the measurements made in an Ar atmosphere, the results calibrated by the synthetic CaCO3 and NIST glass standards differed by 25-40%. It was demonstrated that the LA-ICP-MS system can provide quantitative analysis of REE concentrations in carbonate samples using non matrix-matched standards of NIST glasses. PMID:17386560

  19. Sample Preparation Problem Solving for Inductively Coupled Plasma-Mass Spectrometry with Liquid Introduction Systems I. Solubility, Chelation, and Memory Effects

    PubMed Central

    Pappas, R. Steven

    2015-01-01

    This tutorial was adapted from the first half of a course presented at the 7th International Conference on Sector Field Inductively Coupled Plasma Mass Spectrometry in 2008 and the 2012 Winter Conference on Plasma Spectrochemistry on sample preparation for liquid introduction systems. Liquid introduction in general and flow injection specifically are the most widely used sample introduction methods for inductively coupled plasma-mass spectrometry. Nevertheless, problems persist in determination of analytes that are commonly investigated, as well as in specialty applications for those seldom considered by most analysts. Understanding the chemistry that is common to different groups of analytes permits the development of successful approaches to rinse-out and elimination of memory effects. This understanding also equips the analyst for development of successful elemental analytical approaches in the face of a broad spectrum of matrices and other analytical challenges, whether the sample is solid or liquid. PMID:26321788

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

    NASA Astrophysics Data System (ADS)

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

    2006-11-01

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

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

    PubMed

    Liu, Chenhui; Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

    2016-05-01

    Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been successfully applied in the rapid and high-precision measurement for sulfur isotope ratios in recent years. During the measurement, the presence of matrix elements would affect the instrumental mass bias for sulfur and these matrix-induced effects have aroused a lot of researchers' interest. However, these studies have placed more weight on highlighting the necessity for their proposed correction protocols (e.g., chemical purification and matrix-matching) while less attention on the key property of the matrix element gives rise to the matrix effects. In this study, four groups of sulfate solutions, which have different concentrations of sulfur (0.05-0.60mM) but a constant sequence of atomic calcium/sulfur ratios (0.1-50), are investigated under wet (solution) and dry (desolvation) plasma conditions to make a detailed evaluation on the matrix effects from calcium on sulfur isotope measurement. Based on a series of comparative analyses, we indicated that, the matrix effects of calcium on both measured sulfur isotope ratios and detected (32)S signal intensities are dependent mainly on the absolute calcium concentration rather than its relative concentration ratio to sulfur (i.e., atomic calcium/sulfur ratio). Also, for the same group of samples, the matrix effects of calcium under dry plasma condition are much more significant than that of wet plasma. This research affords the opportunity to realize direct and relatively precise sulfur isotope measurement for evaporite gypsum, and further provides some suggestions with regard to sulfur isotope analytical protocols for sedimentary pore water. PMID:26946020

  2. High temperature liquid chromatography-inductively coupled plasma mass spectrometry for the determination of arsenosugars in biological samples.

    PubMed

    Terol, Amanda; Ardini, Francisco; Grotti, Marco; Todolí, José Luis

    2012-11-01

    The potential of high temperature liquid chromatography (HTLC) with detection by inductively coupled plasma mass spectrometry (ICP-MS) for the determination of arsenosugars in marine organisms was examined for the first time. The retention behavior of four naturally occurring dimethylarsinoylribosides was studied on a graphite column using plain water as mobile phase. An aqueous solution of pH 8, ionic strength 13.8mM and containing 2% (v/v) of methanol, along with a column temperature of 120°C and a liquid flow rate of 1.0 mL/min, were selected as the optimal conditions, as they allowed the separation of the four arsenosugars in less than 18 min, without any interferences due to other common arsenic species (arsenite, arsenate, dimethylarsinate, methylarsonate and arsenobetaine). The run time could be further decreased to 12 min by working at 1.5 mL/min, although with a 3-4 times loss of sensitivity. The procedural limits of detection were 0.03-0.04 μg As/g dry mass, and the precision of the procedure ranged from 4% for arsenosugar glycerol to 18% for arsenosugar sulfate (RSD%, n=5). The developed method was applied to a number of representative biological samples, such as algae and crustaceans, providing results consistent with previous studies. In the red algae samples, the most of extracted arsenic was as arsenosugars (81-97%), mainly arsenosugar phosphate (56-94%). On the other hand, lower concentrations of these compounds were found in the crustacean, accounting for about 15% of the extracted arsenic. PMID:22995196

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

    PubMed

    Abad-Álvaro, Isabel; Peña-Vázquez, Elena; Bolea, Eduardo; Bermejo-Barrera, Pilar; Castillo, Juan R; Laborda, Francisco

    2016-07-01

    The quality of the quantitative information in single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS) depends directly on the number concentration of the nanoparticles in the sample analyzed, which is proportional to the flux of nanoparticles through the plasma. Particle number concentrations must be selected in accordance with the data acquisition frequency, to control the precision from counting statistics and the bias, which is produced by the occurrence of multiple-particle events recorded as single-particle events. With quadrupole mass spectrometers, the frequency of data acquisition is directly controlled by the dwell time. The effect of dwell times from milli- to microseconds (10 ms, 5 ms, 100 μs, and 50 μs) on the quality of the quantitative data has been studied. Working with dwell times in the millisecond range, precision figures about 5 % were achieved, whereas using microsecond dwell times, the suitable fluxes of nanoparticles are higher and precision was reduced down to 1 %; this was independent of the dwell time selected. Moreover, due to the lower occurrence of multiple-nanoparticle events, linear ranges are wider when dwell times equal to or shorter than 100 μs are used. A calculation tool is provided to determine the optimal concentration for any instrument or experimental conditions selected. On the other hand, the use of dwell times in the microsecond range reduces significantly the contribution of the background and/or the presence of dissolved species, in comparison with the use of millisecond dwell times. Although the use of dwell times equal to or shorter than 100 μs offers improved performance working in single-particle mode, the use of conventional dwell times (3-10 ms) should not be discarded, once their limitations are known. PMID:27086011

  4. Parallel path nebulizer: Critical parameters for use with microseparation techniques combined with inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

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

    2005-04-01

    Four different, low flow parallel path Mira Mist CE nebulizers were evaluated and compared in support of an ongoing project related to the use of microseparation techniques interfaced to inductively coupled plasma mass spectrometry for the quantification of cobalamin species (Vitamin B12). For the characterization of the different Mira Mist CE nebulizers, the nebulizer orientation as well as the effect of methanol on analytical response was the focus of the study. The position of the gas outlet on the nebulizer which consistently provided the maximum signal was when it was rotated to the 11 o'clock position when the nebulizer is viewed end-on. With this orientation the increased signal may be explained by the fact that the cone angle of the aerosol is such that the largest percentage of the aerosol is directed to the center of the spray chamber and consequently into the plasma. To characterize the nebulizer's performance, the signal response of a multielement solution containing elements with a variety of ionization potentials was used. The selection of elements with varying ionization energies and degrees of ionization was essential for a better understanding of observed increases in signal enhancement when methanol was used. Two different phenomena contribute to signal enhancement when using methanol: the first is improved transport efficiency and the second is the "carbon enhancement effect". The net result was that as much as a 30-fold increase in signal was observed for As and Mg when using a make-up solution of 20% methanol at a 15 μL/min flow rate which is equivalent to a net volume of 3 μL/min of pure methanol.

  5. 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.

  6. Determination of Mercury Content in a Shallow Firn Core from Summit, Greenland by Isotope Dilution Inductively Coupled Plasma Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mann, Jacqueline L.; Long, Stephen E.; Shuman, Christopher A.; Kelly, W. Robert

    2003-01-01

    The total mercury Hg content was determined in 6 cm sections of a near-surface 7 m firn core and in surrounding surface snow from Summit, Greenland (elevation: 3238 m, 72.58 N, 38.53 W) in May 2001 by isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICP-MS). The focus of this research was to evaluate the capability of the ID-CV-ICPMS technique for measuring trace levels of Hg typical of polar snow and firn. Highly enriched Hg-201 isotopic spike is added to approximately 10 ml melted core and thoroughly mixed. The Hg(+2) in the sample is reduced on line with tin (II) chloride (SnCl2) and the elemental Hg (Hg(0)) vapor pre-concentrated on to gold gauze using a commercial amalgam system. The Hg is then thermally desorbed and introduced into a quadrupole ICP-MS. The blank corrected Hg concentrations determined for all samples ranged from 0.25 ng/L to 1.74 ng/L (ppt) (average 0.59 ng/L plus or minus 0.28 ng/L) and fall within the range of those previously determined by Boutron et al., 1998 (less than or equal to 0.05 ng/L to 2.0 ng/L) for the Summit site. The average blank value was 0.19 ng/L plus or minus 0.045 ng/L (n=6). The Hg values specifically for the firn core range from 0.25 ng/L to 0.87 ng/L (average 0.51 ng/L plus or minus 0.13 ng/L) and show both values declining with time and larger variability in concentration in the top 1.8 m.

  7. Determination of rare earth impurities in high purity samarium oxide using inductively coupled plasma mass spectrometry after extraction chromatographic separation

    NASA Astrophysics Data System (ADS)

    Zhang, Xinquan; Liu, Jinglei; Yi, Yong; Liu, Yonglin; Li, Xiang; Su, Yaqin; Lin, Ping

    2007-01-01

    A method for the determination of trace of 14 rare earth elements (REEs) as impurities in high purity samarium oxide (Sm2O3) using inductively coupled plasma mass spectrometry (ICP-MS) was described. Analytes, such as La, Ce, Pr, Nd, Eu, Gd, Tb, Lu and Y were measured without Sm matrix separation because of no interference problems occurring that could affect the analysis of these elements. On the other hand, analytes, such as Dy, Ho, Er, Tm and Yb were carried out after Sm matrix being eliminated completely by means of 2-ethylhexyl hydrogen-ethylhexy phosphonate (EHEHP) extraction chromatographic separation. The inherent problem associated with matrix-induced suppression was effectively compensated with spiking In as internal standard element and the mass spectra isobaric interferences of atomic and molecular ions arose from Sm matrix had been overcome after the removal of Sm matrix. The limits of quantitations (LOQ) for 14 REEs impurities were from 0.01 to 0.07 [mu]g g-1 together with the recoveries of spiking sample of 14 REEs were found to be in the range of 85-110% and the proposed method precision was less than 5%. A synthetic standard Sm2O3 sample with well-known 14 REEs concentrations was prepared and analysed in order to prove the accuracy and precision of the proposed method together with another high purity Sm2O3 was also measured using ICP-MS. The methodology had been found to be suitable for the determination of trace of 14 REEs in 99.999-99.9999% high purity Sm2O3.

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

    PubMed

    Tan, Jiaojie; Liu, Jingyu; Li, Mingdong; El Hadri, Hind; Hackley, Vincent A; Zachariah, Michael R

    2016-09-01

    The novel hyphenation of electrospray-differential mobility analysis with single particle inductively coupled plasma mass spectrometry (ES-DMA-spICPMS) was demonstrated with the capacity for real-time size, mass, and concentration measurement of nanoparticles (NPs) on a particle-to-particle basis. In this proof-of-concept study, the feasibility of this technique was validated through both concentration and mass calibration using NIST gold NP reference materials. A detection limit of 10(5) NPs mL(-1) was determined under current experimental conditions, which is about 4 orders of magnitude lower in comparison to that of a traditional ES-DMA setup using a condensation particle counter as detector. Furthermore, independent and simultaneous quantification of both size and mass of NPs provides information regarding NP aggregation states. Two demonstrative applications include gold NP mixtures with a broad size range (30-100 nm), and aggregated gold NPs with a primary size of 40 nm. Finally, this technique was shown to be potentially useful for real-world samples with high ionic background due to its ability to remove dissolved ions yielding a cleaner background. Overall, we demonstrate the capacity of this new hyphenated technique for (1) clearly resolving NP populations from a mixture containing a broad size range; (2) accurately measuring a linear relationship, which should inherently exist between mobility size and one-third power of ICPMS mass for spherical NPs; (3) quantifying the early stage propagation of NP aggregation with well-characterized oligomers; and (4) differentiating aggregated NPs and nonaggregated states based on the "apparent density" derived from both DMA size and spICPMS mass. PMID:27479448

  9. Determination of trace elements in biological samples by inductively coupled plasma mass spectrometry with tetramethylammonium hydroxide solubilization at room temperature.

    PubMed

    Batista, Bruno Lemos; Grotto, Denise; Rodrigues, Jairo Lisboa; Souza, Vanessa Cristina de Oliveira; Barbosa, Fernando

    2009-07-30

    A simple method for sample preparation of biological samples for trace elements determination by inductively coupled plasma mass spectrometry (ICP-MS) is described. Prior to analysis, 75 mg of the biological samples were accurately weighed into (15 mL) conical tubes. Then, 1 mL of 50% (v/v) tetramethylammonium hydroxide (TMAH) solution was added to the samples, incubated at room temperature for 12 h and the volume made up to 10 mL with a solution containing 0.5% (v/v) HNO(3), 0.01% (v/v) Triton X-100 and 10 microg L(-1) of Rh. After preparation samples may be stored at -20 degrees C during 3 days until the analysis by ICP-MS. With these conditions, the use of the dynamic reaction cell was only mandatory for chromium determination. Method detection limits were 0.2145, 0.0020, 0.0051, 0.0017, 0.0027, 0.0189, 0.02, 0.5, 0.1, 0.0030, 0.0043, 0.0066, 0.0009, 0.020, 0.0043, 0.1794, 0.1 microg(-1) for Al, As, Ba, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Pb, Sb, Se, Sr, V and Zn, respectively. Validation data are provided based on the analysis of six certified reference materials (CRMs) purchased from the National Institute of Standards and Technology (NIST) and National Research Council Canada (NRCC). Additional validation was provided by the analysis of brain, kidney, liver and heart samples collected from rats and analyzed by the proposed method and by using microwave digestion. PMID:19523552

  10. Automated in situ trace element analysis of silicate materials by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Chen, Z; Canil, D; Longerich, H P

    2000-09-01

    This paper describes the automated in situ trace element analysis of solid materials by laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS). A compact computer-controlled solid state Nd:YAG Merchantek EO UV laser ablation (LA) system has been coupled with the high sensitivity VG PQII S ICP-MS. A two-directional communication was interfaced in-house between the ICP-MS and the LA via serial RS-232 port. Each LA-ICP-MS analysis at a defined point includes a 60 s pre-ablation delay, a 60 s ablation, and a 90 s flush delay. The execution of each defined time setting by LA was corresponding to the ICP-MS data acquisition allowing samples to be run in automated cycle sequences like solution auto-sampler ICP-MS analysis. Each analytical cycle consists of four standards, one control reference material, and 15 samples, and requires about 70 min. Data produced by Time Resolved Analysis (TRA) from ICP-MS were later reduced off-line by in-house written software. Twenty-two trace elements from four reference materials (NIST SRM 613, and fused glass chips of BCR-2, SY-4, and G-2) were determined by the automated LA-ICP-MS method. NIST SRM 610 or NIST SRM 613 was used as an external calibration standard, and Ca as an internal standard to correct for drift, differences in transport efficiency and sampling yield. Except for Zr and Hf in G-2, relative standard deviations for all other elements are less than 10%. Results compare well with the data reported from literature with average limits of detection from 1 ng x g(-1) to 455 ng x g(-1) and less than 100 ng x g(-1) for most trace elements. PMID:11220835

  11. Extraction and analysis of silver and gold nanoparticles from biological tissues using single particle inductively coupled plasma mass spectrometry.

    PubMed

    Gray, Evan P; Coleman, Jessica G; Bednar, Anthony J; Kennedy, Alan J; Ranville, James F; Higgins, Christopher P

    2013-12-17

    Expanded use of engineered nanoparticles (ENPs) in consumer products increases the potential for environmental release and unintended biological exposures. As a result, measurement techniques are needed to accurately quantify ENP size, mass, and particle number distributions in biological matrices. This work combines single particle inductively coupled plasma mass spectrometry (spICPMS) with tissue extraction to quantify and characterize metallic ENPs in environmentally relevant biological tissues for the first time. ENPs were extracted from tissues via alkaline digestion using tetramethylammonium hydroxide (TMAH). Method development was performed using ground beef and was verified in Daphnia magna and Lumbriculus variegatus . ENPs investigated include 100 and 60 nm Au and Ag stabilized by polyvynylpyrrolidone (PVP). Mass- and number-based recovery of spiked Au and Ag ENPs was high (83-121%) from all tissues tested. Additional experiments suggested ENP mixtures (60 and 100 nm Ag ENPs) could be extracted and quantitatively analyzed. Biological exposures were also conducted to verify the applicability of the method for aquatic organisms. Size distributions and particle number concentrations were determined for ENPs extracted from D. magna exposed to 98 μg/L 100 nm Au and 4.8 μg/L 100 nm Ag ENPs. The D. magna nanoparticulate body burden for Au ENP uptake was 613 ± 230 μg/kgww, while the measured nanoparticulate body burden for D. magna exposed to Ag ENPs was 59 ± 52 μg/kgww. Notably, the particle size distributions determined from D. magna tissues suggested minimal shifts in the size distributions of ENPs accumulated, as compared to the exposure media. PMID:24218983

  12. Iodine determination in food by inductively coupled plasma mass spectrometry after digestion by microwave-induced combustion.

    PubMed

    Mesko, Márcia F; Mello, Paola A; Bizzi, Cezar A; Dressler, Valderi L; Knapp, Guenter; Flores, Erico M M

    2010-09-01

    Iodine determination in food samples was performed by inductively coupled plasma mass spectrometry (ICP-MS) after digestion by microwave-induced combustion (MIC). Sample masses up to 500 mg of bovine liver, corn starch, milk powder, or wheat flour were completely combusted using the MIC system. Ammonium nitrate (6 mol l(-1) solution, 50 μl) was used as an aid for ignition and vessels were charged with 15 bar of O(2). The use of H(2)O, 0.9 mmol l(-1) H(2)O(2), 10 to 50 mmol l(-1) (NH(4))(2)CO(3) and 56 mmol l(-1) tetramethylammonium hydroxide was investigated as absorbing solutions, as well as the suitability of performing a reflux step after the combustion process. Digestion of food samples by pressurized microwave-assisted acid digestion, microwave-assisted extraction and conventional extraction of iodine in alkaline solution were also evaluated. Iodine recoveries higher than 99% were obtained using MIC and 50 mmol l(-1) (NH(4))(2)CO(3) or 56 mmol l(-1) tetramethylammonium hydroxide as absorbing solution and with 5 min for the reflux step. Accuracy was evaluated using certified reference materials (bovine muscle, corn bran, and milk powder) and agreement better than 97% was obtained. The limit of quantification by MIC and further ICP-MS determination was 0.002 µg g(-1). Blanks were always low and no memory effects were observed. Digestion by MIC allowed the processing of up to eight samples by each run in 25 min with high efficiency of digestion (residual carbon content lower than 1%) providing a suitable medium for further iodine determination by ICP-MS. PMID:20464381

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

    USGS Publications Warehouse

    Rusk, Brian; Koenig, Alan; Lowers, Heather

    2011-01-01

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

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

    PubMed

    Yan, Neng; Zhu, Zhenli; Jin, Lanlan; Guo, Wei; Gan, Yiqun; Hu, Shenghong

    2015-06-16

    Metal nanoparticles (NPs) determination has recently attracted considerable attention because of the continuing boom of nanotechnology. In this study, a novel method for separation and quantitative characterization of NPs in aqueous suspension was established by coupling thin layer chromatography (TLC) with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Gold nanoparticles (AuNPs) of various sizes were used as the model system. It was demonstrated that TLC not only allowed separation of gold nanoparticles from ionic gold species by using acetyl acetone/butyl alcohol/triethylamine (6:3:1, v/v) as the mobile phase, but it also achieved the separation of differently sized gold nanoparticles (13, 34, and 47 nm) by using phosphate buffer (0.2 M, pH = 6.8), Triton X-114 (0.4%, w/v), and EDTA (10 mM) as the mobile phase. Various experimental parameters that affecting TLC separation of AuNPs, such as the pH of the phosphate buffer, the coating of AuNPs, the concentrations of EDTA and Triton X-114, were investigated and optimized. It was found that separations of AuNPs by TLC displayed size dependent retention behavior with good reproducibility, and the retardation factors (R(f) value) increased linearly with decreasing nanoparticle size. The analytical performance of the present method was evaluated under optimized conditions. The limits of detection were in the tens of pg range, and repeatability (RSD, n = 7) was 6.3%, 5.9%, and 8.3% for 30 ng of 13 nm AuNPs, 34 nm AuNPs, and 47 nm AuNPs, respectively. The developed TLC-LA-ICP-MS method has also been applied to the analysis of spiked AuNPs in lake water, river water, and tap water samples. PMID:26005902

  15. Analysis of laser-produced aerosols by inductively coupled plasma mass spectrometry: transport phenomena and elemental fractionation.

    PubMed

    Koch, J; Wälle, M; Dietiker, R; Günther, D

    2008-02-15

    The transport phenomena of laser-produced aerosols prior to analysis by inductively coupled plasma mass spectrometry (ICPMS) were examined. Aerosol particles were visualized over the cross section of a transport tube attached to the outlet of a conventional ablation cell by light scattering using a pulsed laser source. Experiments were carried out under laminar or turbulent in-cell flow conditions applying throughputs of up to 2.0 L/min and reveal the nature of aerosol transportation to strongly depend on both flow rate and carrier gas chosen. For instance, laser ablation (LA) using laminar in-cell flow and helium as aerosol carrier resulted in stationary but inhomogeneous dispersion patterns. In addition, aerosols appear to be separated into two coexisting phases consisting of (i) dispersed particles that accumulate at the boundary layer of several vortex channel flows randomly arranged along the tube axis and (ii) larger fragments moving inside. The occurrence of these fragments was found to affect the accuracy of Si-, Zn-, and Cd-specific ICPMS analyses of aerosols released by LA of silicate glass (SRM NIST610). Accuracy drifts of more than 10% were observed for helium flow rates of >1 L/min, most probably, due to preferential evaporation and diffusion losses of volatile constituents inside the ICP. The utilization of turbulent in-cell flow made the vortex channels collapse and resulted in an almost complete aerosol homogenization. In contrast, LA using argon as aerosol carrier generally yielded a higher degree of dispersion, which was nearly independent of the flow conditions applied. To illustrate the differences among laminar and turbulent in-cell flow, furthermore, the velocity field inside the ablation cell was simulated by computational fluid dynamics. PMID:18205331

  16. Determination of Hg and Pb in fuels by inductively coupled plasma mass spectrometry using flow injection chemical vapor generation.

    PubMed

    Chen, Feng-yi; Jiang, Shiuh-Jen

    2009-12-01

    An isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) method has been developed for the determination of Hg and Pb in fuels using flow injection vapor generation (VG) as the sample introduction system. A simple and inexpensive in-situ nebulizer/vapor generator was employed in this study. An emulsion containing 10% v/v fuel, 2% m/v Triton X-100 and 1.0% m/v tartaric acid was injected into VG-ICP-MS system for the determination of Hg and Pb. Sodium borohydride was used for vapor generation. Since the sensitivities of Hg and Pb in emulsion and those in aqueous solution are quite different, isotope dilution and standard addition methods were used for the determination of Hg and Pb in selected fuel samples. The influences of vapor generation conditions and emulsion preparation on the ion signals are reported. This method has been applied for the determination of Hg and Pb in various fuel samples such as diesel, gasoline and engine oil obtained locally. The analytical results obtained by isotope dilution and standard addition methods were in good agreement with each other and also with those of digested samples analyzed by pneumatic nebulization ICP-MS. Under the optimum operating conditions, the detection limits obtained were 0.02 and 0.03 ng mL(-1) for Hg and Pb, respectively, in prepared emulsified solutions, corresponding to 0.2 and 0.3 ng mL(-1) of Hg and Pb, respectively, in the original fuel samples. PMID:20009337

  17. Lead levels in fur of rats treated with inorganic lead measured by inductively coupled argon plasma mass spectrometry

    PubMed Central

    Lesage, François-Xavier; Deschamps, Frédèric; Millart, Hervé

    2010-01-01

    The aim of this study was to investigate the relationship between continuous lead exposure and the concentration of this metal in fur. The two main questions we wanted to answer were: 1) Are the fur lead concentrations different according to exposure level? 2) Is the kinetics of lead concentration linear in different compartments? For 12 weeks, 6 rats were force-fed with water containing lead acetate in the following quantities: 0.5 and 50 µg/day. Furs were sampled every two weeks. The lead content of the samples was measured by inductively coupled argon plasma mass spectrometry (ICP-MS). There was a statistical difference (p<0.0001) between fur lead concentration and the three groups (control, low level exposure and high level exposure), between fur lead concentration and time exposure (p<0.0001), and between fur lead concentration and each exposure group at different time exposure (p<0.0001). Thus the level exposure factor and the time exposure factor have an effect on fur lead concentration. Since the determination coefficients were weak for the two exposed groups (0.032 and 0.032), a linear correlation cannot be concluded. The kinetic curves of fur lead concentration are similar for all the exposition groups. Two peaks (at 2 and 8 weeks of exposure) were noted for the two exposed groups. This experimental study cannot conclude a linear relationship to exist between fur lead concentration and exposition duration. It highlights the lack of understanding of mechanisms involved in hair incorporation of metals and raises the question of a cyclic accumulation in hair. A better understanding of the kinetic incorporation of lead in body growths is required. PMID:21331176

  18. 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

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

    NASA Astrophysics Data System (ADS)

    García-Poyo, M. Carmen; Grindlay, Guillermo; Gras, Luis; de Loos-Vollebregt, Margaretha T. C.; Mora, Juan

    2015-03-01

    Results of a systematic study concerning non-spectral interferences from sulfuric acid containing matrices on a large number of elements in inductively coupled plasma-mass spectrometry (ICP-MS) are presented in this work. The signals obtained with sulfuric acid solutions of different concentrations (up to 5% w w- 1) have been compared with the corresponding signals for a 1% w w- 1- nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for 128Te+, 78Se+ and 75As+ were significantly higher when using sulfuric acid matrices (up to 2.2-fold for 128Te+ and 78Se+ and 1.8-fold for 75As+ in the presence of 5 w w-1 sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for 31P+ is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for 128Te+, 78Se+, 75As+ and 31P+ are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S+ species in the plasma. Theoretical data suggest that Os, Sb, Pt, Ir, Zn and Hg could also be involved in sulfur-based charge transfer reactions, but no experimental evidence has been found. The presence of sulfuric acid gives rise to lower ion signals (about 10-20% lower) for the other nuclides tested, thus indicating the negative matrix effect caused by changes in the amount of analyte loading of the plasma. The elemental composition of a certified low-density polyethylene sample (ERM-EC681K) was determined by ICP-MS after two different sample digestion procedures, one of them including sulfuric acid. Element concentrations were in agreement with the certified values, irrespective of the acids used for the digestion. These results demonstrate that the use of matrix-matched standards allows the accurate determination of the tested elements in a sulfuric acid matrix.

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

    USGS Publications Warehouse

    Karakus, M.; Hagni, R.D.; Koenig, A.; Ciftc, E.

    2008-01-01

    Natural sphalerite associated with copper, silver, lead-zinc, tin and tungsten deposits from various world-famous mineral deposits have been studied by cathodoluminescence (CL), laser ablasion inductively coupled plasma mass spectrometry (LA-ICP-MS), electron probe microanalysis (EPMA) and electron paramagnetic resonance (EPR) to determine the relationship between trace element type and content and the CL properties of sphalerite. In general, sphalerite produces a spectrum of CL colour under electron bombardment that includes deep blue, turquoise, lime green, yellow-orange, orange-red and dull dark red depending on the type and concentration of trace quantities of activator ions. Sphalerite from most deposits shows a bright yellow-orange CL colour with ??max centred at 585 nm due to Mn2+ ion, and the intensity of CL is strongly dependent primarily on Fe2+ concentration. The blue emission band with ??max centred at 470-490 nm correlates with Ga and Ag at the Tsumeb, Horn Silver, Balmat and Kankoy mines. Colloform sphalerite from older well-known European lead-zinc deposits and late Cretaceous Kuroko-type VMS deposits of Turkey shows intense yellowish CL colour and their CL spectra are characterised by extremely broad emission bands ranging from 450 to 750 nm. These samples are characterised by low Mn (<10 ppm) and Ag (<1 ppm), and they are enriched in Tl (1-30 ppm) and Pb (80-1500 ppm). Strong green CL is produced by sphalerite from the Balmat-Edwards district. Amber, lime-green and red-orange sphalerite produced weak orange-red CL at room temperatures, with several emission bands centred at 490, 580, 630, 680, 745, with ??max at 630 nm being the strongest. These emission bands are well correlated with trace quantities of Sn, In, Cu and Mn activators. Sphalerite from the famous Ogdensburg and Franklin mines exhibited brilliant deep blue and orange CL colours and the blue CL may be related to Se. Cathodoluminescence behaviour of sphalerite serves to characterise ore

  1. Linearization of calibration curves by aerosol carrier effect of CCl 4 vapor in electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Kántor, Tibor; de Loos-Vollebregt, Margaretha T. C.

    2005-03-01

    Carbon tetrachloride vapor as gaseous phase modifier in a graphite furnace electrothermal vaporizer (GFETV) converts heavy volatile analyte forms to volatile and medium volatile chlorides and produces aerosol carrier effect, the latter being a less generally recognized benefit. However, the possible increase of polyatomic interferences in inductively coupled plasma mass spectrometry (GFETV-ICP-MS) by chlorine and carbon containing species due to CCl 4 vapor introduction has been discouraging with the use of low resolution, quadrupole type MS equipment. Being aware of this possible handicap, it was aimed at to investigate the feasibility of the use of this halogenating agent in ICP-MS with regard of possible hazards to the instrument, and also to explore the advantages under these specific conditions. With sample gas flow (inner gas flow) rate not higher than 900 ml min -1 Ar in the torch and 3 ml min -1 CCl 4 vapor flow rate in the furnace, the long-term stability of the instrument was ensured and the following benefits by the halocarbon were observed. The non-linearity error (defined in the text) of the calibration curves (signal versus mass functions) with matrix-free solution standards was 30-70% without, and 1-5% with CCl 4 vapor introduction, respectively, at 1 ng mass of Cu, Fe, Mn and Pb analytes. The sensitivity for these elements increased by 2-4-fold with chlorination, while the relative standard deviation (RSD) was essentially the same (2-5%) for the two cases in comparison. A vaporization temperature of 2650 °C was required for Cr in Ar atmosphere, while 2200 °C was sufficient in Ar + CCl 4 atmosphere to attain complete vaporization. Improvements in linear response and sensitivity were the highest for this least volatile element. The pyrolytic graphite layer inside the graphite tube was protected by the halocarbon, and tube life time was further increased by using traces of hydrocarbon vapor in the external sheath gas of the graphite furnace. Details

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

    SciTech Connect

    Niu, Hongsen

    1995-02-10

    The fundamental and practical aspects are described for extracting ions from atmospheric pressure plasma sources into an analytical mass spectrometer. Methodologies and basic concepts of inductively coupled plasma mass spectrometry (ICP-MS) are emphasized in the discussion, including ion source, sampling interface, supersonic expansion, slumming process, ion optics and beam focusing, and vacuum considerations. Some new developments and innovative designs are introduced. The plasma extraction process in ICP-MS was investigated by Langmuir measurements in the region between the skimmer and first ion lens. Electron temperature (T{sub e}) is in the range 2000--11000 K and changes with probe position inside an aerosol gas flow. Electron density (n{sub e}) is in the range 10{sup 8}--10{sup 10} {sup {minus}cm }at the skimmer tip and drops abruptly to 10{sup 6}--10{sup 8} cm{sup {minus}3} near the skimmer tip and drops abruptly to 10{sup 6}--10{sup 8} cm{sup {minus}3} downstream further behind the skimmer. Electron density in the beam leaving the skimmer also depends on water loading and on the presence and mass of matrix elements. Axially resolved distributions of electron number-density and electron temperature were obtained to characterize the ion beam at a variety of plasma operating conditions. The electron density dropped by a factor of 101 along the centerline between the sampler and skimmer cones in the first stage and continued to drop by factors of 10{sup 4}--10{sup 5} downstream of skimmer to the entrance of ion lens. The electron density in the beam expansion behind sampler cone exhibited a 1/z{sup 2} intensity fall-off (z is the axial position). An second beam expansion originated from the skimmer entrance, and the beam flow underwent with another 1/z{sup 2} fall-off behind the skimmer. Skimmer interactions play an important role in plasma extraction in the ICP-MS instrument.

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

    PubMed Central

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

    2012-01-01

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

  4. Hydrodynamic chromatography online with single particle-inductively coupled plasma mass spectrometry for ultratrace detection of metal-containing nanoparticles.

    PubMed

    Pergantis, Spiros A; Jones-Lepp, Tammy L; Heithmar, Edward M

    2012-08-01

    Nanoparticle (NP) determination has recently gained considerable interest since a growing number of engineered NPs are being used in commercial products. As a result, their potential to enter the environment and biological systems is increasing. In this study, we report on the development of a hyphenated analytical technique for the detection and characterization of metal-containing NPs, i.e., their metal mass fraction, size, and number concentration. Hydrodynamic chromatography (HDC), suitable for sizing NPs within the range of 5 to 300 nm, was coupled online to inductively coupled plasma mass spectrometry (ICPMS), providing for an extremely selective and sensitive analytical tool for the detection of NPs. However, a serious drawback when operating the ICPMS in its conventional mode is that it does not provide data regarding NP number concentrations and, thus, any information about the metal mass fraction of individual NPs. To address this limitation, we developed single particle (SP) ICPMS coupled online to HDC as an analytical approach suitable for simultaneously determining NP size, NP number concentration, and NP metal content. Gold (Au) NPs of various sizes were used as the model system. To achieve such characterization metrics, three calibrations were required and used to convert ICPMS signal spikes into NPs injected, NP retention time on the HDC column to NP size, and ions detected per signal spike or per NP to metal content in each NP. Two calibration experiments were required in order to make all three calibrations. Also, contour plots were constructed in order to provide for a convenient and most informative viewing of this data. An example of this novel analytical approach was demonstrated for the analysis of Au NPs that had been spiked into drinking water at the ng Au L(-1) level. The described technique gave limits of detection for 60 nm Au NPs of approximately 2.2 ng Au L(-1) or expressed in terms of NP number concentrations of 600 Au NPs mL(-1

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

    PubMed

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

    2012-05-15

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

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

    PubMed

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

    2004-03-24

    In this work the quantitative determination and analytical speciation of arsenic were undertaken in different types of nuts, randomly purchased from local markets. The hardness of the whole nuts and high lipid content made the preparation of this material difficult for analysis. The lack of sample homogeneity caused irreproducible results. To improve the precision of analysis, arsenic was determined separately in nut oil and in the defatted sample. The lipids were extracted from the ground sample with the two portions of a mixture of chloroform and methanol (2:1). The defatted material was dried and ground again, yielding a fine powder. The nut oil was obtained by combining the two organic extracts and by evaporating the solvents. The two nut fractions were microwave digested, and total arsenic was determined by inductively coupled plasma mass spectrometry (ICP-MS). The results obtained for oils from different types of nuts showed element concentration in the range 2.9-16.9 ng g(-)(1). Lower levels of arsenic were found in defatted material (<0.1 ng g(-)(1) with the exception of Brazil nuts purchased with and without shells, 3.0 and 2.8 ng g(-)(1) respectively). For speciation analysis of arsenic in nut oils, elemental species were extracted from 2 g of oil with 12 mL of chloroform/methanol (2:1) and 8 mL of deionized water. The aqueous layer, containing polar arsenic species, was evaporated and the residue dissolved and analyzed by ion chromatography-ICP-MS. The anion exchange chromatography enabled separation of As(III), dimethylarsinic acid (DMAs(V)), monomethylarsonic acid (MMAs(V)), and As(V) within 8 min. Several types of nuts were analyzed, including walnuts, Brazil nuts, almonds, cashews, pine nuts, peanuts, pistachio nuts, and sunflower seeds. The recovery for the speciation procedure was in the range 72.7-90.6%. The primary species found in the oil extracts were As(III) and As(V). The arsenic concentration levels in these two species were 0.7-12.7 and 0

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

    PubMed

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

    2015-01-01

    The fast sequential multi-element determination of 11 elements present at different concentration levels in environmental samples and drinking waters has been investigated using high-resolution continuum source flame atomic absorption spectrometry. The main lines for Cu (324.754 nm), Zn (213.857 nm), Cd (228.802 nm), Ni (232.003 nm) and Pb (217.001 nm), main and secondary absorption lines for Mn (279.482 and 279.827 nm), Fe (248.327, 248.514 and 302.064 nm) and Ca (422.673 and 239.856 nm), secondary lines with different sensitivities for Na (589.592 and 330.237 nm) and K (769.897 and 404.414 nm) and a secondary line for Mg (202.582 nm) have been chosen to perform the analysis. A flow injection system has been used for sample introduction so sample consumption has been reduced up to less than 1 mL per element, measured in triplicate. Furthermore, the use of multiplets for Fe and the side pixel registration approach for Mg have been studied in order to reduce sensitivity and extend the linear working range. The figures of merit have been calculated and the proposed method was applied to determine these elements in a pine needles reference material (SRM 1575a), drinking and natural waters and soil extracts. Recoveries of analytes added at different concentration levels to water samples and extracts of soils were within 88-115% interval. In this way, the fast sequential multi-element determination of major and minor elements can be carried out, in triplicate, with successful results without requiring additional dilutions of samples or several different strategies for sample preparation using about 8-9 mL of sample. PMID:25479863

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  9. Multi-element analysis of pyrite ores using polarized energy-dispersive X-ray fluorescence spectrometry.

    PubMed

    Ustündağ, Zafer; Ustündağ, Ilknur; Kağan Kadioğlu, Yusuf

    2007-07-01

    X-ray fluorescence (XRF) spectrometry is used worldwide in geological material analysis. This study, applies polarized energy-dispersive X-ray fluorescence (PEDXRF) Spectrometer and compares in the samples of Rize-Cayeli and Mardin pyrite ores. The samples of pyrite ore were collected from the Rize and Mardin in Turkey. The prepared samples were analyzed using a PEDXRF spectrometer. The result of the analysis shows the presence of many elements including rare-earth elements (from Na to Th). The accuracy and precision of the technique for chemical analysis is demonstrated by analyzing USGS standards, GEOL, GBW 7109 and GBW-7309 sediment. PMID:17459714

  10. Methyl mercury in nail clippings in relation to fish consumption analysis with gas chromatography coupled to inductively coupled plasma mass spectrometry: a first orientation.

    PubMed

    Krystek, Petra; Favaro, Paulo; Bode, Peter; Ritsema, Rob

    2012-08-15

    For the identification of human exposure to one of the most toxic compounds, which is methyl mercury (MeHg(+)), fingernail clippings were selected as the matrix of interest. Within this pilot study, six samples from different origins and from people with different food consumption patterns were chosen. Species-analysis of MeHg(+) was performed according to the following procedure: dissolution of the sample material in tetramethylammonium hydroxide (TMAH), derivatisation of MeHg(+) with sodium tetraethylborate (NaBEt(4)), extraction into iso-octane and measurement with gas chromatography hyphenated to inductively coupled plasma mass spectrometry (GC-ICPMS) for the quantification MeHg(+). PMID:22841050

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

    PubMed

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

    2016-02-01

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

  12. Multi-element determination in acid-digested soy protein formulations by inductively coupled plasma-optical emission spectrometry.

    PubMed

    Morte, Elane S Boa; Costa, Leticia M; Nobrega, Joaquim A; Korn, Maria das Gracas A

    2008-05-01

    The concentrations of major (Ca, K, Mg, Na and P) and trace elements (Al, Cu and Fe) in soy protein formulations sold in Bahia (Brazil) were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES). Liquid and powdered soy protein formulation samples, both whole and light, were digested using a conventional heating program on a hot-plate. The powdered samples were prepared according to the label instructions for human consumption. A 5.0-ml aliquot of the soy protein emulsion was transferred to a borosilicate Erlenmeyer and concentrated nitric and sulfuric acid added. After a digestion time of approximately 50 min, hydrogen peroxide was added and heating continued to give a final volume of approximately 5 ml; the colorless digests were then made up to 15.0 ml with deionised water. Residual acid content was determined by acid-base titration. Good agreement between measured and certified values for all analytes in a non-fat milk powder (NIST SRM 1549) indicated that the method was suitable for major and trace elements determination in soy protein formulations. PMID:18473216

  13. Evaluation of Laser Ablation Inductively Coupled Plasma Mass Spectrometry for the Quantitative Determination of Lead in Different Parts of Archeological Human Teeth

    PubMed Central

    Bellis, David J.; Parsons, Patrick J.; Jones, Joseph; Amarasiriwardena, Dula

    2011-01-01

    The lead content of teeth or tooth-parts has been used as a biomarker of cumulative lead exposure in clinical, epidemiological, environmental, and archaeological studies. Through the application of laser ablation inductively coupled plasma mass spectrometry, a pilot study of the micrometer-scale distribution and quantification of lead was conducted for two human teeth obtained from an archeological burial site in Manhattan, New York, USA. Lead was highly localized within each tooth, with accumulation in circumpulpal dentine and cementum. The maximum localized lead content in circumpulpal dentine was remarkably high, almost 2000 μg g-1, compared to the mean enamel and dentine content of about 5 μg g-1. The maximum lead content in cementum was approximately 700 μg g-1. The large quantity of cementum found in the teeth suggested that the subjects had hypercementosis (excess cementum formation) of the root, a condition reported to have been prevalent among African-American slave populations. The distribution of lead in these human teeth was remarkably similar to the distribution that we previously reported in the teeth of present-day lead-dosed goats. The data shown demonstrate the feasibility of using laser ablation inductively coupled plasma mass spectrometry to examine lead exposure in archaeological studies. PMID:22467976

  14. Development of cadmium/silver/palladium separation by ion chromatography with quadrupole inductively coupled plasma mass spectrometry detection for off-line cadmium isotopic measurements.

    PubMed

    Gautier, C; Bourgeois, M; Isnard, H; Nonell, A; Stadelmann, G; Goutelard, F

    2011-08-01

    A separation method was investigated to perform off-line cadmium isotopic measurements on a (109)Ag transmutation target. Ion chromatography (IC) with Q ICPMS detection (quadrupole inductively coupled plasma mass spectrometry detection) was chosen to separate cadmium from the isobarically interfering elements, silver and palladium, present in the sample. The optimization of chromatographic conditions was particularly studied. Several anion and cation columns (Dionex AG11(®), CS10(®) and CS12(®)) were compared with different mobile phases (HNO(3), HCl). The separation procedure was achieved with a carboxylate-functionalized cation exchange CS12 column using 0.5 M HNO(3) as eluent. The developed technique yielded satisfactory results in terms of separation factors (greater than 5) and provides an efficient solution to obtain rapidly purified cadmium fractions (decontamination factors higher 100,000 for silver and palladium) which can directly be analyzed by multi collection inductively coupled plasma mass spectrometry (MC ICPMS). By applying the proposed procedure, accurate and precise cadmium isotope ratios were determined for the irradiated (109)Ag transmutation target. PMID:21703628

  15. Direct determination of trace rare earth elements in ancient porcelain samples with slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Xiang, Guoqiang; Jiang, Zucheng; He, Man; Hu, Bin

    2005-10-01

    A method for the direct determination of trace rare earth elements in ancient porcelain samples by slurry sampling fluorinating electrothermal vaporization inductively coupled plasma mass spectrometry was developed with the use of polytetrafluoroethylene as fluorinating reagent. It was found that Si, as a main matrix element in ancient porcelain sample, could be mostly removed at the ashing temperature of 1200 °C without considerable losses of the analytes. However, the chemical composition of ancient porcelain sample is very complicated, which makes the influences resulting from other matrix elements not be ignored. Therefore, the matrix effect of ancient porcelain sample was also investigated, and it was found that the matrix effect is obvious when the matrix concentration was larger than 0.8 g l - 1 . The study results of particle size effect indicated that when the sample particle size was less than 0.057 mm, the particle size effect is negligible. Under the optimized operation conditions, the detection limits for rare earth elements by fluorinating electrothermal vaporization inductively coupled plasma mass spectrometry were 0.7 ng g - 1 (Eu)-33.3 ng g - 1 (Nd) with the precisions of 4.1% (Yb)-10% (La) ( c = 1 μg l - 1 , n = 9). The proposed method was used to directly determine the trace rare earth elements in ancient porcelain samples produced in different dynasty (Sui, Ming and Qing), and the analytical results are satisfactory.

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

    PubMed

    Stanislawska, Magdalena; Janasik, Beata; Wasowicz, Wojciech

    2013-12-15

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

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

    PubMed

    Bierla, Katarzyna; Flis-Borsuk, Anna; Suchocki, Piotr; Szpunar, Joanna; Lobinski, Ryszard

    2016-06-22

    The reaction of sunflower oil with selenite produces a complex mixture of selenitriglycerides with antioxidant and anticancer properties. To obtain insight into the identity and characteristics of the species formed, an analytical approach based on the combination of high-performance liquid chromatography (HPLC) with (78)Se-specific selenium detection by inductively coupled plasma mass spectrometry (ICP MS) and high-resolution (100 000), high mass accuracy (<1 ppm) molecule-specific detection by electrospray-Orbitrap MS(3) was developed. For the first time, a non-aqueous mobile phase gradient was used in reversed-phase HPLC-ICP MS for the separation of a complex mixture of selenospecies and a mathematical correction of the background signal was developed. The identical chromatographic conditions served for the sample introduction into electrospray MS. Two types of samples were analyzed: sunflower oil dissolved in isopropanol and methanol extract of the oil containing 65% selenium. HPLC-ICP MS showed 14 peaks, 11 of which could also be detected in the methanol extract. Isotopic patterns corresponding to molecules with one or two selenium atoms could be attributed by Orbitrap MS at the retention times corresponding to the HPLC-ICP MS peak apexes. Structural data for these species were acquired by MS(2) and MS(3) fragmentation of protonated or sodiated ions using high-energy collisional dissociation (HCD). A total of 11 selenium-containing triglycerol derivatives resulting from the oxidation of one or two double bonds of linoleic acid and analogous derivatives of glycerol-mixed linoleate(s)/oleinate(s) have been identified for the first time. The presence of these species was confirmed by the targeted analysis in the total oil isopropanol solution. Their identification corroborated the predicted elution order in reversed-phase chromatography: LLL (glycerol trilinoleate), LLO (glycerol dilinoleate-oleinate), LOO (glycerol linoleate-dioleinate), OOO (glycerol

  18. 2D elemental mapping of sections of human kidney stones using laser ablation inductively-coupled plasma-mass spectrometry: Possibilities and limitations

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  19. Identification of gunshot residues in fabric targets using sector field inductively coupled plasma mass spectrometry technique and ternary graphs.

    PubMed

    Freitas, João Carlos D; Sarkis, Jorge E Souza; Negrini Neto, Osvaldo; Viebig, Sônia Bocamino

    2012-03-01

    During criminal investigations involving firearms, the detection of gunshot residues (GSRs) is one of the most important evidences. In the present study, a new method to identify trace evidences of GSRs, deposited around the bullet entrance hole, in different types of fabrics used as targets, is described. The experiments were carried out using a 0.38-inch caliber revolver, and 9-mm and 0.40-inch caliber pistols. Testimonies of 2.25 cm(2) of the fabrics were cut around the bullet entrance and digested with 10% nitric acid. Antimony, barium, and lead were analyzed in the remaining solution using a sector field inductively coupled plasma mass spectrometer. The concentrations of the elements were detected at levels up to few microgram per square centimeter. The use of ternary graphics allowed us to identify specific patterns of distribution for blank samples and the clear distinction between the revolver and pistols used. PMID:22074259

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

    SciTech Connect

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

    1993-01-01

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

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

    SciTech Connect

    LaFerriere, Brian D.; Maiti, Tapas C.; Arnquist, Isaac J.; Hoppe, Eric W.

    2015-03-01

    This study describes a novel sample preparation and assay method developed in support of the MAJORANA DEMONSTRATOR experiment for the determination of thorium and uranium levels in copper and lead shielding components. Meticulously clean sample preparation methods combined with novel anion exchange separations for analyte pre-concentration and matrix removal were developed. Quantification was performed by inductively coupled plasma mass spectrometry. Detection limits of 0.0084 pg 232Th/g and 0.0106 pg 238U/g were determined for copper, while detection limits of 0.23 pg 232Th/g and 0.46 pg 238U/g were achieved for lead. These methods allow the Majorana Collaboration to accurately assay detector components and ensure that the experiment’s stringent radiopurity requirements are met.

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

    PubMed

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

    2012-08-15

    Analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for determination of lanthanides in plant materials was investigated and compared with neutron activation analysis (NAA) as well as ion chromatography (IC) with UV-VIS detection. Two sample preparation protocols were tested: (i) microwave assisted digestion by concentrated nitric acid; (ii) microwave digestion involving silica and fluoride removal, followed by the selective and quantitative lanthanides group separation from the plant matrix. Several Certified Reference Materials (CRM) of plant origin were used for the evaluation of the accuracy of the applied analytical procedures. The consistency of results, obtained by various methods, enabled to establish the tentative recommended values (TRV) for several missing elements in one of CRMs. The ICP-MS, due to its very high sensitivity, has the potential to contribute to this aim. The discrepancy of the results obtained by various methods was discussed in a view of possible matrix effects related to the composition of investigated materials. PMID:22841084

  3. Ultra-trace determination of iodine in sediments and biological material using UV photochemical generation-inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Grinberg, Patricia; Sturgeon, Ralph E.

    2009-03-01

    Several sample preparation techniques have been evaluated for the determination of iodine using UV-photochemical generation-quadrupole inductively coupled plasma mass spectrometry. Thermal decomposition of samples at 1000 °C followed by capture of the liberated iodine in dilute acetic acid permitted subsequent UV-photochemical generation of a volatile iodine species that serves to enhance sensitivity 25-fold over conventional solution nebulization, delivering reagent blank detection limits of 8.75 pg g -1 127I and 0.075 pg g -1 129I for solid samples (400 mg test mass). The methodology was validated through determination of total iodine in several Standard Reference Materials, including NIST 1572 Citrus leaves, NIST 1549 Non-fat milk powder, NIST 1566a Oyster tissue and NIST 2709 San Joaquin Soil. Liberation of iodine from samples and its collection as well as photochemical generation were quantitative, permitting calibration to be achieved using standards prepared in dilute acetic acid.

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

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

    SciTech Connect

    Witte, Travis

    2011-01-01

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

  6. Intercomparison of inductively coupled plasma mass spectrometry, quantitative neutron capture radiography, and prompt gamma activation analysis for the determination of boron in biological samples.

    PubMed

    Schütz, C L; Brochhausen, C; Hampel, G; Iffland, D; Kuczewski, B; Otto, G; Schmitz, T; Stieghorst, C; Kratz, J V

    2012-10-01

    Boron determination in blood and tissue samples is a crucial task especially for treatment planning, preclinical research, and clinical application of boron neutron capture therapy (BNCT). Comparison of clinical findings remains difficult due to a variety of analytical methods, protocols, and standard reference materials in use. This paper addresses the comparability of inductively coupled plasma mass spectrometry, quantitative neutron capture radiography, and prompt gamma activation analysis for the determination of boron in biological samples. It was possible to demonstrate that three different methods relying on three different principles of sample preparation and boron detection can be validated against each other and yield consistent results for both blood and tissue samples. The samples were obtained during a clinical study for the application of BNCT for liver malignancies and therefore represent a realistic situation for boron analysis. PMID:22918535

  7. Quantification of modifiers in advanced materials based on zinc oxide by total reflection X-ray fluorescence and inductively coupled plasma mass spectrometry

    NASA Astrophysics Data System (ADS)

    Filatova, Daria G.; Alov, Nikolai V.; Vorobyeva, Natalia A.; Rumyantseva, Marina N.; Sharanov, Pavel Yu.; Seregina, Irina F.; Gaskov, Alexander M.

    2016-04-01

    A novel approach to quantification of Ga and Zn modifiers in advanced materials based on zinc oxide is presented. The approach includes a combination of total reflection X-ray fluorescence (TXRF) and inductively coupled plasma mass spectrometry (ICP-MS) for determination and validation of the results. It is suggested to use aqueous standards for the direct determination of elements in powder samples by TXRF with a relative standard deviation no more than sr = 0.11. The accuracy of these results was proved by ICP-MS after the sample decomposition, sr(In) = 0.05, sr(Ga) = 0.06 and sr(Zn) = 0.06. It was established that there is a possibility to determine indium above 300 ppb on the background of K-M3 line of argon.

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

    SciTech Connect

    Havrilla, George Joseph; Gonzalez, Jhanis

    2015-06-10

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

  9. Ultra-Sensitive Elemental Analysis Using Plasmas 5.Speciation of Arsenic Compounds in Biological Samples by High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry System

    NASA Astrophysics Data System (ADS)

    Kaise, Toshikazu

    Arsenic originating from the lithosphere is widely distributed in the environment. Many arsenicals in the environment are in organic and methylated species. These arsenic compounds in drinking water or food products of marine origin are absorbed in human digestive tracts, metabolized in the human body, and excreted viatheurine. Because arsenic shows varying biological a spects depending on its chemical species, the biological characteristics of arsenic must be determined. It is thought that some metabolic pathways for arsenic and some arsenic circulation exist in aqueous ecosystems. In this paper, the current status of the speciation analysis of arsenic by HPLC/ICP-MS (High Performance Liquid Chromatography-Inductively Coupled Plasma Mass spectrometry) in environmental and biological samples is summarized using recent data.

  10. Determination of rare earth elements in human hair and wheat flour reference materials by inductively coupled plasma mass spectrometry with dry ashing and microwave digestion

    NASA Astrophysics Data System (ADS)

    Ming, Yin; Bing, Li

    1998-09-01

    A method was developed for the determination of all rare earth elements (REEs) at sub ng g -1 levels in human hair (GBW 09101, SRM, Republic of China) and wheat flour (GBW 08503, SRM, Republic of China) by Inductively coupled plasma mass spectrometry (ICP-MS). The values obtained by dry ashing and microwave oven digestion procedures were compared with those obtained by traditional open vessel acid digestion method. The validity of the analytical procedure was examined by analyzing spiked samples and two vegetables (GBW 07603 and GBW 07605, SRMs, Republic of China). The results are satisfactory. The detection limits for 14 REEs ranged from 0.0039 to 0.0003 ng cm -3 in solution and the quantification limits ranged from 0.16 to 0.01 ng g -1 in solid sample. The precision for most REEs were less than 10% RSD.

  11. Portable x-ray fluorescence for assessing trace elements in rice and rice products: Comparison with inductively coupled plasma-mass spectrometry.

    PubMed

    Fleming, David E B; Foran, Kelly A; Kim, Jong Sung; Guernsey, Judy R

    2015-10-01

    Portable x-ray fluorescence (XRF) was investigated as a means of assessing trace elements in rice and rice products. Using five measurement trials of 180 s real time, portable XRF was first used to detect arsenic (As), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), and zinc (Zn) in a variety of rice samples. The same samples were then microwave-digested and used to determine elemental concentrations using inductively coupled plasma-mass spectrometry (ICP-MS). The concentrations of As, Mn, Fe, Cu, and Zn determined by ICP-MS were found to be consistent with other recent studies involving various types of rice and rice products. When assessing for As, Mn, Fe, Cu, and Zn, comparison of results between XRF amplitude and ICP-MS concentration (wet weight) demonstrated a linear relationship with a significant correlation. A significant correlation between XRF amplitude and ICP-MS concentration was not found when assessing for Ni. PMID:26203871

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Claverie, Fanny; Pécheyran, Christophe; Mounicou, Sandra; Ballihaut, Guillaume; Fernandez, Beatriz; Alexis, Joël; Lobinski, Ryszard; Donard, Olivier F. X.

    2009-07-01

    A 2D high repetition rate femtosecond laser ablation strategy (2-mm wide lane) previously developed for the detection of selenoproteins in gel electrophoresis by inductively coupled plasma mass spectrometry was found to increase signal sensitivity by a factor of 40 compared to conventional nanosecond ablation (0.12-mm wide lane) [G. Ballihaut, F. Claverie, C. Pécheyran, S. Mounicou, R. Grimaud and R. Lobinski, Sensitive Detection of Selenoproteins in Gel Electrophoresis by High Repetition Rate Femtosecond Laser Ablation-Inductively Coupled Plasma Mass Spectrometry, Anal. Chem. 79 (2007) 6874-6880]. Such improvement couldn't be explained solely by the difference of amount of material ablated, and then, was attributed to the aerosol properties. In order to validate this hypothesis, the characterization of the aerosol produced by nanosecond and high repetition rate femtosecond laser ablation of polyacrylamide gels was investigated. Our 2D high repetition rate femtosecond laser ablation strategy of 2-mm wide lane was found to produce aerosols of similar particle size distribution compared to nanosecond laser ablation of 0.12-mm wide lane, with 38% mass of particles < 1 µm. However, at high repetition rate, when the ablated surface was reduced, the particle size distribution was shifted toward thinner particle diameter (up to 77% for a 0.12-mm wide lane at 285 µm depth). Meanwhile, scanning electron microscopy was employed to visualize the morphology of the aerosol. In the case of larger ablation, the fine particles ejected from the sample were found to form agglomerates due to higher ablation rate and then higher collision probability. Additionally, investigations of the plasma temperature changes during the ablation demonstrated that the introduction of such amount of polyacrylamide gel particles had very limited impact on the ICP source (Δ T~ 25 ± 5 K). This suggests that the cohesion forces between the thin particles composing these large aggregates were weak

  14. Inductively coupled plasma mass spectrometry as a simple, rapid, and inexpensive method for determination of uranium in urine and fresh water: Comparison with LIF

    SciTech Connect

    Karpas, Z.; Halicz, L.; Roiz, J.

    1996-12-01

    A simple method, based on inductively coupled plasma mass spectrometry, for determination of uranium in urine at levels that indicate occupational exposure, is presented. Sample preparation involves a fifty-fold dilution of the urine by nitric acid (2% HNO{sub 3}) and no other chemical treatment or separation. The analysis itself is completed in under 3 min. The analytical procedure is fully autominated so that a technician may perform over 100 analyses per day. With proper control of the blank contribution, a lower limit of detection of 3 ng L{sup {minus}1} in the original urine sample was achieved. Uranium concentrations in the range 6-30 ng L{sup {minus}1} were found in urine samples of people that are not occupationally exposed. The validity of the results was demonstrated through measurement of standards, controlled uranium addition experiments and, at higher concentrations, by comparison with results obtained by an independent method based on laser induced fluorescence. The laser induced fluorescence technique was found to be sufficient for detection of occupational exposure at an action level of 1.5 {mu}g L{sup {minus}1}. Use of internal standards, indium, and thallium, improved quantification by about 10%, but was not deemed necessary for routine analysis. The inductively coupled plasma mass spectrometry is also ideally suited for monitoring uranium in fresh water and drinking water, as no sample dilution is required and the lower limit of detection is below 0.15 ng L{sup {minus}1}. 41 refs., 4 figs., 5 tabs.

  15. Measurement of airborne gunshot particles in a ballistics laboratory by sector field inductively coupled plasma mass spectrometry.

    PubMed

    Diaz, Ernesto; Sarkis, Jorge E Souza; Viebig, Sônia; Saldiva, Paulo

    2012-01-10

    The present study aimed determines lead (Pb), antimony (Sb) and barium (Ba) as the major elements present in GSR in the environmental air of the Ballistics Laboratory of the São Paulo Criminalistics Institute (I.C.-S.P.), São Paulo, SP, Brazil. Micro environmental monitors (mini samplers) were located at selected places. The PM(2.5) fraction of this airborne was collected in, previously weighted filters, and analyzed by sector field inductively coupled plasma mass spectrometer (SF-HR-ICP-MS). The higher values of the airborne lead, antimony and barium, were found at the firing range (lead (Pb): 58.9 μg/m(3); barium (Ba): 6.9 μg/m(3); antimony (Sb): 7.3 μg/m(3)). The mean value of the airborne in this room during 6 monitored days was Pb: 23.1 μg/m(3); Ba: 2.2 μg/m(3); Sb: 1.5 μg/m(3). In the water tank room, the air did not show levels above the limits of concern. In general the airborne lead changed from day to day, but the barium and antimony remained constant. Despite of that, the obtained values suggest that the workers may be exposed to airborne lead concentration that can result in an unhealthy environment and could increase the risk of chronic intoxication. PMID:21831549

  16. Determination of trace impurities in high purity gold by inductively coupled plasma mass spectrometry with prior matrix removal by electrodeposition

    NASA Astrophysics Data System (ADS)

    Sun, Y. C.; Hsieh, C. H.; Lin, T. S.; Wen, J. C.

    2000-09-01

    A novel method for the determination of 11 trace impurities (Be, Mg, Cr, Mn, Ni, Cu, Zn, Ag, Pd, Sn and Pb) in high purity gold with a combination of electrochemical deposition separation and inductively coupled plasma mass spectrometric measurement was investigated. In the present study, an efficient separation procedure was developed to remove the gold matrix by the electrodepositon method on the basis of the difference in reduction potential of gold and the other trace impurities. The effects of deposition potential, deposition time and composition of the electrolyte on the separation efficiency were studied. According to our experimental results, most impurities, except for silver, can remain in the electrolyte and the interference from gold can be completely removed through the application of electrodeposition at suitable potential. To achieve simultaneous separation of silver from the gold matrix, a unique complexation reaction between silver ions and ammonia ions was successfully employed to alter the reduction potential of silver ion. By way of a suitable adjustment of the deposition potential and the composition of electrolytes, the spike recoveries of 11 interesting impurities were found to be in the range of 85-105%. The limit of detection (based on the 3-σ criterion) of these elements was 10 -1-10 -2 μg g -1. The applicability of the proposed method has also been validated by the analysis of high purity gold reference materials (FAU9 and FAU11, Royal Canadian Mint). Comparing with the certified values, the recoveries of interesting elements were found to be in the range of 82-118% through the use of proposed method.

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

    NASA Astrophysics Data System (ADS)

    Ivanov, Krasimir; Zaprjanova, Penka; Petkova, Milena; Stefanova, Violeta; Kmetov, Veselin; Georgieva, Deyana; Angelova, Violina

    2012-05-01

    The most widely used method for determination of total phosphorus in soils is perchloric acid digestion, followed by a colorimetric assay to measure the concentration of P in solution. The first part of this study compares an alternative digestion method, using aqua regia (ISO 11466 and EPA Method 3052), with perchloric acid digestion procedure, and also compares inductively coupled plasma mass spectroscopy (ICP-MS) with colorimetry for the measurement of P on the basis of five internationally certified standard soils and 20 real-life soils with widely different extractability of phosphorus. The phosphorus concentration was determined by means of the reduced phosphomolybdenum blue and ICP-MS. The relationship between methods has been examined statistically. Good agreement of the results from colorimetry and ICP-MS was established for all certified soils. The microwave-assisted digestion with aqua regia was comparable, both in precision and accuracy, with the hot plate aqua regia method. The phosphorus concentration found with the HF + HClO4 digestion method was in good agreement with the certified mean values, while the superiority in extracting phosphorus, when compared to other methods, was obvious. Soil testing for plant-available phosphorus in Bulgaria and many European countries is most commonly conducted using acid Ca-lactate extraction (Egner-Riehm test) and alkaline sodium bicarbonate extraction (BDS ISO 11263:2002), based on Olsen test, followed by a colorimetric assay to measure the concentration of P in solution. The second part of this study reports the differences between Egner-Riehm test and BDS ISO 11263:2002 measured colorimetrically and by ICP-MS. Fifty soils were selected from South Bulgaria to represent a wide range of soil properties. It was established that ICP-MS consistently yielded significantly higher P concentrations than the colorimetric method in both extraction tests, and the relative differences were greatest in soils with lower P

  18. Solid-phase microextraction low temperature plasma mass spectrometry for the direct and rapid analysis of chemical warfare simulants in complex mixtures.

    PubMed

    Dumlao, Morphy C; Jeffress, Laura E; Gooding, J Justin; Donald, William A

    2016-06-21

    Solid-phase microextraction (SPME) is directly integrated with low temperature plasma ionisation mass spectrometry to rapidly detect organophosphate chemical warfare agent simulants and their hydrolysis products in chemical mixtures, including urine. In this sampling and ionization method, the fibre serves: (i) to extract molecules from their native environment, and (ii) as the ionization electrode that is used to desorb and ionize molecules directly from the SPME surface. By use of a custom fabricated SPME fibre consisting of a stainless steel needle coated with a Linde Type A (LTA) zeolitic microporous material and low temperature plasma mass spectrometry, protonated dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP) and pinacolyl methylphosphonic acid (PinMPA) can be detected at less than 100 ppb directly in water and urine. Organophosphates were not readily detected by this approach using an uncoated needle in negative control experiments. The use of the LTA coating significantly outperformed the use of a high alumina Zeolite Socony Mobil-5 (ZSM-5) coating of comparable thickness that is significantly less polar than LTA. By conditioning the LTA probe by immersion in an aqueous CuSO4 solution, the ion abundance for protonated DMMP increased by more than 300% compared to that obtained without any conditioning. Sample recovery values were between 96 and 100% for each analyte. The detection of chemical warfare agent analogues and hydrolysis products required less than 2 min per sample. A key advantage of this sampling and ionization method is that analyte ions can be directly and rapidly sampled from chemical mixtures, such as urine and seawater, without sample preparation or chromatography for sensitive detection by mass spectrometry. This ion source should prove beneficial for portable mass spectrometry applications because relatively low detection limits can be obtained without the use of compressed gases, fluid pumps, and lasers. Moreover, the

  19. Mercury speciation analysis in sea water by solid phase microextraction?gas chromatography?inductively coupled plasma mass spectrometry using ethyl and propyl derivatization. Matrix effects evaluation

    NASA Astrophysics Data System (ADS)

    Bravo-Sánchez, Luis R.; Ruiz Encinar, Jorge; Fidalgo Martínez, José I.; Sanz-Medel, Alfredo

    2004-01-01

    An approach to the speciation analysis of mercury in sea-water samples at sub-ppt levels by means of the hyphenation of solid phase microextraction to gas chromatography-inductively coupled plasma mass spectrometry was developed. Blank values turned out to be the limiting factor for lower detection limits of inorganic mercury. Thus, all the reagents were thoroughly cleaned using laboratory made microcolumns packed with 8-hydroxyquinoline on TSK gel. Sodium tetrapropylborate (NaBPr 4) synthesized for the purpose of derivatization of the mercury species resulted in better analytical performances of the method, probably due to lower mercury contamination, than commercial sodium tetraethylborate (NaBEt 4). Detection limits down to a few picogram per liter for both mercury and methylmercury were obtained using NaBPr 4. The high salt content of sea-water samples was responsible for strong matrix effects, which were overcome by using standards additions to the samples. The validation of the methodology was carried out by direct comparison of the results for inorganic mercury with those obtained using a flow injection system followed by preconcentration/trapping of the species and its detection by atomic absorption spectrometry. The proposed method was applied to the determination of mercury and methylmercury in coastal sea-water samples from Gijón (Asturias, Spain) and results obtained are discussed in the light of the butyltin levels previously determined in the same area.

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

    NASA Astrophysics Data System (ADS)

    Hubert, Amélie; Claverie, Fanny; Pécheyran, Christophe; Pointurier, Fabien

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

  1. Determination of trace phosphorus in high purity tantalum materials by inductively coupled plasma mass spectrometry subsequent to matrix separation with on-line anion exchange/coprecipitation.

    PubMed

    Kozono, Shuji; Takahashi, Shigeto; Haraguchi, Hiroki

    2002-02-01

    An on-line matrix separation/inductively coupled plasma mass spectrometry (ICP-MS) method is proposed for the determination of trace amounts of phosphorus in high purity tantalum metal, tantalum (V) oxide, and tantalum pentaethoxide. In the present method, the matrix tantalum in the sample solution was adsorbed on the anion exchange resin, and phosphorus (phosphate ion) was eluted with the carrier solution of HF and HNO3 mixture. Then, the effluent solution was subsequently mixed with bismuth solution and aqueous ammonia solution to coprecipitate phosphate together with bismuth hydroxide. The precipitate formed was collected on the in-line membrane filter to wash out nitric acid with pure water, and then dissolved with hydrochloric acid. The obtained phosphorus sample solution was introduced directly into the nebulizer of ICP-MS for the determination of phosphorus. Phosphorus was determined at the molecular ion signal of 31P16O+ (m/z 47). The detection limit (3sigma) of phosphorus in the present method was 1.3 ng mL(-1) as the sample solution basis, and the relative standard deviation for 30 ng mL(-1) of phosphorus in the standard solution was 4.3% in the replicate measurements (n=11). The present method was applied to the analysis of high purity tantalum materials. The concentrations of phosphorus in tantalum samples were in fairly good agreement with those obtained by glow discharge mass spectrometry (GDMS). PMID:11939629

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

    NASA Astrophysics Data System (ADS)

    de Gois, Jefferson Santos; Pereira, Éderson R.; Welz, Bernhard; Borges, Daniel L. G.

    2015-03-01

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

  3. Determination of major elements by wavelength-dispersive X-ray fluorescence spectrometry and trace elements by inductively coupled plasma mass spectrometry in igneous rocks from the same fused sample (110 mg)

    NASA Astrophysics Data System (ADS)

    Amosova, Alena A.; Panteeva, Svetlana V.; Chubarov, Victor M.; Finkelshtein, Alexandr L.

    2016-08-01

    The fusion technique is proposed for simultaneous determination of 35 elements from the same sample. Only 110 mg of rock sample was used to obtain fused glasses for quantitative determination of 10 major elements by wavelength dispersive X-ray fluorescence analysis, 16 rare earth elements and some other trace elements by inductively coupled plasma mass spectrometry analysis. Fusion was performed with 1.1 g of lithium metaborate and LiBr solution as the releasing agent in platinum crucible in electric furnace at 1100 °C. The certified reference materials of ultramafic, mafic, intermediate and felsic igneous rocks have been applied to obtain the calibration curves for rock-forming oxides (Na2O, MgO, Al2O3, SiO2, P2O5, K2O, CaO, TiO2, MnO, Fe2O3) and some trace elements (Ba, Sr, Zr) determination by X-ray fluorescence analysis. The repeatability does not exceed the allowable standard deviation for a wide range of concentrations. In the most cases the relative standard deviation was less than 5%. Obtained glasses were utilized for the further determination of rare earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and some other (Ba, Sr, Zr, Rb, Cs, Y, Nb, Hf, Ta, Th and U) trace elements by inductively coupled plasma mass spectrometry analysis with the same certified reference materials employed. The results could mostly be accepted as satisfactory. The proposed procedure essentially reduces the expenses in comparison with separate sample preparation for inductively coupled plasma mass spectrometry and X-ray fluorescence analysis.

  4. Optimization of determination of platinum group elements in airborne particulate matter by inductively coupled plasma mass spectrometry.

    PubMed

    Bujdoš, Marek; Hagarová, Ingrid; Matúš, Peter; Canecká, Lucia; Kubová, Jana

    2012-03-01

    Determination of automotive traffic-emitted platinum group metals (PGM) by inductively coupled plasma quadrupole mass spectrometry (ICP-MS) was optimized. The interferences from Sr, Cu, Pb, Y, Cd, Zr and Hf were evaluated using model solutions. Plasma radiofrequency (RF) power and nebulizer gas flow were optimized for 103Rh, 105Pd, 108Pd and 195Pt. Two standard reference materials were analyzed: SARM-7 Platinum ore and BCR-723 Road dust. The optimized procedure was used to analyze samples of airborne particulate matter collected in the urban site with heavy automotive traffic in the centre of Bratislava, Slovakia. PMID:24061181

  5. Reference measurements for total mercury and methyl mercury content in marine biota samples using direct or species-specific isotope dilution inductively coupled plasma mass spectrometry.

    PubMed

    Krata, Agnieszka; Vassileva, Emilia; Bulska, Ewa

    2016-11-01

    The analytical procedures for reference measurements of the total Hg and methyl mercury (MeHg) mass fractions at various concentration levels in marine biota samples, candidates for certified reference materials (oyster and clam Gafrarium tumidum), were evaluated. Two modes of application of isotope dilution inductively coupled plasma mass spectrometry method (ID ICP-MS), namely direct isotope dilution and species-specific isotope dilution analysis with the use of two different quantification mass spectrometry techniques were compared. The entire ID ICP-MS measurement procedure was described by mathematical modelling and the combined uncertainty of measurement results was estimated. All factors influencing the final results as well as isotopic equilibrium were systematically investigated. This included the procedural blank, the moisture content in the biota samples and all factors affecting the blend ratio measurements (instrumental background, spectral interferences, dead time and mass discrimination effects as well as the repeatability of measured isotopic ratios). Modelling of the entire measurement procedures and the use of appropriate certified reference materials enable to assure the traceability of obtained values to the International System of Units (SI): the mole or the kilogram. The total mass fraction of mercury in oyster and clam biota samples, after correction for moisture contents, was found to be: 21.1 (1.1) 10(-9) kg kg(-1) (U =5.1% relative, k=2) and 390.0 (9.4) 10(-9) kg kg(-1) (U=2.4% relative, k=2), respectively. For the determination of mercury being present as methyl mercury, the non-chromatographic separation on anion-exchange resin AG1-X8 of the blended samples was applied. The content of MeHg (as Hg) in oyster sample was found: 4.81 (24) 10(-9)kgkg(-1) (U=5.0%, k=2) and 4.84 (21) 10(-9)kgkg(-1) (U=4.3%, k=2) with the use of quadrupole (ICP QMS) or sector field (ICP SFMS) inductively coupled plasma mass spectrometers, respectively. In the

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

    SciTech Connect

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

    2010-05-01

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

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

    PubMed

    Zhang, Tieyuan; Bain, Daniel; Hammack, Richard; Vidic, Radisav D

    2015-03-01

    Elevated concentration of naturally occurring radioactive material (NORM) in wastewater generated from Marcellus Shale gas extraction is of great concern due to potential environmental and public health impacts. Development of a rapid and robust method for analysis of Ra-226, which is the major NORM component in this water, is critical for the selection of appropriate management approaches to properly address regulatory and public concerns. Traditional methods for Ra-226 determination require long sample holding time or long detection time. A novel method combining Inductively Coupled Mass Spectrometry (ICP-MS) with solid-phase extraction (SPE) to separate and purify radium isotopes from the matrix elements in high salinity solutions is developed in this study. This method reduces analysis time while maintaining requisite precision and detection limit. Radium separation is accomplished using a combination of a strong-acid cation exchange resin to separate barium and radium from other ions in the solution and a strontium-specific resin to isolate radium from barium and obtain a sample suitable for analysis by ICP-MS. Method optimization achieved high radium recovery (101 ± 6% for standard mode and 97 ± 7% for collision mode) for synthetic Marcellus Shale wastewater (MSW) samples with total dissolved solids as high as 171,000 mg/L. Ra-226 concentration in actual MSW samples with TDS as high as 415,000 mg/L measured using ICP-MS matched very well with the results from gamma spectrometry. The Ra-226 analysis method developed in this study requires several hours for sample preparation and several minutes for analysis with the detection limit of 100 pCi/L with RSD of 45% (standard mode) and 67% (collision mode). The RSD decreased to below 15% when Ra-226 concentration increased over 500 pCi/L. PMID:25642997

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

    PubMed

    Khan, Naeem; Choi, Ji Yeon; Nho, Eun Yeong; Jamila, Nargis; Habte, Girum; Hong, Joon Ho; Hwang, In Min; Kim, Kyong Su

    2014-09-01

    This study aimed at analyzing the concentrations of 23 minor and trace elements in aromatic spices by inductively coupled plasma-mass spectrometry (ICP-MS), after wet digestion by microwave system. The analytical method was validated by linearity, detection limits, precision, accuracy and recovery experiments, obtaining satisfactory values in all cases. Results indicated the presence of variable amounts of both minor and trace elements in the selected aromatic spices. Manganese was high in cinnamon (879.8 μg/g) followed by cardamom (758.1 μg/g) and clove (649.9 μg/g), strontium and zinc were high in ajwain (489.9 μg/g and 84.95 μg/g, respectively), while copper was high in mango powder (77.68 μg/g). On the whole some of the minor and essential trace elements were found to have good nutritional contribution in accordance to RDA. The levels of toxic trace elements, including As, Cd, and Pb were very low and did not found to pose any threat to consumers. PMID:24731332

  9. Quantitative imaging of the tissue contrast agent [Gd(DTPA)]²⁻ in articular cartilage by laser ablation inductively coupled plasma mass spectrometry.

    PubMed

    Sussulini, Alessandra; Wiener, Edzard; Marnitz, Tim; Wu, Bei; Müller, Berit; Hamm, Bernd; Sabine Becker, J

    2013-01-01

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is an emerging analytical technique in the generation of quantitative images of MR contrast agent distribution in thin tissue sections of articular cartilage. An analytical protocol is described that includes sample preparation by cryo-cutting of tissue sections, mass spectrometric measurements by LA-ICP-MS and quantification of gadolinium images by one-point calibration, standard addition method (employing matrix-matched laboratory standards) and isotope dilution analysis using highly enriched stable Gd-155 isotope (abundance 92 vs 14.8% in the [Gd(DTPA)]²⁻ contrast agent). The tissue contrast agent concentrations of [Gd(DTPA)]²⁻ in cartilage measured in this work are in agreement with findings obtained by magnetic resonance imaging and other analytical methodologies. The LA-ICP-MS imaging data also confirm the observation that the spatial distribution of [Gd(DTPA)]²⁻ in the near-equilibrium state is highly inhomogeneous across cartilage thickness with the highest concentration measured in superficial cartilage and a strong decrease toward the subchondral bone. In the present work, it is shown for the first time that LA-ICP-MS can be applied to validate the results from quantitative gadolinium-enhanced MRI technique of articular cartilage. PMID:23281293

  10. [Determination of trivalent chromium and hexavalent chromium in dried edible fungi by microwave ashing-liquid chromatography with inductively coupled plasma mass spectrometry].

    PubMed

    Ni, Zhanglin; Tang, Fubin; Qu, Minghua; Mo, Runhong

    2014-02-01

    An analytical method using liquid chromatography with inductively coupled plasma mass spectrometry (LC-ICP-MS) for the determination of trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) in dried edible fungi was established. Edible fungi sample was ashed by a microwave ashing system and Na2 EDTA was added to the ashing sample to stabilize the Cr(III). An anion exchange column (250 mm x 4.6 mm, 10 microm) with a 60 mmol/L nitric acid (pH 9.3) solution as mobile phase was used for the separation and using ICP-MS as a detector for the determination of trivalent chromium and hexavalent chromium. The calibration curves were linear in the range of 0.5-50 microg/L and the correlation coefficients were 0. 999 9 for Cr(III) and Cr(VI). The average recoveries of Cr(III) and Cr(VI) ranged from 78.0% to 90.7% with the relative standard deviations (RSDs, n = 6) less than 4%. The limits of quantification (LOQ) of Cr(III) and Cr(VI) were 0.5 microg/L. The method is efficient, reliable and sensitive, and can meet the requirement for the determination of Cr(III) and Cr(VI) in dried edible fungi. PMID:24822453

  11. Quantitative imaging of platinum based on laser ablation-inductively coupled plasma-mass spectrometry to investigate toxic side effects of cisplatin.

    PubMed

    Köppen, C; Reifschneider, O; Castanheira, I; Sperling, M; Karst, U; Ciarimboli, G

    2015-12-01

    This work presents a quantitative bioimaging method for platinum based on laser ablation-inductively coupled plasma-mass spectrometry and its application for a biomedical study concerning toxic side effects of cisplatin. To trace the histopathology back to cisplatin, platinum was localized and quantified in major functional units of testicle, cochlea, kidney, nerve and brain sections from cisplatin treated mice. The direct consideration of the histology enables precise interpretation of the Pt images and the novel quantitative evaluation approach allows significantly more precise investigations than the pure image. For the first time, platinum was detected and quantified in all major injured structures including organ of Corti of cochlea and seminiferous tubule of testicle. In this way, proximal tubule in kidney, Leydig cells in testicle, stria vascularis and organ of Corti in cochlea and nerve fibers in sciatic nerves are confirmed as targets of cisplatin in these organs. However, the accumulation of platinum in almost all investigated structures also raises questions about more complex pathogenesis including direct and indirect interruption of several biological processes. PMID:26477751

  12. Microwave-assisted Extraction of Rare Earth Elements from Petroleum Refining Catalysts and Ambient Fine Aerosols Prior to Inductively Coupled Plasma - Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Mittlefehldt, David W.; Kulkarni, Pranav; Chellam, Shankar

    2006-01-01

    In the absence of a certified reference material, a robust microwave-assisted acid digestion procedure followed by inductively coupled plasma - mass spectrometry (ICP-MS) was developed to quantify rare earth elements (REEs) in fluidized-bed catalytic cracking (FCC) catalysts and atmospheric fine particulate matter (PM2.5). High temperature (200 C), high pressure (200 psig), acid digestion (HNO3, HF, and H3BO3) with 20 minute dwell time effectively solubilized REEs from six fresh catalysts, a spent catalyst, and PM2.5. This method was also employed to measure 27 non-REEs including Na, Mg, Al, Si, K, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Zr, Mo, Cd, Cs, Ba, Pb, and U. Complete extraction of several REEs (Y, La, Ce, Pr, Nd, Tb, Dy, and Er) required HF indicating that they were closely associated with the aluminosilicate structure of the zeolite FCC catalysts. Internal standardization using 115In quantitatively corrected non-spectral interferences in the catalyst digestate matrix. Inter-laboratory comparison using ICP-optical emission spectroscopy (ICP-OES) and instrumental neutron activation analysis (INAA) demonstrated the applicability of the newly developed analytical method for accurate analysis of REEs in FCC catalysts. The method developed for FCC catalysts was also successfully implemented to measure trace to ultra-trace concentrations of La, Ce, Pr, Nd, Sm, Gd, Eu, and Dy in ambient PM2.5 in an industrial area of Houston, TX.

  13. Direct determination of bromine in plastics by electrothermal vaporization/inductively coupled plasma mass spectrometry using a tungsten boat furnace vaporizer and an exchangeable sample cuvette system.

    PubMed

    Okamoto, Yasuaki; Komori, Hiromi; Kataoka, Hiroko; Tsukahara, Satoshi; Fujiwara, Terufumi

    2010-05-15

    A tungsten boat furnace vaporization inductively coupled plasma mass spectrometry (TBF/ICP-MS) method has been applied to the direct determination of bromine in plastic samples. In the pretreatment, the plastic sample is spread over a small sample cuvette made of tungsten by treating it with a strongly basic organic solution, e.g., octanol or diisobutyl ketone in the presence of potassium hydroxide. The cuvette is placed on a tungsten boat furnace, with which the electrothermal vaporizer is equipped. At the vaporization step, a widely spread thin layer of the sample facilitates its efficient evaporation and introduction into an ICP mass spectrometer. The most remarkable feature is that all the bromine species in plastic samples are decomposed to form a thermally stable inorganic salt during the pretreatment procedure. Therefore, the bromine content in plastic samples can be measured by a calibration curve method constructed with an aqueous standard solution of potassium bromate(V). The detection limit (3sigma) was estimated to be 0.77 pg of bromine, which corresponds to a concentration of 0.31 ng g(-1) of bromine in plastic samples when a sample amount taken of 2.5 mg is studied. The relative standard deviation was calculated to be 2.2%. Analytical results of some plastic samples, which contained both inorganic bromide salts and also organic bromine species, are given. PMID:20391597

  14. Comparison of digestion procedures and methods for quantification of trace lead in breast milk by isotope dilution inductively coupled plasma mass spectrometry

    PubMed Central

    Amarasiriwardena, Chitra J.; Jayawardene, Innocent; Lupoli, Nicola; Barnes, Ramon M.; Hernandez-Avila, Mauricio; Hu, Howard

    2014-01-01

    Measurement of lead in breast milk is an important public health consideration and can be technically quite challenging. The reliable and accurate determination of trace lead in human breast milk is difficult for several reasons including: potential for contamination during sample collection, storage, and analysis; complexities related to the high fat content of human milk; and poor analytic sensitivity at low concentrations. Breast milk lead levels from previous published studies should therefore be reviewed with caution. Due to the difficulty in identifying a method that would successfully digest samples with 100% efficiency, we evaluated three different digestion procedures including: (1) dry ashing in a muffle furnace, (2) microwave oven digestion, and (3) digestion in high pressure asher. High temperature, high pressure asher digestion was selected as the procedure of choice for the breast milk samples. Trace lead analysis was performed using isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS). Measured lead concentrations in breast milk samples (n = 200) from Mexico ranged from 0.2 to 6.7 ng ml−1. The precision for these measurements ranged from 0.27–7.8% RSD. Use of strict contamination control techniques and of a very powerful digestion procedure, along with an ID-ICP-MS method for lead determination, enables us to measure trace lead levels as low as 0.2 ng ml−1 in milk (instrument detection limit = 0.01 ng ml−1). PMID:24808927

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

    PubMed

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

    2012-03-01

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

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

    PubMed

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

    2015-11-01

    Pangxidong composite granitoid pluton located in the southwestern margin of Yunkai massif. The metamorphic grade of this pluton increases from outside to inside, that is, banded-augen granitic gneisses, gneissoid granites and granites distribute in order from edge to core. X-Ray Fluorescence Spectroscopy and Plasma Mass Spectrometry are conducted to study the geochemical characteristics of the three types of rocks. The result shows that all the three types of rocks are peraluminous rocks and their contents of main elements and rare earth elements change gradually. From granitic gneisses to granites, the contents of Al₂O₃, CaO, MgO, TiO₂, total rare earth elements and light rare earth elements increase, but the contents of SiO₂ and heavy rare earth elements decrease. It is suggested that the phylogenetic relationship exists between granitic gneisses, gneissoid granites and granites during the multi-stage tectonic evolution process. Furthermore, the remelting of metamorphosed supracrustal rocks in Yunkai massif is probably an important cause of granitoid rocks forming. The evolutionary mechanism is probably that SiO₂ and heavy rare earth elements were melt out from the protolith and gradually enriched upward, but Al₂O₃, CaO, MgO, TiO₂ and light rare earth elements enriched downward. PMID:26978933

  17. Speciation and determination of bioavailable arsenic species in soil samples by one-step solvent extraction and high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

    PubMed

    Sun, Jing; Ma, Li; Yang, Zhaoguang; Lee, Hsiaowan; Wang, Lin

    2015-03-01

    A new analytical method was developed to determine the bioavailable arsenic species (arsenite, arsenate, monomethylarsonic acid, and dimethylarsonic acid) in soil samples using high-performance liquid chromatography with inductively coupled plasma mass spectrometry. Bioavailable arsenic was extracted with ammonium phosphate buffer by a simplified one-step solvent extraction procedure. To estimate the effect of variables on arsenic extraction, a two-level Plackett-Burman factorial design was conducted to screen the significant factors that were further investigated by a separate univariate approach. The optimum conditions were confirmed by compromising the stability of arsenic species and the extraction efficiency. The concentration of arsenic species was determined in method blank and soil-certified reference materials both spiked with standard solutions of arsenic species. All the target arsenic species were stable during the whole extraction procedure. Furthermore, the proposed method was applied to release bioavailable arsenic from contaminated soil samples, showing that the major arsenic species in soil samples were inorganic arsenic: arsenite and arsenate, of which the latter was dominant. PMID:25594186

  18. Profiling the iron, copper and zinc content in primary neuron and astrocyte cultures by rapid online quantitative size exclusion chromatography-inductively coupled plasma-mass spectrometry.

    PubMed

    Hare, Dominic J; Grubman, Alexandra; Ryan, Timothy M; Lothian, Amber; Liddell, Jeffrey R; Grimm, Rudolf; Matsuda, Toshiaki; Doble, Philip A; Cherny, Robert A; Bush, Ashley I; White, Anthony R; Masters, Colin L; Roberts, Blaine R

    2013-12-01

    Metals often determine the chemical reactivity of the proteins to which they are bound. Each cell in the body tightly maintains a unique metalloproteomic profile, mostly dependent on function. This paper describes an analytical online flow injection quantitative size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS) method, which was applied to profiling the metal-binding proteins found in primary cultures of neurons and astrocytes. This method can be conducted using similar amounts of sample to those used for Western blotting (20-150 μg protein), and has a turnaround time of <15 minutes. Metalloprotein standards for Fe (as ferritin), Cu and Zn (as superoxide dismutase-1) were used to construct multi-point calibration curves for online quantification of metalloproteins by SEC-ICP-MS. Homogenates of primary neuron and astrocyte cultures were analysed by SEC-ICP-MS. Online quantification by external calibration with metalloprotein standards determined the mass of metal eluting from the column relative to time (as pg s(-1)). Total on-column Fe, Cu and Zn detection limits ranged from 0.825 ± 0.005 ng to 13.6 ± 0.7 pg. Neurons and astrocytes exhibited distinct metalloprotein profiles, featuring both ubiquitous and unique metalloprotein species. Separation and detection by SEC-ICP-MS allows appraisal of these metalloproteins in their native state, and online quantification was achieved using this relatively simple external calibration process. PMID:24132241

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

    NASA Astrophysics Data System (ADS)

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

    2011-01-01

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

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

    PubMed

    Shih, Tsung-Ting; Hsieh, Cheng-Chuan; Luo, Yu-Ting; Su, Yi-An; Chen, Ping-Hung; Chuang, Yu-Chen; Sun, Yuh-Chang

    2016-04-15

    Herein, a hyphenated system combining a high-throughput solid-phase extraction (htSPE) microchip with inductively coupled plasma-mass spectrometry (ICP-MS) for rapid determination of trace heavy metals was developed. Rather than performing multiple analyses in parallel for the enhancement of analytical throughput, we improved the processing speed for individual samples by increasing the operation flow rate during SPE procedures. To this end, an innovative device combining a micromixer and a multi-channeled extraction unit was designed. Furthermore, a programmable valve manifold was used to interface the developed microchip and ICP-MS instrumentation in order to fully automate the system, leading to a dramatic reduction in operation time and human error. Under the optimized operation conditions for the established system, detection limits of 1.64-42.54 ng L(-1) for the analyte ions were achieved. Validation procedures demonstrated that the developed method could be satisfactorily applied to the determination of trace heavy metals in natural water. Each analysis could be readily accomplished within just 186 s using the established system. This represents, to the best of our knowledge, an unprecedented speed for the analysis of trace heavy metal ions. PMID:27016435

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

    PubMed

    de Gois, Jefferson S; Pereira, Éderson R; Welz, Bernhard; Borges, Daniel L G

    2014-12-10

    A new method for the direct analysis of coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis was developed, aiming at the determination of Br and Cl. The procedure does not require any significant sample pretreatment and allows simultaneous determination of both elements to be carried out, requiring small mass aliquots of sample (about 0.5 mg). All operating parameters, including carrier gas flow-rate and RF power, were optimized for maximum sensitivity. The use of modifiers/aerosol carriers (Pd, Pd+Al and Pd+Ca) was evaluated, and the mixture of Pd and Ca was chosen, allowing pyrolysis and vaporization temperatures of 700°C and 1900°C, respectively. Chlorine was accurately determined using calibration against solid standards, whereas Br could also be determined using calibration against aqueous standard solutions. The limits of quantification were 0.03 μg g(-1) for Br and 7 μg g(-1) for Cl, and no spectral interferences were observed. PMID:25441883

  2. Study on the in vivo toxic mechanism of xixin based on trace elements determination by inductively coupled plasma-mass spectrometry

    PubMed Central

    Yong-Rui, Bao; Xin-Xin, Yang; Shuai, Wang; Xian-Sheng, Meng; Rui-Qing, Zhu; Yue-Ming, Xia; Lin, Cai

    2014-01-01

    Background: Xixin has been widely used as a traditional Chinese medicine for headache, toothache and inflammatory diseases. Clinical investigation indicated that adverse drug reactions occurred with an overdose of xixin, but the toxic mechanism of xixin in vivo based on trace elements has not been researched yet. Objective: To explore the in vivo toxic mechanism of xixin induced by trace elements. Materials and Methods: The contents of trace elements in the serum and liver of mice were determined by inductively coupled plasma-mass spectrometry (ICP-MS) after obtaining xixin extracts. Principal component analysis (PCA) and cluster analysis (CA) were performed between the trace elements’ content and dosage using the software GeneSpring 12.1 to analyze the main toxic elements in vivo. Results: Trace elements’ contents were obviously raised after xixin extracts were taken as a dosage of 150 mg/mL and 50 mg/mL, respectively. Na, Ca, Cu and Cd in serum and Ca and Zn in liver were the main trace elements inducing the toxic reaction of xixin. Conclusion: Xixin possesses the potential function of indirectly upregulating trace elements in vivo. This study, for the first time, elucidated the in vivo toxic mechanism of xixin based on trace elements. This method could also be utilized in the research of corresponding aspects. PMID:24914279

  3. Fast determination of arsenosugars in algal extracts by narrow bore high-performance liquid chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Todolí, José Luis; Grotti, Marco

    2010-11-19

    The potential of narrow bore high-performance liquid chromatography (HPLC) with detection by inductively coupled plasma mass spectrometry (ICP-MS) for fast determination of arsenosugars in algal extracts was explored. The retention behavior of four naturally occurring dimethylarsinoylribosides on an anion-exchange microbore column was investigated, with the mobile phase flow rate ranging from 60 to 200μLmin(-1). A low sample consumption system consisting of a micronebulizer and a low inner volume cyclonic spray chamber was used as the interface between the micro-column and the ICP mass spectrometer. Both the high efficiency nebulizer, HEN, and the PFA micronebulizer were tested, with the former providing 20-50% greater sensitivity than PFA (depending on the liquid flow rate), but comparable limits of detection and slightly lower chromatographic resolution. With the setup employed and under the optimal conditions, a satisfactory separation of the arsenosugars was achieved in less than 5min. The instrumental limit of detection was 0.20μgAsL(-1) and the precision was better than 3% (RSD%, n=5). The accuracy of the determination was verified by the analysis of a reference algal extract, obtaining values in good agreement with the reference ones. PMID:20965508

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

    NASA Astrophysics Data System (ADS)

    Zhang, Xing; Chen, Beibei; He, Man; Zhang, Yiwen; Xiao, Guangyang; Hu, Bin

    2015-04-01

    The absolute quantification of glycoproteins in complex biological samples is a challenge and of great significance. Herein, 4-mercaptophenylboronic acid functionalized magnetic beads were prepared to selectively capture glycoproteins, while antibody conjugated gold and silver nanoparticles were synthesized as element tags to label two different glycoproteins. Based on that, a new approach of magnetic immunoassay-inductively coupled plasma mass spectrometry (ICP-MS) was established for simultaneous quantitative analysis of glycoproteins. Taking biomarkers of alpha-fetoprotein (AFP) and carcinoembryonic antigen (CEA) as two model glycoproteins, experimental parameters involved in the immunoassay procedure were carefully optimized and analytical performance of the proposed method was evaluated. The limits of detection (LODs) for AFP and CEA were 0.086 μg L- 1 and 0.054 μg L- 1 with the relative standard deviations (RSDs, n = 7, c = 5 μg L- 1) of 6.5% and 6.2% for AFP and CEA, respectively. Linear range for both AFP and CEA was 0.2-50 μg L- 1. To validate the applicability of the proposed method, human serum samples were analyzed, and the obtained results were in good agreement with that obtained by the clinical chemiluminescence immunoassay. The developed method exhibited good selectivity and sensitivity for the simultaneous determination of AFP and CEA, and extended the applicability of metal nanoparticle tags based on ICP-MS methodology in multiple glycoprotein quantifications.

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

    PubMed

    Zhao, Yan-Fang; Wu, Ji-Fa; Shang, De-Rong; Ning, Jin-Song; Ding, Hai-Yan; Zhai, Yu-Xiu

    2014-01-01

    Arsenite [As (III)], arsenate [As (V)], methylarsonate (MMA), and dimethylarsinate (DMA) in five edible seaweeds (the brown algae Laminaria japonica, red algae Porphyra yezoensis, brown algae Undaria pinnatifida, brown algae Hizikia fusiformis, and green algae Enteromorpha prolifera) were analyzed using in vitro digestion method determined by high-performance liquid chromatography inductively coupled plasma mass spectrometry. The results showed that DMA was found in the water extracts of all samples; As (III) were detected in L. japonica and U. pinnatifida and about 23.0 and 0.15 mg/kg of As (V) were found in H. fusiformis and E. prolifera respectively. However, after the gastrointestinal digestion, As (V) was not detected in any of the five seaweeds. About 0.19 and 1.47 mg/kg of As (III) was detected in the gastric extracts of L. japonica and H. fusiformis, respectively, and about 0.31 and 0.10 mg/kg of As (III) were extracted from the intestinal extracts of Porphyra yezoensis and U. pinnatifida, respectively. The present results successfully reveal the differences of As species and levels in the water and biomimetic extracts of five edible seaweeds. The risk assessment of the inorganic arsenic in the five edible seaweeds based on present data showed almost no hazards to human health. PMID:26904630

  6. Determination of actinides in environmental and biological samples using high-performance chelation ion chromatography coupled to sector-field inductively coupled plasma mass spectrometry.

    PubMed

    Truscott, J B; Jones, P; Fairman, B E; Evans, E H

    2001-08-31

    High-performance chelation ion chromatography, using a neutral polystyrene substrate dynamically loaded with 0.1 mM dipicolinic acid, coupled with sector-field inductively coupled plasma mass spectrometry has been successfully used for the separation of the actinides thorium, uranium, americium, neptunium and plutonium. Using this column it was possible to separate the various actinides from each other and from a complex sample matrix. In particular, it was possible to separate plutonium and uranium to facilitate the detection of the former free of spectral interference. The column also exhibited some selectivity for different oxidation states of Np, Pu and U. Two oxidation states each for plutonium and neptunium were found, tentatively identified as Np(V) and Pu(III) eluting at the solvent front, and Np(IV) and Pu(IV) eluting much later. Detection limits were 12, 8, and 4 fg for 237Np, 239Pu, and 241Am, respectively, for a 0.5 ml injection. The system was successfully used for the determination of 239Pu in NIST 4251 Human Lung and 4353 Rocky Flats Soil, with results of 570+/-29 and 2939+/-226 fg g(-1), respectively, compared with a certified range of 227-951 fg g(-1) for the former and a value of 3307+/-248 fg g(-1) for the latter. PMID:11589474

  7. Application of Microwave-Induced Combustion and Isotope Dilution Strategies for Quantification of Sulfur in Coals via Sector-Field Inductively Coupled Plasma Mass Spectrometry.

    PubMed

    Christopher, Steven J; Vetter, Thomas W

    2016-05-01

    In recent years, microwave-induced combustion (MIC) has proved to be a robust sample preparation technique for difficult-to-digest samples containing high carbon content, especially for determination of halogens and sulfur. National Institute of Standards and Technology (NIST) has applied the MIC methodology in combination with isotope dilution analysis for sulfur determinations, representing the first-reported combination of this robust sample preparation methodology and high-accuracy quantification approach. Medium-resolution mode sector-field inductively coupled plasma mass spectrometry was invoked to avoid spectral interferences on the sulfur isotopes. The sample preparation and instrumental analysis scheme was used for the value assignment of total sulfur in Standard Reference Material (SRM) 2682c Subbituminous Coal (nominal mass fraction 0.5% sulfur). A description of the analytical procedures required is provided, along with metrological results, including an estimation of the overall method uncertainty (<1.5% relative expanded uncertainty) calculated using the IDMS measurement function and a Kragten spreadsheet approach. PMID:27032706

  8. Theoretical Investigation of Small Polyatomic Ions Observed in Inductively Coupled Plasma Mass Spectrometry: HxCO+ and HxN2+ (x = 1, 2, 3)

    SciTech Connect

    Sears, K.; Ferguson, J.; Dudley, T.; Houk, R.; Gordon, M.

    2008-03-01

    Two series of small polyatomic ions, H{sub x}CO{sup +} and H{sub x}N{sub 2}{sup +} (x = 1, 2, 3), were systematically characterized using three correlated theoretical techniques: density functional theory using the B3LYP functional, spin-restricted second-order perturbation theory, and singles + doubles coupled cluster theory with perturbative triples. On the basis of thermodynamic data, the existence of these ions in inductively coupled plasma mass spectrometry (ICP-MS) experiments is not surprising since the ions are predicted to be considerably more stable than their corresponding dissociation products (by 30-170 kcal/mol). While each pair of isoelectronic ions exhibit very similar thermodynamic and kinetic characteristics, there are significant differences within each series. While the mechanism for dissociation of the larger ions occurs through hydrogen abstraction, the triatomic ions (HCO{sup +} and HN{sub 2}{sup +}) appear to dissociate by proton abstraction. These differing mechanisms help to explain large differences in the abundances of HN{sub 2}{sup +} and HCO{sup +} observed in ICP-MS experiments.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    PubMed

    Hachmöller, Oliver; Aichler, Michaela; Schwamborn, Kristina; Lutz, Lisa; Werner, Martin; Sperling, Michael; Walch, Axel; Karst, Uwe

    2016-05-01

    A laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method is developed and applied for the analysis of paraffin-embedded liver needle biopsy specimens of patients with Wilson's disease (WD), a rare autosomal recessive disorder of the copper metabolism causing various hepatic, neurological and psychiatric symptoms due to a copper accumulation in the liver and the central nervous system. The sample set includes two WD liver samples and one negative control sample. The imaging analysis was performed with a spatial resolution of 10 μm. Besides copper, iron was monitored because an elevated iron concentration in the liver is known for WD. In addition to this, both elements were quantified using an external calibration based on matrix-matched gelatine standards. The presented method offers low limits of detection of 1 and 5 μg/g for copper and iron, respectively. The high detection power and good spatial resolution allow the analysis of small needle biopsy specimen using this method. The two analyzed WD samples can be well differentiated from the control sample due to their inhomogeneous copper distribution and high copper concentrations of up to 1200 μg/g. Interestingly, the WD samples show an inverse correlation of regions with elevated copper concentrations and regions with high iron concentrations. PMID:27049132